DE102009019550A1 - Producing a phase-stable oil-in-water emulsion, useful as e.g. binders, comprises mixing an oil phase from a fat/oil component with a polysaccharide, dispersing in an aqueous phase and subsequently finely emulsifying the emulsion - Google Patents

Abstract

Producing a phase-stable oil-in-water emulsion with a dry mass (5-60 wt.%), comprising a protein (0.2-10 wt.%), a polar polysaccharide (0.3-10 wt.%), a fat/oil component (0.1-60 wt.%) and a polyol (0-30 wt.%), comprises mixing an existing phase (oil phase) essentially from the fat/oil component or optionally with the polar polysaccharide or its part, dispersing in an aqueous phase comprising the protein and optionally the polar polysaccharide and then subsequently finely emulsifying the emulsion. Independent claims are also included for: (1) a composition obtained by the above mentioned method; (2) producing a sensory, functional and/or nutritional properties modified food comprising (i) providing the oil-in-water emulsion comprising the protein (0.2-10.0 wt.%), the polar polysaccharide (0.3-10 wt.%), the fat/oil component (0.1-60 wt.%), a flavoring oil component (0-30 wt.%), the polyol (0-30 wt.%), a flavoring agent (0-1 wt.%) and an acid (0-1 wt.%), where the particle size of the dispersed oil or fat droplets lies in a distribution maximum (X 5 0 . 3) of = 10 mu m (volume-based median) and dried mass of the emulsion is 5-60 wt.% and (ii) mixing the emulsion with a food base for producing a food product, where the emulsion based on the food base is present in a ratio of 0.1-75 wt .%; (3) a formulation comprising the composition which is a food product, health care product, medicinal product, agricultural product or industrial product; and (4) a food obtained by the above mentioned method.

Description

Technical area

In general, the present invention relates to biopolymer-based compositions having a continuous aqueous phase and a dispersed fatty or oily phase and a simple and continuous process for their preparation. The dispersed oil phase is stable and does not separate even on prolonged standing. The stability of these compositions with respect to the separation of water and oil phases is based on the unique process used to make them and does not require additional emulsifying or dispersing agents. These compositions have unique properties which make them suitable for use as thickeners, suspending agents, coating materials and as fat replacers in food products. In addition, products made in accordance with this invention may be dried and subsequently rehydrated to yield compositions having substantially the same properties as the undried compositions.

background

Creamy and / or full-bodied foods and other products such as cosmetics typically rely on the addition of hydrocolloids and / or finely-dispersed particles (eg, as microparticles or emulsified fat) to produce the desired consistency. This emulsified fat is generally supplied by liquid or spray-dried non-dairy creamers, whole milk or reduced fat milk. The amount of fat commonly found in these products provides inadequate consistency and / or water binding benefits, often resulting in deposition after prolonged storage.

An alternative approach is to use ingredients that increase the consistency (viscosity) of the product. Hydrocolloid gums and water-soluble starches are typically used to give a consistency to beverages, i. H. to increase the viscosity. However, hydrocolloid gums often lead to negative consistency properties, which appear to be "slimy" or "sticky".

Water-soluble starches can also be used to increase the viscosity. However, the amount of water-soluble starch required to produce these properties is usually higher in gums, so more solid must be added. This means an additional high solids content for instant products. The fullness and creaminess can be increased by a higher dosage of solids. Since this means a larger volume of end product, difficulties arise in the formulation of products whose aim is to obtain a high-quality end product with low raw material input.

Prior art of the present invention

Representative of the state of the art, for example, the international application WO03 / 003850 which proposes compositions consisting essentially of pectin, alginate and cellulose for stabilizing and increasing the viscosity of cosmetics, health articles, foodstuffs and beverages. In the EP 340 035 A2 , aqueous dispersions of insoluble, microfragmented, ionic polysaccharide / protein complex are described for use as nutrients, viscosity or texture controlling agents in both conventional and novel food products. However, the prior art does not describe a process for preparing a water-oil emulsion which imparts a creamy mouthfeel to edible formulations to a wide range of food and drug products, impart creaming stability and in others, including industrial products, for example, reduces or completely eliminates water separation suppressed.

Summary of the invention

The present invention relates to a process for the preparation of an oil-in-water (O / W) emulsion (also referred to herein as "PPS" or protein polysaccharide stabilizer) consisting essentially of protein, polysaccharide, oil or fat and optionally water. More particularly, the present invention relates to a process for preparing an oil-in-water (O / W) emulsion containing, based on the total weight of the emulsion, 0.2-10.0% by weight protein; 0.3-10.0% by weight polar polysaccharide; 0.1-60% by weight. a fat / oil component; and optionally 0-30.0 wt .-% polyol. If desired, in addition 0-1.0 wt .-% of a flavoring; 0-1.0% by weight of a dye; 0-0.2% by weight of preservatives; and or 0-1.0% by weight of an acid and active substances which are introduced or formulated into a desired end product by means of PPS, for example enzymes in detergents, vitamins, essential fatty acids, pigments and metals such as titanium oxide in foods or health care preparations such as sunscreen lotions, therapeutically active agents such as Taxol in drug products, fungicides in crop protection agents, aluminum hydroxide in Bohrkühlwasser, etc.

The present invention is based on the surprising discovery that a stable and non-separable emulsion composed of microscopic oil droplets dispersed throughout an aqueous phase of a biopolymer or biopolymer mixture are prepared in the absence of conventional emulsifying or dispersing agents can by dispersing a substantially consisting of a fat / oil component phase (oil phase) in a protein and polysaccharide-containing aqueous phase and finely emulsified, wherein for the preparation of the aqueous phase protein and polysaccharide are first dissolved separately with stirring and subsequently be mixed. Alternatively, to prepare the emulsion according to the invention, the oil phase is mixed with at least part of the polysaccharide with stirring, and then dispersed and finely emulsified in an aqueous phase containing the protein and optionally also partially polysaccharide. The particle size of the dispersed oil or fat droplets of PPS lies in the distribution _maximum at x _50.3 ≤ 10 μm (volume-related median value). The dry matter of PPS is preferably between 5 and 60% by weight.

The resulting emulsions are characterized by the following properties: (1) they are stable and do not phase separate into their oil and water components upon prolonged standing; (2) they are characterized by a relatively high water binding; (3) Depending on the type, they form slightly viscous liquids to creamy pastes which, in the absence of dispersed fat by the application of heat, can easily be transformed into pourable liquids; (4) they can be dried, for example using a roller dryer, to give solid compositions that feel less oily when touched; and (5) dried compositions readily hydrate and are readily redissolved in water to provide smooth, stable and lump-free emulsions that are identical or similar in their properties to aqueous compositions before drying that have never been dried. The smoothness and suppleness of the emulsion of the invention make it suitable for use as thickeners, suspending agents and fat replacers in foods. The presence of the oil component in the emulsion also causes them to act as emulsifying and dispersing agents and makes them receptive to the addition of a variety of water immiscible materials, for example, other fat, volatile and essential (essential) and flavoring oils, and food flavorings, antioxidants, medicinal compositions, agricultural chemicals, etc. The compositions are also useful as a seed coating since the oil component provides a significant level of compatibility between the dried composition and the waxy coating found in many seed varieties.

In accordance with this finding, it is an object of the invention to provide a new class of biopolymer-based emulsions which provides a uniform and stable distribution of oil at all levels up to at least 60% by weight. have the emulsion. When dried, these compositions do not feel substantially oily upon contact, especially those in which the particle size of the emulsion is of the order of 1 micron and / or which are loaded with less than about 30% by weight of oil, based on the combined weight of the aqueous emulsion. In aqueous distribution, the compositions of the invention have a non-greasy but lubricious structure.

The present invention further includes compositions and formulations, especially dry compositions containing, among other ingredients, 0.001-99.9% by weight of the emulsion of the invention. In products containing the emulsion according to the invention, this acts as a stabilizer of the distributions of solids and liquids contained in the respective product. In principle, the emulsion according to the invention can be used in the manufacture of any product in which oil-in-water emulsions are used, in particular lotions, gels, creams, pastes, lubricants, etc.

Other objects and advantages of the present invention will become apparent from the following discussion.

Detailed description of the invention

definitions

As used herein, the terms "instant" and "soluble" are used interchangeably to refer to products and compositions, such as instant coffee products, soluble detergent powders, and tablets, which are relatively soluble in water, especially hot water. A mixture (either in the form of a powder, dry mix, concentrate or emulsion) is sold by the manufacturer and typically mixed by the consumer with an aqueous liquid or diluent (i.e., water or other aqueous medium) to form a ready-to-use Provide product.

Unless otherwise noted, all amounts, parts, ratios and percentages used herein are by weight.

Lipid (or fat) is a generic term that refers to substances that are in living cells and are composed of only a non-polar hydrocarbon moiety or a hydrocarbon moiety with polar functional groups (see Encyclopedia of Chemistry, 3rd Edition, Editors CA Hampel and GG Hawley, 1973, page 632 ). Most fats are insoluble in water and are soluble in fat solvents such as ether and chloroform. Fats are a major class of the lipid family. Fats are glycerol esters of fatty acids that are predominantly palmitic, stearic, oleic and linoleic acids, although many other fatty acids are found in nature. Most fats are present as triesters of glycerine. Hackh's Chemical Dictionary, 4th Edition, publisher G. Grant, 1969, defined on page 470 an oil as a liquid that is immiscible with water, is generally combustible, and is soluble in ether. Oils are divided into three categories: (1) fatty substances from plant and animal organisms; (2) volatile or essential (essential) oils, ie the scent principles of plant organisms; and (3) mineral oils, fuel oils and lubricants, ie hydrocarbons derived from petroleum and its products.

Although any fat is useful in making the compositions of the present invention, the flowable and edible vegetable oils, for example, soybean oil, corn oil, cottonseed oil, sunflower oil, palm oil, coconut oil, rapeseed oil, MCT oils and olive oil, and the semi-solid hydrogenated vegetable oils, the fats are more animal Origin, such as fish oil, butter, bacon or tallow, and the refined and non-toxic mineral oils commonly referred to as paraffin oil. Also included are oils and fats, which may be partially or fully hydrogenated or otherwise modified, as well as non-toxic modified fats which have properties similar to triglycerides and are referred to herein as partially or completely nondigestible fat. Low calorie fats and edible nondigestible fats, oils or fat substitutes may be included in the term. The terms "fat" or "oil" also refer to 100% non-toxic fatty materials which have properties similar to those of triglycerides. The terms "fat" or "oil" generally also include fat substitutes, which materials may be partially or fully nondigestible.

In the following disclosure, the invention will be described primarily with reference to the addition of oil as a built-in grease. It should be understood that the term "oil" is often used interchangeably with the terms "lipid" and "fat" herein, and may be replaced by other lipids (i.e., fats and hydrocarbons). Although those skilled in the art will recognize that emulsifying fats may fall within the scope of the terms "lipid" and "fat", the process of the present invention does not require the inherently emulsifying properties of these materials to yield the highly dispersed biopolymer / oil products of the present invention ,

The "fat component" and "oil component" is enriched in certain embodiments, for example for the preparation of dietary supplements with essential and / or "functional" fatty acids or fatty acid esters such as long-chain, polyunsaturated fatty acids (LC-PUFA), in particular linolenic and linoleic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA) arachidonic acid (AA) or their glycerides or phosphoglycerides. According to the invention any combination of the above-mentioned grease and oil components can be used.

The term "flavoring oil component" includes oils such as herbal or spice oil concentrate, peel oil, fruit oil and other oils and fats as defined above which are capable of imparting particular flavors to a food. The production of enriched vegetable oils (edible oils) preferably from processed, shelled oilseeds with parts of herbs and / or plant parts Spice plants and / or fruits is in itself from the DE 101 01 638 C2 known. Examples of flavoring oils include oil from processed, shelled oilseeds with plant parts of herbal plants such as thyme, basil, coriander and oregano; Herbal plants such as fennel, for example fennel oil concentrate; or fruits such as sea buckthorn, for example, sea buckthorn pulp oil and sea buckthorn kernel oil or citrus fruits.

Polysaccharides (PS) represent a significant group of biopolymers. For the purposes of the present invention, the polysaccharides are preferably hydrocolloids, ie they are high molecular weight polar water-soluble biopolymers ( Dickinson, The role of hydrocolloids in stabilizing particulate dispersions and emulsions; In: Phillips Glyn O, Williams PA, Wedlock DJ (Eds): Gums and stabilizers for the food industry 4, Wrexham 1988; 249-264 ). Preferably, the polysaccharides used are carboxyl group-containing polysaccharides. In this regard, however, with alginate and low methylester pectin, the presence of calcium ions (Ca) should preferably be avoided. Polysaccharides contemplated by the present invention include, but are not limited to xanthan, carboxymethyl-pullulan, carrageenan, chitosan, gellan, Na-carboxymethylcellulose, Na-alginate and pectin.

Pectins (PEs) are polysaccharides found in the cell walls of higher plants. They are isolated from the middle lamella or the primary cell wall. In the middle lamella, pectin serves as a putty, while in the primary cell wall it is actively involved in the water balance of the cell. The extraction takes place from the shells of citrus fruits, from apple or Rübentrestern. Pectins are heterogeneous, complex polysaccharides. They consist of partially esterified α-1,4-linked D-galacturonic acid units ( Kunz, Encyclopedia of Food Technology. Springer Verlag, Heidelberg, 1st edition, 1993 ). This main framework is interrupted by rhamnoses with side chains of neutral sugars (arabinose, galactose). The hydroxyl groups on the C1 or C3 atom of the galacturonic acid units are partly acetylated or substituted by further neutral sugars (such as D-galactose, D-xylose, L-arabinose, L-rhamnose) ( Ebert, Biopolymers: Structure and Properties. BG Teubner Verlag, Stuttgart 1993; Kunz, (1993 ), see above). The carboxyl groups of the polygalacturonic acid are partially esterified or amidated with methanol. The molecular mass of commercial pectins is between 30,000 and 200,000 g / mol ( Switzerland. Food book gelling and thickening agent, 1993 ). In general, pectin can be differentiated by the degree of esterification (DE). The degree of esterification indicates the percentage of the esterified with methanol carboxyl groups. Pectin with a DE> 50 is called highly esterified pectin, while pectin with a DE <50 is low esterified. Amidated pectin is low methylated pectin which additionally contains amide groups. Amidation degree (DA) is defined as the percentage of amidated carboxyl groups ( Rolin, pectin. In: Whistler RL, BeMiller JN (Eds): Industrial gums polysaccharides and their derivatives. Marcel Dekker Inc., New York, 3rd Edition (1993), 257-293 ). Pectins are commercially available from several manufacturers. It is understood that the term "pectins" according to the invention also includes polysaccharides which do not represent pectin in the strict sense, but due to derivatization of, for example, polygalacturonic acid or polysaccharides by hydroxylation, carboxylation, esterification and / or amidation in their properties the same of pectins. or come close, and therefore can be used equivalently. In the EU, pectin is approved under E440 as a food additive for a variety of products.

Sodium carboxymethylcellulose (CMC) is a cellulose-based biopolymer prepared by etherification of cellulose in sodium hydroxide solution with sodium monochloroacetate ( Feddersen et al., Sodium carboxymethylcellulose. In: Whistler RL, BeMiller JN (Eds): Industrial gums polysaccharides and their derivatives. Marcel Dekker Inc., New York, 3rd Edition (1993), 537-578 ). As a measure of the degree of etherification, the degree of substitution (DS) is given. The degree of substitution indicates the average number of etherified hydroxyl groups of a glucose unit. Due to the three reactive hydroxyl groups it is possible to introduce three sodium carboxymethyl groups. The properties of the Na-carboxymethylcellulose depend on the degree of substitution and the degree of polymerization ( Belitz et al., Textbook of Food Chemistry. Springer-Verlag, Berlin, 4th edition, 1992 ). The degree of polymerization indicates how many monomeric molecules are linked on average to the macromolecule during polymerization. The Na-carboxymethylcellulose, which is preferred according to the invention, has an average molecular weight of 125,000 g / mol. The average degree of polymerization is 582 β-D-glucose units. In the EU, Na-carboxymethylcellulose is approved under E466 as a food additive in the thickening and gelling group.

It is understood that the term "Na-carboxymethylcellulose" according to the invention also includes polysaccharides which do not represent Na-carboxymethylcellulose in the true sense, but for example due to derivatization of, for example, cellulose or other polyurea by hydroxylation, carboxylation, esterification and / or etherification in their Properties that are similar and / or close to Na-carboxymethylcellulose, and therefore can be used equivalently.

The term "protein" includes any substantially amino acid peptide and polypeptide. Suitable protein sources for the production of PPS include vegetable proteins (especially oil seed proteins derived from cotton, palm, oilseed rape, safflower, cocoa, sunflower, sesame, soy, pea, potato, peanut and the like), animal proteins such as sodium Caseinate, bovine serum albumin, protein albumin and microbial proteins, such as yeast proteins and so-called "protozoan" proteins.

Preferred proteins include whey protein isolate, milk protein concentrate, Na-caseinate or skimmed milk powder and non-dairy whey proteins such as vegetable proteins, especially soya, pea and lupine proteins; see also the examples. Whey is produced as a by-product of cheese production. It accounts for approximately 80-90% of the total volume of milk and contains many nutrients. An important part of the whey are the whey proteins. Whey proteins are the proteins which remain in the whey after separation of the caseins from the milk by acid or rennet precipitation ( Barth and Behnke, nutritional physiological importance of whey and whey components. Nutrition 41 (1997), 2-12 ).

The term "protein" also includes biologically active proteins such as enzymes used in, for example, yoghurt and cheese manufacture or detergents; Hormones such as insulin for drug products; Antigens for vaccines; Proteases in reagents, etc.

By "polyol" is meant a polyhydric alcohol having at least 4, preferably 4 to 11 hydroxyl groups. Polyols include sugars (these are monosaccharides, disaccharides and trisaccharides), sugar alcohols, other sugar derivatives (these are alkylglucosides), polyglycerol such as diglycerol and triglycerol, pentaerythritol, sugar ethers such as sorbitan and polyvinyl alcohols. Specific examples of suitable sugars, sugar alcohols and sugar derivatives include xylose, arabinose, ribose, xylitol, erythritol, glucose, methylglucoside, mannose, galactose, fructose, sorbitol, maltose, lactose, sucrose, raffinose and maltotriose.

pictures

1 : Schematic representation of the process according to the invention for the preparation of the oil-in-water (O / W) emulsion according to the invention (also referred to herein as "PPS"). In one embodiment (A), a phase consisting essentially of the fat / oil component (oil phase) is dispersed in an aqueous phase containing the protein and polysaccharide; see also Example 1. In another embodiment (B) the oil phase is mixed with a polysaccharide and subsequently dispersed in an aqueous phase containing the protein; see also Example 2. In a further embodiment (C), part of the intended amount of polysaccharide (PS) according to variant B is introduced into the oil phase and the oil + PS phase according to variant A is dispersed in the P + PS phase , wherein preferably their amount of polysaccharide (PS) is adjusted according to the amount of PS already present in the oil phase. The process temperature in all cases until the emulsion is obtained should be below the denaturation temperature range of the proteins (eg whey protein not higher than 60 ° C).

option A

• A ¹ : Oil and / or fat component (s) (O) are heated to about 50 ° C or until all the fat is melted at 60 ° C (oil phase). Ideally, the oil phase has a density of about 1.0 g / cm ^3.
• A ² : polysaccharide (PS) is slowly added to the aqueous phase (about 50-90 ° C., preferably 70 ° C.) using a magnetic stirrer or stirrer RW 16 basic with a stirrer (IKA Laboratory Technology, Staufen, Germany) at about 1500 rpm C for pectin or CMC) was added and dissolved for about 1-2 h until a clear solution was obtained. In the presence of a polyol such as sucrose, the polysaccharide is dry-mixed with it and then dispersed in the aqueous phase. The proportion of water for dissolving the polysaccharides and optionally polyol is preferably about 75% of the total amount of water. Before further use, the PS solution can be sterilized at 95 ° C for 10 minutes.
• A ³ : Protein (P) is slowly added to the aqueous phase (about 50 ° C.) at 1000 to 1500 rpm using a magnetic stirrer or a star stirrer (modified stirrer disc) and dissolved for about 1 h. When foam is formed, the speed of rotation of the stirrer is reduced. The proportion of water for dissolving the proteins is preferably about 25% of the total amount of water. If the protein has an acidic pH and is therefore poorly soluble (eg, the potato protein EMVITAL K5), the protein dispersion is mixed with the polysaccharide or the oil phase by adding 1% NaOH before mixing. Solution (eg 1.96 g of 1% NaOH per g protein) neutralized. Before use, it may be advisable to sterile filter the P solution, for example by means of a 0.2 micron ceramic membrane at 4 MPa.
• A ⁴ : The aqueous P solution is slowly mixed into the aqueous PS solution using a stirrer.
• A ⁵ : In the aqueous P-PS phase, the oil phase is incorporated with continuous stirring at 1500 U / min and subsequently z. B. using a rotor-stator dispersion (CAT-X620, M. Zipperer GmbH / Staufen) at about 20,500 to 24,000 rev / min and 15 s to 1 min nachemulgiert. On a laboratory scale, the addition of the oil phase is carried out dropwise within 20 s by means of a Pasteur pipette or slowly by means of a 5 ml macro pipette. In the preparation of the emulsion by means of process plants, the slow addition of the pre-dosed oil fraction takes place via an intake manifold.
• A ⁶ : Under laboratory conditions, the fine dispersion of the emulsion is carried out with the EmulsiFlex C5 high-pressure emulsifier (AVESTIN, Canada) at 20 to 80 MPa, preferably 50 MPa or with other suitable pressure emulsifiers (eg laboratory pressure homogenizer HH 20 (Scientific Equipment Construction, Zentralinstitut für Ernährung . DE 195 30 247 A1 ) at 8 MPa. The mean drop size of the oil drops in the emulsion is about 1 μm ± 0.2.

Alternatively, the incorporation and fine dispersion of the oil phase into the aqueous P-PS phase can also be carried out batchwise on a large scale, for example by using the vacuum processing system FrymaKoruma MaxxD 200 (FrymaKoruma GmbH, Neuchâtel, Germany), which is based on the sprocket dispersing principle (sprocket rotor and Stator) and is able to produce high viscosity emulsions having a particle size of x ₅₀ 1.2-2.5 microns. This particle size is sufficient if higher-viscosity food products are to be produced, in particular with the aim of influencing the consistency.

Variant B

• B ¹ : = A ¹
• B ² : Polysaccharide (PS) is stirred and dispersed using a stirrer preferably with dispersing ring at 1300 U / min for about 15 minutes in the oil phase and so that an oil-PS mixture is obtained.
• B ³ : same as A ³ , except that the water content in mm of the proteins is 100% of the total amount of water.
• B ⁴ : In the aqueous P-phase, the oil-PS mixture is incorporated as indicated in A ⁵ and post-emulsified. It is important for emulsion formation that the dispersion process takes place rapidly (in a few seconds), since the viscosity of the continuous phase increases considerably as the polysaccharide content in the oil increases immediately as the drop surface area increases (m ² / ml of oil). The emulsification process should therefore be carried out in such a way that it ends with a high polysaccharide content in the oil before the emulsion no longer flows because of too high a viscosity.
• B ⁵ as indicated in A ⁶ .

Variant C

• C ¹ : = A ₁ = B ¹
• C ² : = A ² and B ² , wherein in each case only a part of the total amount of polysaccharide (PS) according to variant A or B is used.
• C ³ : = A ³
• C ⁴ : = A ⁴
• C ⁵ : = A ⁵ , wherein only a part of the total amount of polysaccharide (PS) according to variant A is used. Preferably, the amount used, together with the amount of PS used in step C ² , gives the total amount that would be used in variant A or B.
• C ⁶ : = A ⁶

Available emulsion (PPS)

The emulsion obtained basically has an acidic or neutral pH and should have a particle size of x ₅₀ <10 μm, preferably <1.5 μm. If necessary, the emulsion can be adjusted to the desired pH before further processing, for example by acidification with 0.1% citric acid (10% strength solution), lactic acid or ascorbic acid. The acid is added slowly with stirring.

The methods of variants B and C allow the preparation of emulsions with high oil and very high polysaccharide content. Such emulsions are particularly suitable for low water compositions and formulations, for example, less than 50% by weight water.

If desired, further components may be added to the emulsion with stirring, such as polyols, flavorings, dyes, preservatives and / or active ingredients. In this case, subsequent emulsification may be required. Preferably, an addition of further components is omitted.

PPS can be detected by checking the prevention of oil droplet aggregation in pH reduction (particle size determination with and without Na dodecyl sulfate addition), pH measurement and phase stability with longer life (stability against segregation). PPS of variants B and C may additionally be identified by the presence of polysaccharide in the oil phase; See also the following general description of the method according to the invention.

Preparation of the formulations

In one embodiment, the liquid viscous consistency emulsion is used by slow mixing with a flowable to liquid base having preferably acidic pH such as dressings or buffer solutions for, for example, biologically active proteins, or may be used immediately or further processed to obtain the desired product. While in most applications PPS is advantageously mixed into the respective base, it has proven advantageous to slowly mix strong acid solutions in PPS, so that the pH reduction is not "shock-like".

In another embodiment, the emulsion of creamy to pasty consistency is incorporated into a viscous, pasty, spreadable or doughy base preferably having a neutral pH in order to obtain the corresponding product. If necessary, the pH may be lowered prior to further processing of the food base, for example by acidification with an acid otherwise customary for the product, such as lactic acid or citric acid. Alternatively, the emulsion itself forms the matrix for the product, for example as an ointment or cream, in which active ingredients suitable for the respective application are incorporated. Of course, this can also take place during the production process of the emulsion, for example as part of the oil, protein or polysaccharide component.

PPS can be easily dried to mix with other components such as food ingredients, active ingredients or building materials on a dry basis. There are several drying methods available; See also Examples 12 and 13. Depending on the specific requirements of the intermediate or end product, the appropriate method should be selected. If convenience properties (eg slight solubility) are desired and these are not yet provided by the selected drying process, further processes, such as. B. Agglomerate connect. The dried emulsion is then incorporated into a dry or dried composition with other ingredients to obtain the corresponding product. Alternatively, according to the embodiments, the emulsion may also be incorporated with the other ingredients of the composition and subsequently dried or freeze-dried.

2 : Schematic representation of the preparation of the emulsion used in the process according to the invention using PPS7 (A) and PPS20 (B) and various sources of protein and polysaccharide.

Detailed description of the invention

• (i) 0,2–10,0 Gew.-% Protein;
• (ii) 0,3–10,0 Gew.-% polares Polysaccharid;
• (iii) 0,1–60,0 Gew.-% einer Fett/Öl-Komponente;
• (iv) 0–30,0 Gew.-% Polyol; wobei

eine im Wesentlichen aus der Fett/öl-Komponente (iii) bestehende Phase (Öl-Phase), die gegebenenfalls mit dem Polysaccharid (ii) oder einem Teil davon vermischt wird, in eine wässrige Phase dispergiert wird, die das Protein (i) und gegebenenfalls das Polysaccharid (ii) oder einen Teil davon enthält, und nachfolgend die Emulsion feinemulgiert wird, wobei die Partikelgröße der dispergierten Öl- bzw. Fetttropfen im Verteilungsmaximum bei x_50.3 ≤ 10 μm (volumenbezogener Medianwert) liegt. Vorzugsweise ist die Menge an Wasser im Flüssigen oder Fließfähigen (einschließlich jeglichem in anderen Inhaltsstoffen vorhandenem Wasser) im Bereich von 20 bis 95 Gew.-%, bevorzugter von 30 bis 80 Gew.-%.In general, the present invention relates to an agent, ie emulsion (hereinafter also referred to as "PPS"), which is suitable in the preparation of a variety of products, which are characterized in that they are creamy, lubricious and / or rich in consistency and in the case have a full mouthfeel of food products and meet nutritional needs. Accordingly, the present invention relates to a process for the preparation of a phase-stable oil-in-water (O / W) emulsion having a dry matter between 5 and 60 wt .-%, containing, based on the total weight of the emulsion, the following components:

• (i) 0.2-10.0% by weight protein;
• (ii) 0.3-10.0% by weight polar polysaccharide;
• (iii) 0.1-60.0% by weight of a fat / oil component;
• (iv) 0-30.0 weight percent polyol; in which

a phase consisting essentially of the fat / oil component (iii) (oil phase) optionally mixed with the polysaccharide (ii) or a part thereof is dispersed in an aqueous phase containing the protein (i) and optionally the polysaccharide (ii) or a part thereof, and subsequently the emulsion is finely emulsified, wherein the particle size of the dispersed oil or fat drops in the distribution maximum at x _50.3 ≤ 10 microns (volume median median). Preferably, the amount of water in the liquid or fluid (including any water present in other ingredients) is in the range of from 20 to 95% by weight, more preferably from 30 to 80% by weight.

The emulsion of the invention is characterized by aggregation and phase stability and creamy consistency. The present invention is based on the surprising observation that a large number of products can be modified and produced by an emulsion consisting essentially of only three components, ie protein, polar polysaccharide and liquid lipid (oil, liquid fat), see also the examples, which have not been satisfactorily produced today with commercial oil / fat emulsions and emulsifiers, inter alia, due to flocculation of the dispersed fatty phase, phase instability or water separation. The object of the present invention is mainly described by the use of an emulsion comprising pectin, (PE), Na-carboxymethylcellulose (CMC) and Na-alginate (Alg) as polysaccharide component and whey protein (MPI) and lupine protein (Lup) as protein Component contains. Unless otherwise specified, the embodiments described herein include equally embodiments in which the emulsion used contains alternative or equivalent polysaccharide and protein components. Furthermore, it is understood that an embodiment of the present invention or features thereof described herein may be combined with one or more other embodiments described herein and features thereof, unless the respective embodiments are excluded.

The emulsion used in the process according to the invention can in principle be prepared by two or three processes, as in 1 sketched and the legend too 1 explained. In one embodiment (variant A), the emulsion is obtainable by dispersing a phase consisting essentially of the fat / oil component (oil phase) into an aqueous phase containing the protein and polysaccharide; see also example 1 and 2 , In another embodiment (variant B), the emulsion is obtained by mixing the oil phase with the polysaccharide and then dispersing it in an aqueous phase containing the protein; see also Example 2. In a further embodiment (variant C), part of the intended amount of polysaccharide according to variant B is introduced into the oil phase and the oil and polysaccharide phase according to variant A is dispersed in the aqueous phase containing protein and polysaccharide , wherein preferably their amount of polysaccharide is adjusted according to the already in the oil phase containing amount of polysaccharide.

A process for preparing an emulsion according to variant A is in the German application DE 10 2006 019 241 A1 initially, without addition of acid, mixing an oil phase and a biopolymer mixture consisting of an aqueous phase with proteins (eg whey proteins) and a polysaccharide (eg Na-carboxymethylcellulose or amidated low-esterified pectin) to give a neutral emulsion and then the pH of this emulsion is lowered after addition to an acidic aqueous phase. The disclosure of the DE 10 2006 019 241 A1 , in particular the examples for the preparation of an emulsion, are hereby incorporated by reference into the present specification. However, in the DE 10 2006 019 241 A1 as well as in the additional application based thereon DE 10 2006 058 506 A1 the use of the emulsion described therein described only as an additive for acidic non-alcoholic and alcoholic cold drinks. In one embodiment of the present invention, those in the DE 10 2006 019 241 A1 and DE 10 2006 058 506 A1 expressly excluded emulsions and / or processes for the preparation of cold drinks. In another embodiment of the present invention, an emulsion according to the DE 10 2006 019 241 A1 or DE 10 2006 058 506 A1 produced, but instead of whey proteins, a vegetable protein is used.

Further, according to the present invention, in contrast to the method of DE 10 2006 019 241 A1 a lowering of the pH of the emulsion for further use in the preparation of the desired product is not necessary. In the embodiments of the process according to the present invention, an acidic or pH neutral emulsion is used, the pH being determined by the polysaccharide used and the buffering capacity of the protein. While in the embodiment of the invention using Na-CMC, the pH of the emulsion is in the neutral range (pH 6.9-7.6), the pH of the emulsions made with pectin (eg, high ester pectin) is between 4.2 to 5.0. Therefore, in a preferred embodiment of the process according to the invention, PPS is produced without any reduction in the pH due to subsequent acid addition.

In order to achieve the desired effects of the emulsion according to the invention, it has proved to be advantageous to dissolve the protein and polysaccharide components individually in water and then to mix them first. Preferably, an aqueous protein-polysaccharide phase is prepared by mixing a solution containing the protein in a solution containing the polysaccharide, see also the scheme for variant A in 1 ,

In a particularly preferred embodiment of the process according to the invention, the polysaccharide used in the emulsion is a pectin product. In a particularly preferred embodiment, the pectin used is highly esterified pectin. In a further particularly preferred embodiment of the method according to the invention, the polysaccharide used in the emulsion is Na-carboxymethylcellulose (CMC).

In one embodiment of the present invention, the oil phase of the emulsion contains a flavoring oil. If a very low emulsion emulsion prepared according to the present invention is to be used for food flavoring or fragrance of cosmetics containing a flavoring oil, the emulsion used should be stable even at high dilution. Since such taste-influencing oils generally have a lower density than the continuous phase (. Eg dispersed phase <0.930 g / cm ^3; continuous phase> 1.000 g / cm ^3), is not only a very small drop size of the dispersed oil, but also avoiding droplet aggregation and an additional increase in the density of the dispersed phase required. The higher density of the oil phase, which should be adapted to the density of the surrounding phase, then leads, for example, in liquids to sufficient suspension of the dispersed drops and thus to the stable turbidity of, for example, a tincture or a lotion.

With strong dilution of the emulsion according to the invention, in particular in liquid and flowable products, it is therefore preferable to ensure that the oil phase of the emulsion has a density above 0.995 g / cm ³ . In the German application DE 10 2007 026 090 A1 describes the preparation of cloudy light drinks using an emulsion consisting of an oil phase and an aqueous protein and polysaccharide-containing phase in which the oil phase of the emulsion contains at least one flavoring oil, preferably from processed, shelled oilseeds with plant parts of herbal and / or spice plants and / or fruits, and has a density of more than 0.850 to 1.135 g / cm ³ , preferably from 0.995 to 1.020 g / cm ³ . Is made such an emulsion as in the DE 10 2006 019 241 A1 described from an oil phase and an aqueous phase, wherein initially without acid addition oil and a biopolymer mixture consisting of an aqueous phase with proteins, preferably whey proteins, and a polysaccharide, preferably Na-carboxymethylcellulose or amidated low methylester pectin, are mixed to form a neutral emulsion and then the pH of this emulsion is lowered after addition to an acidic aqueous phase.

In contrast to that in the DE 10 2006 019 241 A1 described processes are used for the emulsion formation one or more flavoring and prepared from processed, shelled oilseeds with plant parts of herbal and / or aromatic plants and / or fruits oils and / or other, preferably vegetable flavoring oils. Before emulsification, the flavoring oils with a Glycerinester the fractionated vegetable fatty acids are C ₈ and C _10, which is linked to succinic acid and a density of 1.00 to 1.02 g / cm ³ (z. B. Miglyol ^® 829, Sasol Germany GmbH), mixed and increased in density. Alternatively, other oil or fat components capable of increasing the density of the oily phase containing the taste-affecting oils in the range of 0.850 to 1.135 g / cm ^3, preferably 0.995 to 1.020 g / cm ^3, may be used in the present invention , In one embodiment of the method according to the invention, the use of an emulsion is as in DE 10 2007 026 090 A1 described, for the production of drinks, especially light drinks excluded. In another embodiment of the method according to the invention, an emulsion is used which according to the DE 10 2007 026 090 A1 however, instead of whey proteins, a vegetable protein is used.

In a further embodiment of the present invention, the aqueous phase of the emulsion used contains polyol. For example, the addition of 1-3% of a polyol such as granulated sugar facilitates dispersing Na-CMC and reduces the heat sensitivity of the whey protein. Generally, it is common practice in the industry to improve the dispersibility of easily clumping powders (when mixed in water) with other materials that are less prone to clumping. So it is recommended to mix pectin or even Na-CMC with sugar, if the recipe contains granulated sugar. Although the use of a process system for emulsion preparation may generally omit the presence of a polyol, in some embodiments of the present invention it may be desirable for the emulsion used to contain at least 1% of a polyol, ie, sugar (eg, sucrose, sorbitol, or isomalt ), because these sugars cause additional techno-functionality. In addition to improving the freeze-thaw behavior of the emulsions (avoiding oiling out of the emulsion upon freezing), sorbitol also results in lower water activity (better microbial shelf life) and isomalt for reduced hygroscopicity of dried emulsions. The presence of isomalt in the The emulsion used is also of advantage for the production of food products in which prolonged energy supply is desired (sports drinks).

In a further embodiment of the present invention, the oil phase of the emulsion used contains a weighting agent, for example, sucrose acetate isobutyrate (SAIB). The presence of a denaturant can be advantageous if the emulsion is to be used as a flavoring emulsion in high dilution. Instead of SAIB can, as in the DE 10 2007 026 090 A1 also succinic acid esters of fatty acid glycerides can be used as the weighting agent or a polysaccharide bound in the oil phase; see the above discussed DE 10 2007 057 258.3 and Example 2.

In a preferred embodiment of the present invention, the emulsion used is substantially free of synthetic emulsifiers, weighters, and / or polyols. For example, in the emulsion preparation with the FrymaKoruma process plant (ROMACO, Frymakoruma GmbH, Neuchâtel, Germany), the presence of a polyol in the emulsion is not required because the high shear forces do not cause the above-discussed lump formation. In a further preferred embodiment of the present invention, the emulsion used is substantially free of flavoring oil components, flavorings, dyes, preservatives, acids and / or other excipients.

In a particularly preferred embodiment of the present invention, the protein used in the emulsion is a vegetable protein. As explained above, in the DE 10 2006 019 241 A1 . DE 10 2006 058 506 A1 and DE 10 2007 026 090 A1 describe the preparation of an emulsion made exclusively with whey proteins and intended only for use in the manufacture of beverages. Only in the context of the present invention experiments were carried out, which surprisingly revealed that emulsions, for example, by a method as in DE 10 2006 019 241 A1 or DE 10 2007 026 090 A1 , but were prepared with vegetable proteins instead of whey proteins, have a very high phase and acid stability and are outstandingly suitable for incorporation in a variety of products, especially on a purely vegetable basis.

Advantageously, therefore, according to the invention, emulsions can be prepared which instead of whey proteins contain plant proteins such as lupine proteins, whereby, for example, allergic reactions to products with whey proteins, under which consumers can suffer, are avoided in these emulsions. Furthermore, by using vegetable proteins, pea protein, soy protein or potato protein in the emulsion can be influenced on the amino acid composition, thus providing a nutritionally-altered food. In addition, in connection with the use of a vegetable oil for the oil phase and a plant polysaccharide such as pectin in the emulsions according to the present inventive method products can be produced on a purely vegetable basis. Thus, the needs of certain consumer groups from the raw material side can be easily and well taken into account. Therefore, in a particularly preferred embodiment of the process according to the invention for preparing the emulsion, the constituents are essentially of vegetable origin.

In a further preferred embodiment of the process according to the invention for preparing the emulsion, the polysaccharide used is Na carboxymethyl cellulose (CMC) or pectin (PE). Although pectin and Na-CMC are carbohydrates, they are not taken into account in the nutritional calculation because they are pure fiber and are not metabolized directly. In some embodiments, pectin is also found to contain nutritional information (eg, 100 kcal or 425 kJ per 100 g) when the pectin contains sugar for standardization (for uniform gel strength). The addition of sugar to the pectin is very different, in the example mentioned for the nutritional information, the sugar content is about 25%. In the case of Na-CMC, no further carbohydrate additions are preferably carried out to set the desired properties.

In one embodiment of the process of the invention, the pectin used to make the emulsion is highly esterified (HV) or amidated low methylester pectin (P-am). P-am has been shown to produce very stable turbidity in light beverages, but should a wider use of the flavored PPS emulsion be provided on products containing calcium, the reaction of calcium with the pectin may lead to undesired product changes (flocculation, gelation , Phase separation, etc.). This is also true if incorporation into dairy products is envisaged. Therefore, in another embodiment, the pectin used in the emulsion is highly esterified pectin.

For the process according to the invention for preparing the emulsion, the ratio of protein to polysaccharide is 4: 1 to 1: 4, the emulsion preferably containing essentially 0.75-5.0% by weight of protein, 0.5-2.5% Wt .-% polysaccharide and 5.0-50.0 wt .-% fat / oil component. If a higher polysaccharide content (eg pectin) is desired, this can be achieved by adding it to the oil phase prior to emulsion preparation according to the methods described in US Pat 1 illustrated and explained in the figure legend embodiments B or C can be realized.

As already explained above, the present invention is based on the surprising observation that a variety of products can be modified and produced by an emulsion consisting essentially of only three components, ie protein, polar polysaccharide and neutral vegetable oil, see also the examples. In a particularly preferred embodiment of the present invention, therefore, the emulsion consists essentially of the components protein, polysaccharide and oil. Particularly preferred compositions are summarized in Table 1 below. Table 1: Preferred compositions of the emulsion according to the invention used together with typing under the name "PPS" according to the dry mass of the emulsion. PPS typing Composition (% by weight) 7 20 34 51 protein 1 2 2 3 Polysaccharide PE (Na-CMC) 1 3 2 3 (2) oil 5 15 30 45 water 93 80 66 49

The absolute amounts of protein and polysaccharide, as well as their relationship to each other, depend on the desired application (the polysaccharide content also determines the viscosity) and thus vary accordingly, preferably both components together with the designated as PPS 7 emulsion with 1 , 5-2.5 wt .-%, with PPS 20 between 3.5-6.0 wt .-%, PPS 34 between 3.0-5.0 wt .-% and PPS 51 between 4.0- 7.0% by weight. The amount of fat / oil components preferably remains unchanged, with deviations of max. 10% tolerated. Preferably, the ratio of protein to polysaccharide in the aqueous phase is 1: 1 to 1: 1.25.

In the above table different protein-polysaccharide ratios are given, which are based on the fact that the proportion of protein must increase with increasing proportion of oil. With increasing drop surface per ml of oil, a higher protein content is required for the interface occupancy. If the protein content per m ^{2 of} surface / ml of oil is too low, the drops are no longer stable to coalescence. On the other hand, the water content in the emulsion decreases and at too high a Na-CMC or pectin concentration in the aqueous phase, the emulsion is no longer flowable. By means of the pectin content or proportion of Na-CMC, it is thus possible to adjust the flow properties or also the pasty consistency. In a particularly preferred embodiment of the present invention, the emulsion used has substantially one of the compositions shown in Table 2. Table 2: Preferred compositions of the emulsion according to the invention used together with typing under the name "PPS" according to the dry matter of the emulsion. Ingredients per 100 g PPS 7 PPS 20 PPS 34 PPS 51 1a 1b 2a 2 B 3a 3b 4a 4b Na-CMC 1000 GA 1.0 - 3.0 - 2.0 - 2.0 - Pectin AS 501 - 1.0 - 3.0 - 2.0 - 3.0 minor protein 1.0 1.0 2.0 2.0 2.0 2.0 3.0 3.0 vegetable oil 5.0 5.0 15.0 15.0 30.0 30.0 45.0 45.0 water 93.0 93.0 80.0 80.0 66.0 66.0 50.0 49.0 total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0

For the process according to the invention, the mass ratio of protein / polysaccharide in the emulsion used can vary by 1: 1, as in US Pat DE 10 2006 019 241 A1 indicated (1: 0.25 to 1: 2.0). This essentially applies to the combination of protein with pectin and Na-CMC, while for the combinations Protein with other polysaccharides it is advisable to carry out appropriate preliminary experiments. The dry matter of the emulsion used is preferably between 7.0 and 55.0 wt .-%.

In a preferred embodiment, the emulsion preferably contains more than 1.5% by weight protein and / or more than 1.0% by weight, preferably more than 1.5% by weight, of polysaccharide, the dry matter (TS) being preferably, a total of about 20 wt .-% or greater. As indicated in Tables 1 and 2 above, in this case, the emulsion preferably contains at least 2.0% by weight of protein and / or at least 2.0% by weight of polysaccharide.

The particle size of the emulsion obtainable by the process according to the invention is preferably x _50.3 <5 _μm , more preferably x _50.3 <1.5. This particle size is sufficient if the emulsion is used to higher viscosity products, especially with the aim of consistency control. Such emulsions with a particle size <1.5 μm additionally give a higher degree of turbidity on dilution and have a slower creaming rate. The emulsification experiments with a process unit show that under certain emulsifying conditions, the sprocket dispersing principle can lead to even smaller drops in emulsions.

In a preferred embodiment, the emulsion of the invention is over a long period of time, i. H. at least three months, preferably six months, more preferably 12 months and advantageously 24 months in closed packaging when stored frozen at -18 ° C and stable, d. H. that no phase separation occurs before use. The moist product as well as preferably the dry product should be stored cool before use and protected from direct sunlight.

In this connection, the emulsion according to the invention can be used without further processing as thickening agent, suspending agent, binder, water retention agent and for lowering the fat content. Economical considerations, however, require that the emulsions be dried and processed and marketed as a substantially dry composition. Although drying can be performed by any method known to those skilled in the art, drum drying is the preferred method.

For instant application, for example, PPS can be dried in a spray dryer using standard dairy conditions. Another advantage is the freeze-drying. In the event that PPS should be dried prior to admixture with other ingredients of a formulation, the first step is to freeze the emulsion to perform lyophilization. This is a high freezing stability to avoid large crystal formation, which destroys the interface to the oil droplets and thus the. Drop coalescence (may be advantageous.) Addition of polyol such as sugar, in particular in the form of mono- or disaccharides (as "cryoprotectant agent") may increase freeze stability.

This embodiment is particularly advantageous for instant products in which the emulsion used can effect lightening of coffee and tea beverages as an imitation of milk additive. In instant products of the prior art, in which milk substitutes are used for this purpose, this is achieved in particular by the combination of proteins with low molecular weight emulsifiers. In the emulsion used in the present invention can advantageously be dispensed with the addition of low molecular weight emulsifiers.

A composition of PPS is considered dry for purposes of the invention when its moisture content (free water content) is less than about 20%. As a rule, the products obtained are dried to about 5 to 12% moisture. Dry compositions may then be comminuted, milled or pulverized to any desired particle size. Those skilled in the art will recognize that other drying methods can be used, provided that the viscosity or moisture content of PPS is adjusted to the process conditions prior to drying. Depending on the application, the proportion by weight of PPS in dry mixtures is from 0.1 to 99% by weight, preferably from 2.0 to 98% by weight, more preferably from 5 to 90% by weight, and particularly preferably from 50 to 50% by weight 80% by weight. Dried products can be easily redissolved in water by high shear mixing to yield the useful aqueous compositions of the present invention. When water is added to essentially pure PPS-based dry compositions, essentially the respective starting emulsion or, when larger amounts of water are added, a corresponding dilution of the respective PPS type is produced.

As already explained above, the dried compositions according to the invention have unique properties which can be determined by suitable selection of the constituents, fractions and Processing conditions for specific end applications can be tailored. These compositions predominantly hydrate rapidly and give distributions which are not only smooth and more or less viscous depending on typing, but also have excellent creaminess and very good film-forming properties with low sliding resistance.

Compositions of the present invention having a higher solid fat content to give viscous pastes at room temperature become sufficiently thin upon heat so that they can be cast. Heated compositions then solidify again after cooling. These properties are similar to those of a typical meltable fat or shortening. When the biopolymer / oil emulsion is prepared with solids contents exceeding about 30%, the resulting products tend to be thick and well adherent, favoring use as a coating emulsion and film-forming agent, and their use as a lightweight adhesive also appears feasible leaves.

Depending on the desired formulation, a suitable PPS type can be used. For example, PPS7-PE is useful as a liquid viscous, odorless, and slightly acidic emulsion especially for liquid formulations such as tinctures and lotions, while PPS7-CM and PPS20-PE are more thick and tasteless emulsions for gels and flowable matrix of active ingredients in capsules. PPS20-CM as a thick creamy, low-flow emulsion and PPS34-PE, PPS34-CM, PPS51-PE and PPS51-CM as thick-cream odorless and taste-neutral pastes are particularly advantageous for the preparation of ointments, creams, sealants, etc. In this context, it is understood that the higher concentrated PPS types can be diluted and also used in liquid formulations. As explained above, in addition to the use of the desired polysaccharide, the viscosity can also be influenced by the production of PPS according to variants B and C of the process according to the invention by increasing the proportion of polysaccharides in the oil phase. Furthermore, the adjustment of the particle size can influence whether PPS is more or less oily in solid to dry form. For example, results of spray drying of PPS show that as the particle size of the oil drops decreases, the powders become "drier", that is, they dry up. H. dry at about 1 micron, while at a particle size of about 5 microns PPS is more oily and can be easily triturated in this form, which is advantageous in the application of PPS as a cream, ointment or make-up powder. The variety of properties of the compositions of the invention thus make them suitable for and in the preparation of a variety of products in which emulsions are typically used.

In the food sector, include, but are not limited to, formulations in which compositions of the invention may be incorporated, sour cream, yoghurt, ice cream, cheese, cream cheese, baking mix, biscuits, dry roasted peanut coatings, salad dressings, meats, margarine, powdered shortening, pasta, Ready-to-serve gravy and confectionery. For these applications, the compositions may be formulated at about 5% to about 60% fat, based on the weight of the emulsion. Further, the compositions of the present invention are useful as carriers of volatile flavors and aromas and as low-fat coatings to enhance the taste and easy "puffing" of popcorn in a microwave oven.

In the health care product sector, the compositions of the present invention are useful as carriers or vehicles in pharmaceutical, cosmetic and personal care product formulations. Examples of such formulations include, without limitation, hand and body lotions and creams, bath oils, shampoos and hair conditioners, sun lotions, lipsticks, eye shadows, talcum powder, foot powders, medicinal oils, vitamins, antibiotics, antifungals and the like. For the preparation of a skin cream or ointment, for example, 50% by weight of PPS20 are used as the basic substance and the ingredients of creams and ointments otherwise customary in the prior art are added. In particular, PPS may contain, as a pharmaceutical or cosmetic composition, the following constituents individually or else in any combination: hydrophilically modified silicones; Plant extracts; Amino acids, peptides, proteins and their derivatives; oligonucleotides; other polymers; vitamins; flavonoids; isoflavones; Ubiquinol compounds; UV filter substances; serum regulating agents; deodorants; Antioxidants. For concrete examples of the constituents mentioned as well as other active ingredients, auxiliaries and additives, see, for example, the German Offenlegungsschrift DE 10 2006 031 500 A1 , the disclosure of which is hereby incorporated by reference into the present specification.

In the seed coating art, these compositions are similarly useful as carriers for antifungals, herbicides, nematocides, growth regulators, hormones, fertilizers, germination stimulators and other agents as known in the art.

As a dispersing or emulsifying agent, PPS is useful in the food industry to emulsify other oils or volatile agents, flavors, fragrances, fresh fruit extracts and the like. PPS can also be used in agriculture, as a coating for fruits and vegetables to delay spoilage or inhibit oxidation, and could also be used to protect buds and bulbs. Furthermore, PPS is considered in the production of fertilizers.

Industrial applications for PPS include the formulation of coating agents, adhesives, window sizing, as thickeners for paints, inks, polishes, tinctures, paint removers, detergents, lubricants, toners and drilling muds, binders in concrete and sealants, and as fillers in plastic formulations with improved compatibility with hydrophobic additives and plastics.

In this context, the surprisingly high water binding of PPS is also advantageous in its use in the building materials sector, for example as a water retention agent and setting retarder. Therefore, the present invention also relates to PPS-based building material dry blends and their use. In the prior art, for example, building material dry mixtures based on calcium sulfate are known; See, for example, the German Offenlegungsschrift DE 10 2007 027 477 A1 , the disclosure of which is hereby incorporated by reference into the present specification. According to the invention, PPS can be used in such building material dry mixtures, for example to partially replace calcium sulfate and / or to contribute to water retention. The building material dry mixture according to the invention can be used, for example, as a joint filler for gypsum boards but also as a filler and gypsum plaster. In one embodiment, PPS is included as a set retardant in a dry kiln dry blend of 0.01 to 2.0 weight percent. For other possible components of the dry building material mixture see the published patent application DE 10 2007 027 477 A1 ,

In another embodiment of the present invention, PPS is used in a detergent, for example as a tablet, powder, granule, liquid, gel or in single portions. In one embodiment, by selecting appropriate oils, PPS will be used as the skin care compound of a detergent portion, as described, for example, in German Offenlegungsschrift DE 10 2006 029 837 A1 are described, the disclosure of which is hereby incorporated by reference into the present specification. In this case, PPS can be used as a component of the system for controlling the solubility of the detergent-active substances as described in US Pat DE 10 2006 029 837 A1 are described. Further detergent, cleaning agent and care agent portions, which consist of an outer rest form, containing one or more fillings are known to those skilled in principle; see also the German patent application DE 102 44 802 A1 , the disclosure of which is hereby incorporated by reference into the present specification. The cited prior art can also be taken from the usual ingredients for detergents, cleaners and care products.

Formulations of PPS can be made by any suitable conventional technique according to the type of composition. Such techniques are well known to those skilled in the art and need not be further described here, but may include blending, mixing, extrusion homogenizing, high pressure homogenizing, emulsifying, dispersing or extruding. Foodstuffs may be subjected to a heat treatment step, for example pasteurization or UHT treatment. Finally, in another embodiment of the invention, PPS or the formulation obtained with PPS may be packaged in a suitable container and / or stored under suitable conditions.

The invention will be described in more detail below with reference to a preferred embodiment, but without limiting the subject matter of the present invention.

EXAMPLES

material

proteins

• Na caseinate DSE 7894, NZMP, NZ / Fonterra (Europe) GmbH, D
• Milk protein concentrate DSE 9148, ditto
• Whey protein isolate DSE 5669, ditto
• Whey protein concentrate NuDr 8080, partially denatured, Arla Foods amba, DK
• Organic skimmed milk powder, HEIRLER CENOVIS GmbH, D
• Pea protein PISANE M9, Cosucra Group, B / Georg Breuer GmbH, D
• Soy protein SOYPRO-900 IP, Kerry Group, Ireland / Georg Breuer GmbH, D
• Lupine protein LUPIDOR HP, HOCHDORF Nutrifood, CH / Georg Breuer GmbH, D
• Potato protein EM VITAL K5, Emsland Group, D / Emsland starch GmbH, D

polysaccharides

• Highly esterified pectin Herbacel Classic CU 201 (Pectin HV), Herbstreith & Fox, D
• Highly esterified pectin Herbacel Classic AS 501 (pectin HV), Herbstreith & Fox, D
• Low methylester pectin OP0301 (NVP), OBIPEKTIN, CH
• Amidated low methylester pectin OP0404 (ANVP), OBIPECTIN, CH
• Amidated low methylester pectin GRINDSTED LA 415 (Pectin NV), Danisco A / S, DK
• Gum arabic (GA): spray-dried, Ph. Eur., ROTH GmbH & Co. KG, D
• Alginates FD 120, GRINDSTED, Danisco A / S, DK
• Carrageenan Cerogel, Type CL-07 Lambda, C.E. Roeper GmbH, D
• Amylopectin C * Gel 04201 Waxy maize starch, Cargill Germany GmbH, D
• Na-carboxymethylcellulose WALOCEL CRT 1,000 GA (Na-CMC), Dow Wolff Cellulosics, D

oils

• Miglyol ^® 812 neutral oil (MCT), density 0.9400 g / cm ^3, Sasol Germany GmbH, D
• Neutral oil ^Miglyol® 829, density 1.010 g / cm ³ , Sasol Germany GmbH, D
• Rapeseed oil Rapso, density 0.920 g / cm ³ , VOG AG, A
• Sunflower oil Sonnin, density 0.921 g / cm ³ , Walter Rau Lebensmittelwerke, D
• Herbal Oil Concentrate K-Oil; TH, thyme; PF, peppermint; AN, anise; Chamomile, oregano, density 0.9210 g / cm ³ , EG Ölmühle & Naturprodukte GmbH, Kroppenstedt, D

miscellaneous

• Deionized water (electrical conductivity: <2 μS / cm) or tap water with low hardness
• SAIB, sucrose diacetate hexaisobutyrat (SAIB-SG), Aldrich W51.810-7-K, density 1.1460 g / cm ^3, Sigma-Aldrich, D

methods

Method of measuring oil drop size distribution

In preparing the emulsion, the desired oil drop size distribution is an important parameter. For the particle size analysis, the Coulter Electronics LS 100 measuring device (laser diffraction system, measuring range 0.4-900 μm, wavelength 750 nm) using the MVM module was used. The distribution of the particles of the O / W emulsions was measured in distilled water with and without the addition of SDS (Na dodecyl sulfate). If, after the addition of SDS, a narrower particle size distribution with a smaller average particle size is measured, it can be assumed that droplet aggregates are present in the emulsion investigated (protein-stabilized emulsions not prepared according to the invention generally have droplet aggregation on addition of acid, this also applies to emulsions with heat denatured whey protein). ,

In the evaluation, the volume-related mean diameter d ₄₃ , the surface-related average diameter d ₃₂ , the mode value (value that occurs most frequently in the series of measured values) and the SPAN (factor for the width of the distribution, SPAN (d ₉₀ %). d ₁₀ %) / d ₅₀ %). Since different parameters are often specified for the particle size ranges, the indication of the volume-related median value x ₅₀ is preferably used here. He states that 50% of the drop volume is taken by drops smaller than the indicated drop diameter x ₅₀ . In order for the indication to refer to the volume median value, the further specification x _{50.3 is made} .

Creaming or phase stability

In order to check the stability of the O / W emulsions of different preparation and composition, each 10 ml of these emulsions were filled into a graduated centrifuge tube. After 60 and 120 min (or after longer periods), the determination of the settled serum of creamed emulsion or the oil phase. Furthermore, the phase change with respect to segregation was observed over time (up to 14 days storage at + 16 ° C).

Microscopic examination

To examine the microscopic appearance of the emulsions, the microscope BX61 (OLYMPUS Deutschland GmbH, Hamburg) with ColorView camera (Soff ImagingSystem) and image analysis program analySIS ^® (Soff Imaging System) was used. Prior to observation, the emulsions were diluted 1:10 with deionized water. One drop of each sample was applied to a diagnostic slide (ROTH GmbH & Co. KG) and evaluated at 200X magnification for single drop distribution or drop aggregation. An oil sales was not found in these studies.

Rheological properties

τ

Schubspannung (Pa)

k

Konsistenzfaktor (Pa sⁿ)

n

Fließexponent

γ

Scherrate (s^–1)

To characterize the flow properties of the emulsions, a cone-plate measuring system was used (Rheostress RS 300, THERMO HAAKE, Karlsruhe). For this purpose, a cone with a diameter of 60 mm and an angle of 1 ° was used. The measuring temperature was 23 ° C. About 1 ml of the sample was placed on the plate and tempered for 3 min (thermostat DC30, HAAKE). The shear rate was continuously increased from 0 to 100 s ^-1 . From the measured values obtained, the consistency factor k was determined according to the flow law according to OSTWALD-DE WAELE. τ = k · γ ⁿ

τ

Shear stress (Pa)

k

Consistency factor (Pa s ⁿ )

n

flow index

γ

Shear rate (s ^-1 )

Determination of freeze-thaw stability

Highly viscous stable emulsions were stored as a flat layer (2 mm) between PE film (film bag) at minus 17 ° C (at least 24 hours), then stored at + 20 ° C for 1 hour. Low-viscosity stable emulsions (at least 24 hours in phase stability) were filled in 5 ml cryo-tubes and stored at -17 ° C for at least 24 hours and then stored at + 20 ° C for 1 hr. The appearance of the emulsion was evaluated (degree of preservation of the emulsion). Demixed emulsions (no smooth appearance, water repellency) were classified as non-freeze-thaw stable. An oil (or "oiling out" of the emulsion) was not observed in these studies.

Visual observation

Significant abnormalities were recorded in the preparation of the protein solutions, in the mixing of the solutions, in the emulsion preparation and during the storage of the emulsions.

Measurement of the pH of the emulsions

The pH of the freshly prepared emulsions was measured without dilution with the aid of the HI 1131 (pH meter Hanna Instruments) electrode.

Turbidity properties of the emulsions on dilution

0.05 ml of emulsion are diluted in 7 ml of deionized water and the degree of turbidity subjectively assessed and documented by photo. This was done even after adding 0.1 ml of 10% citric acid to 7 ml of dilute emulsion solution.

General description of the method according to the invention

Protein and polysaccharide and optionally a polyol are dissolved in the amounts indicated in Tables 1 and 2 above using a stirrer separately at 50 ° C and 70 ° C in water, and then mixed (aqueous phase), wherein the aqueous phase preferably by mixing a solution containing the protein into a solution containing the polysaccharide; see also 1 , At the Use of neutral amylopectin instead of charged pectin or CMC, this is preferably used in a concentration of about 2.15% (proportion in the emulsion) and heated to 90 ° C until a bright highly viscous solution by solubility preliminary tests was determined in which Polysaccharidanteilen the aqueous phases still have suitable flow properties for the preparation of the solutions, ie are still flowable. The protein used is preferably whey protein isolate (MPI) (DSE 5669, Fonterra GmbH, Germany) and polysaccharide highly esterified pectin (P-HV) (Classic AS 501, VE 57%, Herbstreith & Fox GmbH, Germany). Before use, it may be advisable to filter the protein solution sterile, for example by means of a 0.2 micron ceramic membrane at 4 MPa.

The oil or fat component and possibly a flavoring oil component are heated to about 50 ° C or until all the fat has melted at 60 ° C (oil phase). Sunflower oil or rapeseed oil and optionally as a flavoring oil component herbal or pulp oil is preferred as the oil component. Preferably, the polysaccharide solution is pasteurized by heating to 95 ° C (10 minutes) before use.

The oil phase is then poured into the aqueous phase z. B. by means of a stirrer at 1500 U / min and a temperature of below 60 ° C, preferably at 40-45 ° C in the aqueous phase and with a rotor-stator emulsifier (for example, CAT-X620, M. Zipperer GmbH, Staufen ) is post-emulsified at 20,500 rpm for about 1 minute so that a median particle size in the range of preferably x ₅₀ <10 μm, preferably <1.5 μm and particularly preferably <1.2 μm is achieved. If necessary, finely emulsify with a high pressure emulsifier such as EmulsiFlex C5 (20 to 50 MPa, AVESTIN, Canada) or other pressure homogenizer to achieve the desired particle size.

If PPS is to be used, for example, in high dilution, a particularly small particle size is advantageous (preferably <1 μm). When added to a high-viscosity food base also satisfies an average particle size of about 5 microns.

The requirement for the emulsifier results from the necessary particle size and from the viscosity of the emulsion. While particle size ranges with x _50.3 = 1.0 μm with low emulsion viscosity are readily realizable by means of conventional high-pressure emulsifiers from a pre-emulsion, this is only possible with high viscosity using special high-pressure emulsifiers or special process equipment (eg with a rotor-stator system suitable for this purpose) ) possible.

For example, with the MaxxD 200 (FrymaKoruma) vacuum processing system, which is based on the principle of toothed ring gear (ring gear rotor and stator), a highly viscous emulsion PPS 20 CMS can be selected by selecting the appropriate ring gear tools with a particle size of x ₅₀ 1,2-2,5 μm are produced. This particle size is sufficient if the emulsion is used to higher viscosity products, especially with the aim of consistency control.

When using a high-pressure homogenizer such as EmulsiFlex C5, a particle size of x _{50 is reached} between 1.1 to 1.3 μm. For this, however, the preparation of a pre-emulsion is necessary (Zahnkranzdispergiergerät or stirrer with high energy input). Such emulsions, which were used for aromatization in high dilution, additionally had a high Aufrahmstabilität, since the oil was added to a denier to increase the density.

The pH of the resulting emulsions with polysaccharides and proteins which have a neutral pH is in the range around pH 7.0. However, if an acidic pH polysaccharide is used (eg, high ester pectin), the pH may be about pH 4.4 to 4.8 upon receipt of the emulsion. The neutral and also the acidic pH range emulsion can be further lowered in pH for example by adding a 10% acid such as citric acid. Preferably, however, the addition of acid is omitted. In the following examples, PPS is used, in whose production is dispensed with an acid addition.

Use of the emulsion PPS in the manufacture of various products

For a representative selection of products, see Examples 3ff, the relevant product data and information were systematically collected, the product as such sensory characterized, and then again after addition of x% (wt) PPS20, unless otherwise specified. This x varies depending on the product area. The PPS type, ie, for example, PPS-CMC or PPS-PE is shown in Tables 1 and 2 with their concrete composition, unless otherwise indicated. The selected% values are mean values which may differ in individual cases. PPS with x% solids was reported as Added component or mixing component for mixed products, with no particular order was observed during mixing. Possibly. followed by an intensive mixing of the end product with PPS with the inclusion of a suitable rotor-stator system to achieve a uniform particle distribution.

Unless otherwise stated, 10%, 20% and 30% PPS20 were incorporated as an adjunct or blending component of the subsequent products to determine the amount or concentration of PPS sufficient for the consistency of a selected food. The products were evaluated and tasted for water separation and, in the case of food, for mouthfeel before and after addition of PPS20 by at least three persons.

Detection of PPS and PPS in mixed products

Basically, PPS consists essentially of a protein, a polar polysaccharide and an oil or fat, and is characterized u. a. (b) there is no protein-polysaccharide incompatibility, (c) no insoluble protein-polysaccharide complexes with low water-binding are formed, and (d) the oil drops in the protein Polysaccharide phase remain well distributed. One detection method for PPS may be to dilute a neutral emulsion, or to lower it undiluted, or to dilute an acidic emulsion, and to perform a zeta potential measurement. In the case of PPS, acid addition does not cause spontaneous flocculation. If an acidic stable emulsion is diluted, it can be checked by microscopy whether a single drop distribution is present which is characteristic of PPS. Furthermore, PPS may contain proteins that usually precipitate upon lowering of pH (eg casein, vegetable protein). PPS containing whey protein remains relatively phase stable even after heating (above 70 ° C) in the acidic pH range, if more neutral hydrocolloids are included, which contribute to the viscosity increase and emulsion stabilization. Here it is therefore necessary to perform such a stability test after dilution of PPS.

In the case of PPSs obtainable by the methods of preparation of variants B and C, see 1 That is, in which prior to emulsification, the oil phase is enriched with a polysaccharide (preferably unstandardized pectin), a portion of the polysaccharide remains in the oil phase and contributes to the higher density of the oil phase. Accordingly, the oil phase of PPS, after dilution of PPS and separation of the oil phase by centrifugation (optionally with addition of proteases or SDS), has an increased density (for example> 0.92 g / cm ³ ) over an oil phase of a conventional one Emulsion or from PPS obtainable according to variant A to the polysaccharides in the oil phase can be analyzed after their isolation by means of chromatographic or spectroscopic methods.

Products prepared with PPSs of variants B and C may also have a high oil and polysaccharide, in particular pectin content. Pectin levels above 2-3% in the aqueous food phase are difficult to achieve in products with high dry matter through the addition of an aqueous solution. A higher pectin content is therefore facilitated by the use of PPS, in particular variants B and C.

Example 1: Example for Providing the Emulsion PPS According to Variant A.

Preparation of the emulsion

Whey and lupine protein as well as the polysaccharides were dissolved separately by means of stirrer RW 16 using a star-shaped stirrer, after which the individual protein and polysaccharide solutions were mixed in different proportions (variation of the protein and polysaccharide concentrations used and variation of the protein-polysaccharide proportions). Whey and lupine protein as well as alginate and carrageenan were dissolved at 50 ° C with stirring, the dispersed amylopectin was heated to 90 ° C until a bright highly viscous solution. It was determined by preliminary solubility tests at which polysaccharide proportions the aqueous phases still have suitable flow properties, ie. H. are still flowable.

As in 2A was illustrated, was dispersed in 95 ml of protein polysaccharide solution rapeseed oil using a star stirrer (agitator RW 16 basic, IKA laboratory technology, 1500 rev / min) (slow addition by means of 5 ml pipette), post-emulsified for 30 seconds and then by means of rotor Stator dispersing rod CAT X 620 (M.Zipperer GmbH, Staufen) post-emulsified at 24,000 rpm for 15 s. This pre-emulsion was prepared using the laboratory pressure homogenizer (HH 20 with ball valve, DE 195 30 247 A1 ) is emulsified at 8 MPa. Sample preparation was carried out under germ-reduced conditions. All containers and equipment were additionally treated with the alcoholic disinfectant "Softasept N" (B. Braun Melsungen). It was Deionized water used to prepare the solutions. Accordingly, PPS20 became as in 2 B illustrated produced.

Determination of freeze-thaw stability

The higher-viscosity stable emulsions were filled into PE bags and stored at -17 ° C for at least 24 hours and then stored at + 20 ° C for 1 hr. In addition, the stable low-viscosity emulsions (stable for at least 24 hours) were filled in 5 ml cryo-tubes and stored at -17 ° C for at least 24 hours and then stored at + 20 ° C for 1 hr. The appearance of the emulsion was evaluated (degree of preservation of the emulsion). Demixed emulsions (no smooth appearance, water repellency) were classified as non-freeze-thaw stable. Oil spilling ("oiling out" of the emulsions) was not observed in these studies. The emulsions according to those in Tables 1 and 2 and 2 The compositions indicated were freeze-thaw stable.

Phase stability of the emulsion

The emulsions were filled in 10 ml centrifuge tubes and stored at + 16 ° C. During storage, phase stability (eg segregation, water turnover) was observed. An oil sales was not found in these studies. The emulsions according to those in Tables 1 and 2 and 2 The compositions indicated were phase stable. Phase stability was also achieved in emulsions with the polysaccharide Na alginate in the absence of Ca ions (use of 1.5% by weight alginate and 1.5% by weight whey protein). Furthermore, a phase stability in the exchange of whey protein against pea, soybean and lupine protein is given (in combination with Na-CMC and highly esterified pectin). However, when the polar polysaccharide is replaced with neutral amylopectin, no additional bodying effect is observed. The vegetable protein emulsions in combination with amylopectin are not stable on acid addition. A somewhat better stability against the emulsions with amylopectin is observed in the combination of the sulfate group-containing lambda carrageenan with whey or vegetable protein, but the stability is lower than that of combinations of charged carboxyl group-containing polysaccharides with proteins in the emulsion production.

Example 2 Preparation of an Emulsion PPS According to Variant B

In one embodiment, the emulsion is preferably prepared according to variant B according to the scheme in 1 prepared by mixing the oil phase with the polysaccharide with stirring, and then dispersed in an aqueous phase containing the protein by means of Hochdruckemulgiergerät, for example, as described in the German patent application DE 10 2007 057 258.3 "Oil-in-water emulsion for organic foods and their preparation and use", filed on Nov. 27, 2007, the disclosure of which, in particular the examples, are incorporated by reference into the specification of the present application.

By way of illustration, here is essentially 2 of the example DE 10 2007 057 258.3 for the preparation of an emulsion of the oil-in-water type (O / W, 20/80) with a thyme-oil concentrate-pectin mixture and production of a bio-beverage.

It is with 200 parts by weight of thyme oil concentrate (density 0.921 g / cm ³ , EG oil mill & natural products GmbH / Kroppenstedt, prepared according to DE 102 01 638 C2 from gently dried organic thyme, Dr. med. Jungharms GmbH / Groß Schierstedt, and peeled organic sunflower seeds, agaSaat / Neukirchen-Vluyn) and 800 parts by weight of protein solution, an oil-in-water emulsion (20/80) prepared, wherein in the oil 100 parts by weight highly esterified Pectin (Classic AS 501, VE 57%, Herbstreith & Fox / Neuenbürg) using a stirrer with dispersing ring at 1300 rev / min stirred and dispersed for about 15 min. When dispersed, the oil obtains a cloudy, high-viscosity consistency (density ~ 1.020 g / cm ³ ). To prepare the aqueous phase of the emulsion, 20 parts by weight of organic whey protein (Bio-P50, ~ 60% protein content, BMI / Landshut) are dissolved in 780 parts by weight of water and used to prepare the oil-in-water emulsion ( 20/80). In 800 parts by weight of this aqueous phase, 200 parts by weight of thyme-oil concentrate-pectin mixture using a rotor-stator dispersing device (CAT-X620, M. Zipperer GmbH / Staufen) incorporated at 20,500 rev / min and 1 nachemulgiert min. Thereafter, the fine dispersion of the emulsion by means of high-pressure emulsifier EmulsiFlex C5 (AVESTIN / Canada) is carried out at 50 MPa. The mean droplet size d _{3.2 of} the oil drops in the emulsion is 0.91 μm.

Instead of apple pectin with 57% VE, also finely powdered citrus pectin CM 201 (VE 68-76%) and / or instead of thyme oil concentrate from a biological peppermint herb after DE 102 01 638 C2 prepared peppermint herb oil concentrate can be used. In another example, instead of herbal oil concentrate organic sea buckthorn pulp oil Sanddorn GbR, KbA Germany) is used for flavoring and after mixing with highly esterified Citruspektin CM 201 at 20 ° C, an O / W emulsion 20/80 prepared. Increasing the oil phase volume from 20/80 to 40/60 in the emulsion is also possible.

Example 3. Enrichment of skimmed milk with vegetable oil

The aim is to produce a full-bodied milk from skimmed milk, which is enriched with vegetable oil. Skimmed milk with 0.1% fat was used. As a comparison milk served with 3.8% fat content. While the skimmed milk without PPS additive tastes bland, thin and flat and has no body and a watery mouthfeel, the addition of 5% by weight of PPS20-CM leads to a distinctly creamy and creamy mouthfeel. When the additive is further increased to 7.5% by weight of PPS20-CM, the mouthfeel of the fortified skim milk (about 1.1% by weight of vegetable oil) is comparable to that of whole milk with 3.8% fat in terms of bulk.

Example 4: Milk with an increased proportion of polyunsaturated fatty acids

The aim is to produce a sensory-responsive milk-skimmed milk that has additional benefits such as prebiotic properties and an increased level of polyunsaturated fatty acids.

4.1 Enrichment with olive oil with the addition of PPS20-CM

It has been tested whether additional fortification of skimmed milk with olive oil is possible with the simultaneous presence of PPS. To 86 parts by weight of skimmed milk (0.1% fat) was added 4.5 parts by weight of PPS 20-CM and 9.5 parts by weight of olive oil (corresponds to 0.7% by weight of sunflower oil of PPS20 and 10 Wt .-% olive oil in the milk). In comparison to whole milk (3.8% fat content), the homogenized skimmed milk was slightly creamy and full-bodied in flavor, creamy, slightly nutty and low in vegetable oil. The mouthfeel was completely round and full-bodied, creamy and not too viscous. The disadvantage of such milk is the fat content of about 10.8%, therefore, further investigations were carried out using different PPS contents while reducing the oil addition.

4.2 Direct enrichment of milk with omega-3 fatty acids

Due to the positive result of Example 3 skim milk (0.1% fat content) with 5 wt .-% PPS20-CM were determined as the basis for further studies on the production of milk with health added value for further investigations.

4.3 Enrichment of skimmed milk with PPS20, omega-3 fatty acid and inulin

a) Omega-3 fatty acid in powder form (CPF n-3 concentrate) was available for these tests. This preparation had an unpleasant, tangy taste. It was investigated whether the combined addition of CPF n-3 concentrate with PPS20 contributes to the masking of the tangy taste. To 94.80 parts by weight of skimmed milk, 4.73 parts by weight of PPS20-CM and 0.47 parts by weight of CPF n-3 concentrate were added and mixed. The milk product was creamy and full-bodied in the mouthfeel, but still slightly low in taste. When the level of skimmed milk is reduced by 0.56% parts and replaced by 0.56 parts by weight of inulin, the consistency of the milk remains unchanged.

It was therefore the task to mask the low-puff taste by additional flavoring (see 4.4).

4.4 Taste of milk with PPS20 enriched with omega-3 fatty acid

For flavoring vanilla flavor in the form of butter vanilla flavor liquid (BVA) was used in combination with sucrose.

The skim milk enriched with PPS20 and omega-3 fatty acid under 4.3 was able to be improved in taste by using 2% by weight of BVA and 3% by weight of sucrose, in addition to the good and full-bodied taste the tepid note was no longer felt. The mouthfeel corresponds to that of whole milk.

Example 5: Consistency improvement of yogurt with PPS

The yogurt with 1.5% fat content 10, 20 or 30 wt .-% PPS20-CM were mixed (hand mixer). The sensory evaluation showed that compared with the O-sample the addition of PPS eliminates the water permeability of the non-smooth and somewhat flaky yoghurt and from 10 wt .-% PPS addition of the yoghurt significantly creamy. After sensory evaluation for consistency and taste, the optimum for the PPS addition is between 10 and 15% by weight.

Example 6: Refinement of mayonnaise with PPS

According to Example 1 Variant A, PPS20-PE is produced using whey protein and highly esterified pectin. As the oil phase, basil oil concentrate is used. 100 parts by weight of delicatessen mayonnaise (80% fat content) are mixed with 5 parts by weight of PPS20-PE. The delicatessen mayonnaise is creamier, has a pleasant herbal taste and is ideal for flavoring salads. Due to its creamy quality and better lubricity, this is also well suited as tubeware. By replacing the herbal oil concentrate with other herbal oil concentrates (thyme, rosemary, tarragon, wild garlic, cumin, etc.), the flavors of the mayonnaise can be varied widely and adjusted in intensity via the PPS content without adversely affecting the consistency.

Example 7: Consistency of remoulade

By adding 15 parts by weight of PPS20-CM to mixtures of 160 parts by weight of Delikatess mayonnaise, 75 parts by weight of fresh chopped herbs and 100 parts by weight of whole milk, a mild remoulade can be prepared, which is pleasantly creamy and soft Mouthfeel. Without the addition of PPS, the remoulade does not have the pleasantly creamy consistency. Such a remoulade can be adjusted well in the consistency in terms of flow behavior and adhesion, if instead of the 15 parts by weight PPS20-CM, a PPS20-PE is used, the preparation of which is carried out according to variant B or C and in which the pectin (highly esterified pectin) in the emulsion is 3% by weight (see Tab. 1).

Example 8: cooked sausage

The production of meat products such as boiled sausage or minced meat in per se known, see, for example, the German patents DE 199 38 434 A1 and DE 10 2006 026 514 A1 , the disclosure of which is hereby incorporated by reference into the present specification. To make boiled sausage, for example, 10 kg of beef and 5 kg of pork bacon are used. The meat is diced, salted with the usual amount of pickling salt and stored overnight in the refrigerator. The following day, it is pulled through the 2-mm disc and, after adding frozen PPS-20-CM (pre-shredded), chopped to the desired fineness. Then the previously finely transmitted bacon and the spice are added and the mixture is nachkkutted to the required fineness. The amount of PPS is 250 g per 1 kg meat mass. The sausage thus obtained is characterized by a fat reduction and shows a pleasant mouthfeel after frying.

Example 9: Dough and bakery products (pizza dough, containing 7.5% by weight of PPS)

300 g of flour, 20 g of yeast, 1/8 liter of warm water, half a teaspoon of salt and two tablespoons of olive oil are processed into a dough with 7.5% by weight of PPS20-PE or PPS20-CM. After the dough has risen, it is topped with tomato pieces and baked in the oven at the usual temperature. The pizza base is loose and pleasant in the taste.

Example 10: Improvement of the Sensory Properties of Coffee-Milk Mixed Drinks

There are a very large number of such mixed drinks, the variability is mainly in the proportion and type of coffee as well as the additionally used formulation components. Likewise, other mixtures of dairy products and aroma-imparting components can be realized in the same direction.

Cappucino, for example, contains a high proportion (about 90%) of low-fat milk, coffee extract, possibly cocoa, sugar and thickening agents (eg carrageenan). An addition of 5-8% PPS20-PE or PPS20-CM results in a round, harmonious taste and a distinctly fuller, creamier mouthfeel, which significantly improves the sensory quality of the cappuccino.

Example 11: Improvement of structure and texture of ice cream

Starting materials for ice cream products are milk, milk fat, fruit, fruit preparations, other flavor components (eg coffee, cocoa), sugar and additives to achieve certain effects in the final product. Depending on the ingredients are varieties such. As ice cream, ice cream, fruit ice cream, simple ice, art ice cream (water ice) realized. Critical to ice is the crystal structure, which arises during the freezing process and during freezing storage decisively influenced by storage temperature and especially the temperature fluctuation and is usually adversely affected. The result is a gritty-grained structure that is irreversible and worsens texture and mouthfeel. This impression can be significantly reduced by the addition of PPS, for example, PPS20-PE or PPS20-CM already with a few% and even prevented.

• – Reduzierung Fett- und Energiegehalt
• – Reduzierung und völliger Ersatz von Zusatzstoffen
• – Herstellung von Lactose freiem Eis
• – Realisierung von völlig neuen Produkten und Rezepturen

In addition to this more general finding, there are a number of sensible uses of PPS in the ice cream field. Examples are above all:

• - Reduction of fat and energy content
• - Reduction and total replacement of additives
• - Production of lactose free ice
• - Realization of completely new products and recipes

Example 12: Drying of PPS

Convenience also plays an important role in the production of dry products. This begins with the use of raw materials and compounds as intermediates for then liquid or pasty end products and ends in complete products that are only available in z. B. water or milk are dissolved. Drying methods are all based on the more or less gentle removal of water. So there are also for the PPS drying process in question, from drum drying on the widely applicable spray drying to more expensive freeze-drying.

In drum drying, PPS flakes are formed, which after rewetting have the same chemical-physical properties as non-dried PPS.

For spray drying, PPS with a TS content of more than 40% should be used. Spray drying results in PPS beads which do not satisfy instant requirements in solubility but also have all the relevant properties fresh after water uptake such as PPS.

Freeze-drying enables a PPS dry product that meets all requirements. However, since the flavor plays no role in PPS and freeze-drying is the most expensive drying variant, one will try to achieve instantaneous properties by other means.

Example 13: Preparation of dry PPS and dry products with PPS with instant properties

Instante properties require a reconstitution capability that enables re-dissolution without significant mechanical support. A well-combinable with drying process method is the agglomeration, in which from individual dry particles, eg. As beads, particle clusters arise in which physical forces rapid water absorption and thus dissolution of the dry material such. B. without stirring effect. So z. As spray drying and subsequent agglomeration Instanteigenschaften convey what is desirable in the case of liquids from the consumer.

• – Herstellung einer Kaffee-Milch-Kombination
• – Vorkonzentrierung auf einen bestimmten TS-Gehalt (abhängig von der Produktviskosität)
• – Sprühtrocknung
• – Agglomerisationsschritt
• – damit Realisierung von Instanteigenschaften
• – Verpacken in Sauerstoff geschützter Atmosphäre
• – Wasserzusatz und Auflösen des Produktes, das dann einem frisch hergestellten bzw. zubereiteten Produkt entspricht

One example would be the preparation of a dried PPS based milk mix to also provide the sensory benefits of using PPS in such a product. A milk mix, e.g. As a coffee-milk mixed drink according to Example 10, can be prepared in this way as follows:

• - Making a coffee-milk combination
• - preconcentration to a certain TS content (depending on the product viscosity)
• - Spray drying
• - agglomeration step
• - thus realization of instant properties
• - Packaging in oxygen-protected atmosphere
• - Adding water and dissolving the product, which then corresponds to a freshly prepared or prepared product

Example 14: Preparation of a creamy emulsion with carvacrol

PPS20-PE, produced using herbal oil concentrate Oregano, spreads well over the skin and leaves no oily film. The emulsion with antibiotic action absorbs quickly into the skin and is well suited for envelopes. It can also be easily diluted in hot or cold drinks and does not show oil.

Example 15: Preparation of a skin cream

PPS34-PE with 30% oil content is composed of 15% natural argan oil and 15% herbal concentrate camomile and 2.5% dexpanthenol. The viscous cream is easy to rub and absorbs quickly.

Example 16: Improvement of a skin cream

In a commercial hand care cream 10% PPS20-CM are mixed, containing 15% herbal oil concentrate chamomile. The resulting cream is smoother in its consistency and absorbs faster into the skin.

Example 17: Environmentally friendly adhesive

PPS20-PE with 2 or 4% PE is easy to apply to hardboard, metal, glass, PET material or fabric and spreads out and quickly absorbs into cardboard, paper, porous wood and fabric. After drying of PPS (shortened on heat supply), the coated and pressurized areas are firmly connected. Overhanging PPS makes a bright movie. PPS glue can also be prepared with fragrance components in the oil phase (for example herbal oil concentrate lavender).

PPS adhesive is ideally suited for the bonding of materials in which the bonding is not durable and easy to be separated with little effort and without damage, for example by moistening or immersion in water or by mechanical action. The advantage of PPS is that it does not use organic solvents that are natural raw materials, that are mechanically very strong, that can be easily separated by wetting, and that the bonded materials can be reused for other purposes without visible splices.

The components of PPS adhesive are environmentally friendly, the adhesive properties, the consistency and the adhesion properties on the materials can be well adjusted by the proportions of biopolymers and dispersed oil. By using linseed oil as a disperse phase, a subsequent increase in the stability of the bond by gumming can be achieved.

Example 18: Decorative paint and color carrier

PPS20-PE with 4% HV pectin is enriched with 1% Brilliant Blue powder (E133). Due to its good adhesion to hydrophilic and hydrophobic surfaces (wood, cardboard, metals, plastics), this intensely blue-colored PPS can be used universally as a decorative ink. This color is easily removable with aqueous solutions.

If PPS with an increased proportion of dyestuff powder is dried on strips (cardboard, plastic) or rods (wood, plastic, metal), they can be applied by dyeing into an aqueous solution for the rapid preparation of dye solutions (eg with Easter eggs or fabric colors). The dried PPS color solution is very stable to mechanical effects and does not discolour in the dry state.

The abovementioned examples are also carried out with other PPS variants, for example with vegetable protein, and give similarly positive results.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• WO 03/003850 [0005]
• EP 340035 A2 [0005]
• DE 10101638 C2 [0018]
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• DE 102006019241 A1 [0040, 0040, 0040, 0040, 0040, 0041, 0045, 0046, 0050, 0050, 0058]
• DE 102006058506 A1 [0040, 0040, 0040, 0050]
• DE 102007026090 A1 [0045, 0046, 0046, 0048, 0050, 0050]
• DE 102007057258 [0048, 0104, 0105]
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Claims (36)

Process for the preparation of a phase-stable oil-in-water (O / W) emulsion having a dry matter content between 5 and 60% by weight, containing, based on the total weight of the emulsion, the following components: (i) 0.2-10.0 wt .-% protein; (ii) 0.3-10.0% by weight polar polysaccharide; (iii) 0.1-60.0% by weight of a fat / oil component; (iv) 0-30.0 weight percent polyol; wherein a substantially consisting of the fat / oil component (iii) phase (oil phase), which is optionally mixed with the polysaccharide (ii) or a part thereof, is dispersed in an aqueous phase containing the protein (i) and optionally the polysaccharide (ii) or a part thereof, and subsequently the emulsion is finely emulsified, wherein in the resulting emulsion the particle size of the dispersed oil or fat drops in the distribution maximum is x _50.3 ≤ 10 μm (volume-median median). The method of claim 1, wherein (A) a substantially consisting of the fat / oil component phase (oil phase) is dispersed in an aqueous phase containing the protein and polysaccharide; or (B) the oil phase is mixed with the polysaccharide, and then dispersed in an aqueous phase containing the protein. The method of claim 1 or 2, wherein the aqueous phase in (a) is prepared by mixing a solution containing the protein into a solution containing the polysaccharide. Method according to one of claims 1 to 3, wherein the aqueous phase contains an oligosaccharide and / or polyol. A method according to any one of claims 1 to 4, wherein the emulsion is substantially free of additional weight, oligosaccharides, polyols, emulsifiers and / or dispersing agents. A method according to any one of claims 1 to 5, wherein the emulsion is substantially free of flavorings, dyes, preservatives, acids and / or other excipients. A method according to any one of claims 1 to 6, wherein the protein comprises whey protein isolate, milk protein concentrate, Na caseinate or skimmed milk powder. A method according to any one of claims 1 to 6, wherein the protein is a vegetable protein. The method of claim 8, wherein the vegetable protein comprises pea protein, soy protein, lupine protein or potato protein. A method according to any one of claims 1 to 9, wherein the polysaccharide comprises Na carboxymethylcellulose (CMC) or pectin (PE). The method of claim 10, wherein PE comprises highly esterified or amidated low methylester pectin. A method according to any one of claims 1 to 11, wherein the ratio of protein to polysaccharide is 4: 1 to 1: 4. The method of any one of claims 1 to 12, wherein the fat / oil component is selected from the group consisting of vegetable oils, essential oils, liquid vegetable fats, animal fats, mineral oils and MCT oils. A method according to any one of claims 1 to 13, wherein the emulsion consists essentially of components (i) to (iii). A process according to any one of claims 1 to 14, wherein the emulsion comprises substantially 0.75-5.0% by weight protein, 0.5-2.5% by weight polysaccharide and 5.0-50.0% by weight. Contains% fat / oil component. The method of claim 15, wherein the emulsion has substantially one of the following compositions: PPS typing Composition (% by weight) 7 20 34 51 protein 1 2 2 3 Polysaccharide PE (Na-CMC) 1 3 2 3 (2) Fat / oil components 5 15 30 45 water 93 80 66 49 A process according to any one of claims 1 to 16, wherein the dry matter (TS) of the emulsion is between 7.0% and 55.0% by weight. The method of claim 17, wherein the emulsion contains more than 1.5% by weight of protein and / or more than 1.0% by weight of polysaccharide, and the total dry matter (TS) is about 20% by weight or greater. Method according to one of claims 1 to 18, wherein the particle size is x _50.3 <1.5 microns. Method according to one of claims 1 to 19, wherein after step (b) in a further step, the pH is lowered. A method according to any one of claims 1 to 20, further comprising a step of concentrating and / or drying the emulsion. The method of claim 21, wherein the drying process is drum drying. The method of claim 21, wherein the emulsion is freeze-dried. Composition obtainable by the process according to one of the preceding claims. A composition according to claim 24, wherein the composition is a flowable, thick viscous, thick creamy liquid, creamy pasty or thick creamy pasty mass. A composition according to claim 24 or 25, which is a dried solid. A composition according to claim 26 wherein the water content is below 10% by weight. A formulation containing the composition of any one of claims 24 to 27, wherein the formulation is selected from the group consisting of food products, health care products, drug products, agricultural products, and industrial products. The formulation of claim 28, wherein the formulation is a food product. A formulation according to claim 29, wherein a fatty ingredient normally present in the food product is wholly or partially replaced by the composition of any one of claims 24 to 27. A formulation according to any one of claims 28 to 30, wherein the formulation is a food product, and wherein the food product is selected from the group consisting of sour cream, yoghurt, ice cream, cheese, cream cheese, baking mix, pastry dough mix, salad dressing, meat, margarine, powdered shortening, and the like Baking mix, ready-made gravy and confectionery. The formulation of claim 28, wherein the formulation is a healthcare product, and wherein the composition of any one of claims 24 to 27 is a carrier or vehicle for active ingredients in the healthcare product. The formulation of claim 32, wherein the product is selected from the group consisting of hand lotion, hand cream, body lotion, body cream, bath oil, shampoo, hair conditioner, sunscreen, lipstick, eye shadow, talcum powder, food powder, medicated oil, vitamin, antibiotic and antifungal. The formulation of claim 28, wherein the formulation is a drug product, and wherein the composition of any one of claims 24 to 27 is a carrier or vehicle for one or more drugs in the drug product. The formulation of claim 28, wherein the formulation is an industrial product selected from the group consisting of paint, ink, polish, paint remover, detergent, adhesive, lubricant, toner, drilling mud, sealant and building material. Use of a formulation according to any one of claims 24 to 27 as a thickener, suspending agent, binder, setting retarder or water retention agent.

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