WO2019048620A1 - Substitut de beurre - Google Patents

Substitut de beurre Download PDF

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Publication number
WO2019048620A1
WO2019048620A1 PCT/EP2018/074159 EP2018074159W WO2019048620A1 WO 2019048620 A1 WO2019048620 A1 WO 2019048620A1 EP 2018074159 W EP2018074159 W EP 2018074159W WO 2019048620 A1 WO2019048620 A1 WO 2019048620A1
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WO
WIPO (PCT)
Prior art keywords
fat
dairy
temperature
casein
solid
Prior art date
Application number
PCT/EP2018/074159
Other languages
English (en)
Inventor
Johannes Antonius Penders
Wilhelmus Hendricus Johannes Tap
Fransiscus Christophorus Gielens
Cornelis KORNET
Original Assignee
Frieslandcampina Nederland B.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Frieslandcampina Nederland B.V. filed Critical Frieslandcampina Nederland B.V.
Publication of WO2019048620A1 publication Critical patent/WO2019048620A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
    • A23D7/00—Edible oil or fat compositions containing an aqueous phase, e.g. margarines
    • A23D7/015—Reducing calorie content; Reducing fat content, e.g. "halvarines"
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
    • A23C13/00—Cream; Cream preparations; Making thereof
    • A23C13/12—Cream preparations
    • A23C13/14—Cream preparations containing milk products or non-fat milk components
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
    • A23C13/00—Cream; Cream preparations; Making thereof
    • A23C13/12—Cream preparations
    • A23C13/16—Cream preparations containing, or treated with, microorganisms, enzymes, or antibiotics; Sour cream
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
    • A23C15/00—Butter; Butter preparations; Making thereof
    • A23C15/12—Butter preparations
    • A23C15/123—Addition of microorganisms or cultured milk products; Addition of enzymes; Addition of starter cultures other than destillates
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
    • A23D7/00—Edible oil or fat compositions containing an aqueous phase, e.g. margarines
    • A23D7/001—Spread compositions
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
    • A23D7/00—Edible oil or fat compositions containing an aqueous phase, e.g. margarines
    • A23D7/005—Edible oil or fat compositions containing an aqueous phase, e.g. margarines characterised by ingredients other than fatty acid triglycerides
    • A23D7/0056—Spread compositions
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
    • A23D7/00—Edible oil or fat compositions containing an aqueous phase, e.g. margarines
    • A23D7/01—Other fatty acid esters, e.g. phosphatides
    • A23D7/013—Spread compositions
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
    • A23D7/00—Edible oil or fat compositions containing an aqueous phase, e.g. margarines
    • A23D7/02—Edible oil or fat compositions containing an aqueous phase, e.g. margarines characterised by the production or working-up
    • A23D7/04—Working-up
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
    • A23D7/00—Edible oil or fat compositions containing an aqueous phase, e.g. margarines
    • A23D7/02—Edible oil or fat compositions containing an aqueous phase, e.g. margarines characterised by the production or working-up
    • A23D7/04—Working-up
    • A23D7/05—Working-up characterised by essential cooling
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
    • A23C2260/00—Particular aspects or types of dairy products
    • A23C2260/10—Spreadable dairy products
    • A23C2260/102—Spreadable fermented dairy product; Dairy spreads prepared by fermentation or containing microorganisms; Cultured spreads; Dairy spreads containing fermented milk products
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
    • A23C2260/00—Particular aspects or types of dairy products
    • A23C2260/10—Spreadable dairy products
    • A23C2260/104—Water-continuous butterlike spreads; spreads from cream prepared without phase inversion

Definitions

  • the invention relates to a fat-containing dairy food composition, which composition is solid at 20°C, and in particular to a fat-containing dairy food composition that is spreadable below room temperature.
  • the invention also relates to a method to prepare this composition and to compositions obtainable by this method.
  • the invention relates to the use of these compositions as a spread for bread or as baking fat instead of butter.
  • Butter is a dairy product with many uses in the preparation of food products.
  • butter is a suspension of the water in oil type. Water droplets are dispersed in the butterfat phase, which makes up about 80 % of the product. The butterfat gives the product a distinct taste, but the high saturated fat content and the high calorific value of butter are also considered a health concern.
  • butter fat provides butter with good spreading properties at room temperature, e.g. on bread, it makes butter rather hard and difficult to spread at lower temperature, in particular at typical refrigerator temperature (about 4 °C).
  • transglutaminases transglutaminases
  • a homogenization treatment is carried out, typically at an elevated temperature after adding the further ingredients at an elevated temperature to the fat- containing phase.
  • a heat treatment of the total mixture to improve shelf life and consistency at pasteurization temperature or higher is typically carried out before homogenization.
  • the present invention relates to a method for preparing a food composition comprising dairy fat and casein which food composition is solid at 20°C, the method in essence comprising subjecting a suspension of the oil-in-water type comprising dairy fat and micellar casein to a treatment wherein casein is coagulated and fat is rebodied.
  • the present invention thus relates to a method for preparing a solid dairy food composition comprising dairy fat and casein, which food composition is (at 20 °C ) a solid suspension of the oil-in-water type, said method comprising the steps of:
  • step a) comprises subjecting a fluid starting suspension of the oil-in-water type comprising dairy fat and micellar casein, which starting suspension comprises dairy cream, to a fat solidification step at a temperature in the range of 0-20 °C until at least 80 wt. % of the fat is solid, thereby providing the fluid suspension of the oil-in-water type comprising solid dairy fat and micellar casein; and/or
  • step b)(i) comprises increasing the temperature of said fluid suspension of the oil-in- water type comprising solid dairy fat and micellar casein to more than 20 °C and step b)(ii) comprises chemically and/or enzymatically coagulating the micellar casein, thereby obtaining the fluid mixture comprising 1.5 to 10 wt.% solid fat based on total fat (preferably 2.5 to about 8 wt.% solid fat based on total fat), liquid fat and coagulated casein; and/or
  • step c) comprises reducing the temperature of the fluid mixture to a value in the range of 0-10 °C, preferably 1-5 °C, thereby obtaining the solid dairy food composition
  • the invention relates to a food composition, which composition is a suspension of the oil-in-water type, which composition is solid at 20°C and spreadable at 15 °C, preferably spreadable at 4 °C, which composition comprises
  • dairy protein 1-6 wt. %, preferably 1-4 wt. %, dairy protein, said dairy protein comprising coagulated casein;
  • the dairy protein, fat and water generally form 80-100 wt.% of the food composition (obtainable) according to the invention.
  • the total content of other ingredients is preferably 0- 10 wt.%.
  • the invention relates to use of a dairy food composition according to the invention or obtainable by a method according the invention as a spread for bread or another baked cereal product, as a baking fat, as a cooking fat, in a bakery cream application, e.g. as a topping or filling for a cake, cookie or in a confectionary application.
  • the invention further relates to a composite food product comprising a solid food composition according the invention and a further food component, such as a baked cereal product, chocolate etc.
  • a method according to the invention is inter alia advantageous it that it is generally carried out whilst maintaining the temperature below a temperature at which undesirable detrimental effects, such as substantial thermal protein denaturation, loss of aroma or other undesired olfactory changes due to thermal effects occur.
  • an optional thermal sanitizing heat treatment e.g.
  • the temperature in a method of the invention typically remains at a temperature at which at least part of the fat remains solid.
  • a suitable maximum temperature can vary dependent on the fat composition. In general, particular good results have been achieved with a method wherein the temperature at least starting from the temperature increase of the fluid suspension comprising solid fat at the beginning of step b) or the end of step a) is maintained below about 45 °C, in particular at a temperature in the range of 0-40 °C.
  • temperature ramping e.g. a linear temperature increase/decrease rate.
  • a method wherein temperature decrease respectively temperature increase are accomplished by placing a container (e.g. a sealed package suitable for selling the composition in)) in an environment (e.g. a storage room, such as a fridge or heating chamber or a liquid bath) having an essentially constant low temperature respectively having an essentially constant high temperature, and letting the container stand therein for a time sufficient to reach the effects of the invention.
  • a container e.g. a sealed package suitable for selling the composition in
  • an environment e.g. a storage room, such as a fridge or heating chamber or a liquid bath
  • a homogenization treatment is not required either.
  • a homogenization treatment may be applied to e.g. the suspension provided in step (a), to a starting material used to provide said suspension, usually at least after step b), and preferably after step a), preparation of the food composition is done without substantial homogenization treatment.
  • the suspension is usually treated without applying substantial shearing.
  • step (c), steps (b) and (c), or each of steps (a) to (c) are carried out in a packaging which packaging is sealed.
  • Preferred Examples of such packaging are typical cups or other containers wherein butter and other fat-based spreads are sold.
  • the volume of such containers is not critical, but in practice usually in the range of 1-5000 ml, in particular 5- 1000 ml, more in particular 10-500 ml.
  • Treatment in the packaging allows simplification over a conventional method requiring homogenization and/or stirring, but carrying out the method in a sealed package is also advantageous from a hygiene perspective.
  • the invention has in particular been found suitable to provide a food composition with both satisfactory firmness and spreadability (by hand using a knife), below or at room temperature, at a relatively low fat content (compared to butter).
  • a food composition according to the invention further has been found to have a taste component reminding of the taste of butter.
  • the present invention provides an excellent alternative for butter in several aspects.
  • the present invention was suitable to provide a solid food composition that did not show unacceptable syneresis, also after more than a week, in particular after two weeks or more of storage.
  • substantially(ly) or “essential(ly)” is generally used herein to indicate that it has the general character or function of that which is specified. When referring to a quantifiable feature, these terms are in particular used to indicate that it is for at least 75 %, more in particular at least 90 %, even more in particular at least 95 %, even more in particular at least 99 % of the maximum that feature.
  • a product is usually considered essentially free of a substance, if the content of the substance is 0- 0.5 wt.%, in particular 0 - 0.2 wt.%, more in particular 0 - 0.1 wt.%, based on total weight of the product in which it is present.
  • the presence in the starting material may be well below 0.5 wt. %, 0.2 wt.% or 0.1 wt. % and still have a significant effect on a property of the product.
  • the term "about” in relation to a value generally includes a range around that value as will be understood by the skilled person.
  • the range is from at least 15 % below to at least 15 % above the value, more in particular from 10 % below to 10 % above the value, more specifically from 5 % below to 5 % above the value.
  • percentages are usually weight percentages unless specified otherwise. Percentages are usually based on total weight, unless specified otherwise.
  • fatty acid' is generally used herein as a genus for free fatty acids and fatty acid residues bound to another organic moiety, in particular as part of an acylglyceride.
  • the term 'fat' is used herein for the lipid phase (fat phase) of a suspension or other composition (used) in accordance with the invention, as is common in the art.
  • the fat generally at least substantially consists of tiglycerides, typically for more than 90 wt.%, in particular for 95- 100 wt.%.
  • Other components that may be present include other lipid components that can be naturally found in natural fat phases, e.g. vegetable oils or milk fat, like fat-soluble vitamins (e.g. vitamin A, D or E).
  • Milk fat is the fat phase of milk.
  • Milk fat is a complex mixture of triglycerides and other lipid components. Milk fat typically consists for the largest part of triglycerides (e.g. about 98 %).
  • the triglycerides generally have a carbon number in the range of 26-54.
  • the carbon number distribution is bimodal, i.e. milk fat has fatty acids with a relatively high content of relatively small acyl groups (4-6 carbons), a relatively high content of relatively large acyl groups (at least 14 carbons) and a relatively low content of acyl groups of intermediate length (8-12 carbons).
  • milk fat In addition to triglycerides, milk fat typically contains several minor components, such as cholesterol, fat-soluble vitamins, free fatty acids, monoglycerides, diglycerides and various other organic components, such as lactones, ketones and aldehydes, contributing to the characteristic flavour or aroma of milk fat.
  • Milk fat isolated from milk
  • AMF anhydrous milk fat
  • the term 'dairy fat' is used as a genus for milk fat and parts of milk fat.
  • Such parts can be any milk fat fraction, combination of milk fat fractions or combination of a milk fat fraction and milk fat.
  • Parts of milk fat in particular include milk fat fractions that can be obtained by a milk fat fraction process.
  • Such processes are generally known in the art and include milk fat crystallisation (also known as dry fractionation) and supercritical fluid extraction, e.g. using supercritical CO2.
  • Milk proteins can be divided into three main groups: caseins, serum proteins, and
  • Whey proteins are used in the art for proteins that remain in the liquid phase after coagulation of casein from milk, e.g. in the preparation of cheese. Whey proteins comprise serum proteins.
  • 'solid' is used herein for matter, in particular a food composition, which essentially remains its shape when a unit of the matter, such as a cube with a size of 1 x 1 x 1 cm, put on a horizontal surface without further support from the sides or top of the matter, at least in air, at a pressure of 1 bar, at a temperature of 20 °. I.e. with the naked eye solid matter is not visibly fluid. Such matter may also be referred to as self- sustaining matter or dimension-stable matter.
  • a solid fat content at a specific temperature can be determined by subjecting the fat fraction of the composition to a solid fat content measurement using pulse NMR or DSC.
  • pulse NMR or DSC To this purpose standardized methodology is available, see WO2013/151423A1.
  • AOCS Cd 16b-93 revised in 2000 can be used.
  • Firmness can be determined penetrometrically, using a texture analyser.
  • the values for firmness as mentioned herein are as determined with a TA- XT2i (Stable Micro Systems, Godalming, England) texture analyser to which a wire cutter probe is attached with a load cell of 50 kg, setting the trigger force to 0.04 N and the test speed to 0.20 mm/s, setting the total penetration distance of the probe through the sample (a cube, having a thickness of 21 mm) at 18.0 mm, determining the force (N) required to press through the sample between 7 and 14 mm penetration; averaging the force required to press through the sample between 7 and 14 mm penetration is the firmness of the composition
  • a composition is considered spreadable if a skilled person can manually, using a knife, take a portion of a composition from the bulk of the composition and distribute the portion on the surface of a food product on which the product needs to be spread, typically bread, toast or another baked cereal product, without substantially disrupting the food product.
  • a skilled person will also be able to grade spreadability (e.g. on a 1-10 scale) taking into account how easy it is to spread a composition essentially evenly and the tendency for the composition to curl up from the surface on which it is applied.
  • rheology measurements For an indication of spreadability one may also make use of rheology measurements. By determining viscosity as a function of shear stress, as described in detail in the Examples, resistance against spreading can be determined.
  • the pH is defined as the apparent pH as measurable by placing a standard pH electrode in the substance (e.g. suspension or solid food composition) of which the pH is measured, at 20 °C, unless specified otherwise.
  • casein As is generally known in the art, casein, as naturally present in milk, is a supramolecular association of individual casein subunits: alpha-sl-, alpha-s2-, beta-, and kappa-casein. These fractions are organized within, a micellar structure according to a balance of interactions involving their hydrophobic and hydrophilic groups.
  • Micellar casein is colloidal, typically essentially spherical, typically having an average diameter of about 200 nm and an average molecular weight of about 108 Da (for casein in cow milk), see e.g. P. Walstra, J. T. M. Wouters, and T. J. Geurts, Dairy Science and Technology, vol. 4. 2006; D. S. Home and J. M.
  • 'Casemate' is a non-micellar protein derived from casein, obtainable by acid precipitation (coagulation) from a fluid containing solubilised casein (casein micelles) e.g. milk, and subsequent neutralization with a base.
  • coagulation acid precipitation
  • casein micelles solubilised casein
  • Coagulation of casein is a treatment that is generally known in the art per se. It is e.g. part of the production of cheese. The inventors found it can also be carried out in a suspension having a relatively high fat content, such as dairy cream.
  • coagulation is usually done by enzymatic coagulation or by addition of a chemical coagulating agent, such as an acid.
  • Enzymatic coagulation is generally done using a protease, in particular an aspartic endopeptidase (EC 3.4.23.4), more in particular a chymosin, preferably bovine chymosin.
  • a protease in particular an aspartic endopeptidase (EC 3.4.23.4), more in particular a chymosin, preferably bovine chymosin.
  • rennet is preferably used. Particularly good results have been achieved with a bovine rennet.
  • the skilled person will be able to apply a suitable pH, based on the enzyme used. Generally, the pH is in the range of about 4.0 to about 7.0.
  • the amount of protease the amount of rennet is usually at least 1 IMCU/1 fluid suspension (e.g. cream).
  • the amount is usually less than 1000 IMCU/1 suspension, preferably about 500 IMCU/1 fluid suspension or less, more preferably about 100 IMCU/1 or less.
  • protease in particular rennet
  • An amount of protease, in particular rennet, in the range of about 7.5 to about 75 IMCU/1 fluid suspension has been found particularly suitable to provide a solid food composition with a satisfactory firmness and spreadability, at about 15 °C or lower, that is particularly suitable as a substitute for butter, e.g. as a spread on bread or another baked cereal product, e.g. toast or cake.
  • Particularly good results have been achieved within a method wherein the protease (such as rennet) is added in an amount of about 30 to about 60 IMCU/1 fluid suspension.
  • Acid coagulation comprises adjusting the pH of the fluid wherein the micellar casein is present to a point at which it precipitates (i.e. around the isoelectric point), typically a pH in the range of 4.0-5.5, preferably of about 4.6.
  • an acid can also be used to adjust a flavour property.
  • An acidic food composition according to the invention in particular a composition having a pH of 4.0-6.0, preferably of about 4.6 has an increased firmness at 15 °C, compared to a comparable food composition having an about neutral pH.
  • an acidic composition is found to be unsatisfactory with respect to spreadability for a specific application, spreadability can be improved by increasing the pH up to about neutral pH, e.g. a pH of about 6.8.
  • the pH can be reduced after coagulation by adding an acid.
  • a salt of a divalent cation such as Mg or Ca cations, for instance calcium chloride or magnesium chloride is suitable to decrease the pH of a fluid suspension or mixture employed in a method according to the invention.
  • the pH can be increased after (acid) coagulation by adding a base.
  • Coagulation is generally carried out during said step b), i.e. at a relatively high temperature within the temperatures generally employed in a method according to the invention.
  • enzyme activity of (conventionally used) enzymes is higher at relatively high temperature.
  • the chemical coagulating agent or enzyme is usually added to the starting suspension prior to step b) or during step b), preferably at the beginning of step b), i.e. whilst the temperature is still increasing (thereby reducing the time needed to accomplish a desired coagulation degree). This is in particular preferred for enzymatic coagulation.
  • Chemical coagulation such as acid coagulation, may also be carried out at a relatively low temperature.
  • step b may be carried out before or after step b), yet before formation of the solid composition in step c).
  • a coagulation agent such as an agent reducing the pH
  • Rebodying also known as tempering of fat
  • Rebodying comprises subjecting a fluid suspension comprising fat to temperature fluctuations, such that the viscosity increases. This is generally caused by a partial coalescence of fat globules in the fluid. Rebodying can occur with or without stirring. No stirring is needed, if the fat content is so high that the fat globules are sufficiently close together to coalesce, (see e.g. K. Boode, C. Bisperink, and P.
  • rebodying of fat is a treatment for which each of the steps a) - c) are relevant; for coagulation of casein, in general at least step b) is used.
  • optimal conditions depend to some extent on desired properties of the solid food composition (such as desired olfactory properties,
  • a fluid suspension of the oil-in-water type comprising solid dairy fat and micellar casein is provided.
  • This suspension generally comprises 1-6 wt. % protein, of which generally 80-100 wt.% preferably essentially all protein is dairy protein.
  • Preferably 70-100 wt.% of the protein is casein more preferably at least 80 wt.%.
  • concentration of 4 wt.% case should be taken to avoid lump formation of the coagulating proteins, notably casein.
  • the concentration of protein is preferably 1-4 wt.%, more preferably 1-3.0 wt.%, based on total weight.
  • the fat content of the suspension that is provided in step a) is generally 20 wt.% or more, based on total weight of the suspension.
  • the fat content of the fluid suspension is usually 25 wt.% or more, preferably at least 30 wt.%, more preferably at least 35 wt.% , in particular at least 38 wt.%. based on the weight of the suspension.
  • a relatively high fat content generally results in a relatively high firmness of the obtained solid food composition.
  • the suspension provided in step a) usually has a fat of 70 wt.% or less, in particular of 60 wt.% or less, to avoid a
  • phase separation in the absence of non-dairy emulsifiers, preferably of about 55 wt.% or less thus providing a composition with reduced fat content compared to butter.
  • an insufficient stability of the oil-in-water suspension can be a problem, at least without addition of (non-dairy) emulsifiers.
  • the fat content of the suspension is 50 wt. % or less Particularly good results have been achieved with a suspension comprising 38-45 wt. % fat.
  • the fat in the provided suspension is dairy fat, preferably 80-100 wt.%, more preferably 90-100 wt.%. Particularly good results have been achieved with a suspension wherein the fat phase essentially consists of milk fat.
  • the fat is a blend of milk fat and another fat.
  • one or more triglycerides comprising an n3-polyunsatured fatty acid (e.g. alpha-linolenic acid (ALA), eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA)) and/or an n6- polyunsatured fatty acid may be included (e.g.
  • LA linoleic acid
  • a specific milk fat fraction can be present, e.g. a stearin fraction of milk fat.
  • Such fraction can advantageously be used to increase the solid fat content at relatively high temperature. This can e.g. be used to allow a relatively high temperature (such as of up to about 45 °C) for step b).
  • a relatively high temperature such as of up to about 45 °C
  • a stearin fraction of milk fat can be done to compensate for a reduction in solid fat content at a relatively high temperature, due to the addition of a fat with a low melting point or range, such as a triglyceride providing a polyunsaturated fatty acid.
  • Dairy cream or a fluid suspension at least substantially consisting of dairy cream is a particularly suitable fluid suspension to provide this fluid suspension.
  • Cream used in a method according to the invention is usually selected from the group of cow milk cream, caprine milk cream and sheep milk cream.
  • milk fat e.g. amorphous milk fat obtained from bovine, caprine or sheep milk, which can be suspended together with dairy protein, e.g. at least partially provide in the form of milk protein isolate.
  • Micellar Casein Isolate (MCI) can also provide all or part of the casein in a fluid suspension provided in step a).
  • Caprine cream or milk fat from caprine cream, or a fraction thereof can also be used to impart a more distinct buttery flavour.
  • a combination of fat from caprine or sheep milk and cow milk can also be used.
  • the fluid suspension provided in step a) comprises solid fat.
  • the fluid suspension is provided (e.g. purchased) as such.
  • a fluid suspension comprising dairy fat and micellar casein has a lower solid fat content prior to step b) than desired for a specific application, said suspension is first subjected to a fat solidification step, generally comprising a reduction of temperature until the intended solid fat content (usually at least about 80 wt.%) is reached.
  • a suitable temperature and duration can be determined empirically.
  • a fat solidification prior to step b) is carried out at a temperature in the range 0-20 °C, preferably at a temperature in the range of 0-10°C, in particular at a temperature of 2-6 °C. In particular good results have been achieved at a temperature of about 5 °C.
  • a preferred duration can be at least about 1 hour, at least about 5 hours, at least about 10 hours or more, e.g. up to 24 hours, up to 48 hours.
  • the provision of the fluid suspension in step a) can comprise a concentration step.
  • Concentration can be accomplished in a manner known per se, e.g. by vacuum evaporation, preferably at a temperature wherein all or at least most of the fat has melted, typically a temperature in the range of about 35 to about 60 °C, preferably about 40 to about 50 °C.
  • a fluid suspension comprising solid fat from a suspension that is essentially free of solid fat, by allowing a sufficient part thereof to solidify (crystallise).
  • the fluid suspension may have been subjected to a heat treatment such as pasteurisation.
  • a heat treatment such as pasteurisation.
  • a dairy cream - wherein at least 80 % of the fat is solidified may have a positive effect on reaching a desired viscosity increased in step c).
  • MFGM milk fat globule membrane
  • casein micelles can associate with the MFGM by disulphide bonding between ⁇ - casein and MFGM components, after heat treatment. This means that casein aggregates could interact with fat granules.
  • a highly packed system is created with two types of particles, fat granules and protein aggregates, which might also be able to interact to a certain extent.
  • step b) the temperature of the fluid suspension comprising solid fat provided in step a) is increased. Temperature and duration are chosen such that a part of the solid fat melts. It is important for rebodying that a part of the fat remains solid.
  • the solid fat provides solid nuclei (usually fat crystals) which in step c) grow (usually comprising fat crystallisation) to form larger particles, which contributes to the formation of the solid food composition.
  • the solid fat content is usually at least 1.0 wt. %, preferably at least 1.5 wt. %, more preferably at least 2.5 wt.%, based on total fat.
  • the solid fat content is 10 wt.% or less, preferably 8 wt.% or less, based on total fat.
  • step b) coagulation of casein takes place.
  • the temperature is usually increased in step b) to a value of at least about 30
  • °C This is desired to allow efficient melting of a sufficient part of the solid fat, at least within a reasonable time span and for efficient coagulation, especially in case of enzymatic coagulation.
  • a temperature in excess of 40 °C is generally not needed.
  • a higher maximum temperature may be employed in step b), typically of up to about 45 °C.
  • the fat phase has about the same end- melting point or a lower end- melting point than milk fat, one may in principle still expose the suspension during step b) to a temperature above 40 °C, provided the duration is sufficiently short to avoid melting of too much solid fat.
  • the temperature during step b) is in the range of 32-38 °C, in particular in the range of 34-36 °C, especially in an embodiment wherein the fat at least substantially consists of bovine milk fat.
  • a lower temperature may be employed, generally at a longer holding time at increased temperature, or a higher temperature at a shorter holding time at increased temperature.
  • the temperature during step b) is preferably in the range of 20-35 °C, more preferably in the range of 22-28 °C.
  • a lower temperature may be employed, generally at a longer holding time at increased temperature, or a higher temperature at a shorter holding time at increased temperature.
  • the skilled person will be able to determine a particularly suitable temperature and duration based on the information disclosed herein, common general knowledge and optionally a limit amount of routine testing.
  • a suitable duration of step b) can be determined routinely, based on common general knowledge and the information disclosed herein, taking into account the desired solid fat content at the end of step b).
  • the duration of step b) is usually at least about 0.5 hr, preferably at least 1.5 hrs, in particular at least 2.0 hours.
  • the duration in step b) is usually about 4 hrs. or less, preferably about 3 hrs or less, in particular about 2.5 hrs or less.
  • step b) is generally carried out without subjecting the suspension to substantial shearing (such as e.g. stirring).
  • step (a) the fluid suspension may be stirred or otherwise be subjected to shearing during step (b) to stimulate partial coalescence of the fat globules which, as explained above, causes the rebodying of the fat.
  • a total fat content of 20 wt.% or more should be sufficiently high to achieve rebodying of fat without any shearing in step b).
  • step b) is carried out in a (consumer) packaging, which is preferably sealed.
  • the resultant fluid mixture After a sufficient part of the solid fat has melted (usually at a point wherein the solid fat content is in the range of about 1 to about 10 wt.% based on total fat) the resultant fluid mixture is subjected to a fat solidification step.
  • the result fluid mixture comprises solid fat particles (nuclei) which are allowed to grow, due to solidification (such as crystallisation) of liquid fat on the solid fat particles. This is generally accomplished by reducing the temperature of the mixture (which is still a fluid suspension).
  • temperature reduction may be initiated before coagulation of the casein as long as a satisfactory casein coagulation has been achieved before the mixture becoming a solid, but as also can be concluded from the remainder of the disclosure, it is generally preferred that first a casein coagulation is carried out and thereafter the fat solidification step c) is proceeded with.
  • step b) The cooling from the relatively high temperature at the end of step b) to the lowest temperature reached in step c), can but does not need to be controlled. Good results have been achieved by placing the fluid mixture obtained in step b) in a refrigerated room.
  • step b) the time needed for the fluid mixture obtained in step b) to cool from the high temperature at the end of step b) to the lowest temperature reached in step c), has an effect on firmness/spreadability of the obtained solid food composition.
  • the average cooling rate to essentially reach the lowest temperature in step c) is usually about 3 °C/min or less, in particular about 1.0 °C /min or less, preferably 0.6 °C /min or less, more preferably 0.5 °C /min or less.
  • the lower limit is usually determined by an acceptable duration of step c), taking into account maintaining microbiological quality and production capacity.
  • the average cooling rate is usually chosen to be such that the cooling is effectuated within 48 hours, in particular within 24 hours, preferably within 12 hours, more preferably within 6 hours.
  • the average cooling rate usually is at least 0.01 °C/min, preferably at least 0.04 °C/min, more preferably at least 0.1 °C/min.
  • the average cooling rate may be determined as [(Temperature at the end of step b) - (Lowest temperature in step c)]/time needed to reduce temperature from Temperature at the end of step b) to Lowest temperature in step c).
  • a method according to the invention may further comprise the addition of one or more optional ingredients. These are usually added prior to solidification of the food composition in step c).
  • an aroma component may be added.
  • a fruit flavour, a chocolate flavour or a vanilla flavour may be added.
  • a sweetener may be includes, e.g. a sugar, a sugar alcohol or a high-intensity sweetener.
  • a vitamin or other component having nutritional value may be added (e.g. a mineral, antioxidant, prebiotic oligosaccharide). . Suitable amounts may be based on what is generally known in the art or the citations mentioned herein about additives for butter- substitutes.
  • the total concentration of components other than protein, fat and water of a composition, suspension or mixture (used) in accordance with the invention is 0- 20 wt.%, based on total weight, preferably 0-10 wt.%, in particular 0-5 wt.% .
  • dietary fibre such as inulin
  • a thickening agent e.g. starch or a dietary fibre with thickening properties may be employed if firmness of s specific composition is found to be unsatisfactory. Good results have been achieved with a food composition without added dietary fibre (other than prebiotic oligosaccharides naturally found in milk) or thickening agent.
  • a thickening agent e.g. starch or a dietary fibre with thickening properties
  • compositions that is essentially free of non-dairy prebiotics and thickening agents is preferred. Further, good results have been achieved with a food composition that is obtained without adding any emulsifiers to the fluid suspension from which it is made. In as far as emulsifiers are used, these are typically emulsifiers naturally present in milk. Thus, usually a food composition according to the invention is essentially free of non-dairy emulsifiers. Apart from having a function in the final product (the solid composition), an ingredient may be added as a processing aid.
  • a (salt of) a divalent cation preferably magnesium or calcium
  • the divalent cation may be added in any form suitable for use in food products. Preferably it is added as an inorganic salt. It was found that addition of such cation is useful to increase firmness. Particularly good results have been achieved with a chloride salt, such as calcium chloride. If present, the concentration usually is in the range of 0.1-100 mmol/1, preferably in the range of 1-90 mmol/1, in particular in the range of about 10 to about 40 mmol/1.
  • the divalent cation is added before step b) or during step b).
  • the present invention further relates to a diary food composition.
  • the food composition can e.g. be prepared by a method as described herein.
  • Preferred preferred contents generally correspond to those given for the fluid suspension provided in step a) or obtained as an intermediate mixture in step b) of a method according to the invention.
  • a dairy food according to the invention is solid at 20°C. At least if it is intended for use as a spread, e.g. on bread or toast, it is usually spreadable at 15 °C, and preferably at 4 °C.
  • the food composition according to the invention comprises 1-6 wt. %, preferably 1-4 wt. %, in particular 1-3 wt. % dairy protein.
  • casein is the major protein (>50 wt.% based on total protein) or only protein present.
  • the presence of protein, in particular coagulated casein, contributes to firmness.
  • the fat content is generally in the range of 20-70 wt.%. Usually 50-100 wt.%, preferably 90-100 wt.% of the fat is dairy fat, e.g. milk fat or a blend of milk fat and a specific milk fat fraction (e.g. a stearin fraction). Fat contributes to firmness of the composition. Accordingly the fat content preferably is 25-55 wt.%, in particular if the protein content is 4 wt.% or less. More preferably the fat content is 30-55 wt.%.
  • the water content is determined by the amount of total other ingredients. In addition to protein and fat, one or more other ingredients as described above may be present in the food composition.
  • the water content generally is in the range of 20-79 wt.%, preferably 40-60 wt. % water, more preferably 45-55 wt.% water.
  • the food product according to the invention comprises
  • the food composition should not have too high a firmness.
  • regular butter general has a firmness at 15 °C in the range of 0.4-1 N. This is rather high, especially if it is to be spread on a soft product, e.g. bread.
  • a solid food composition according to the present invention and least when it needs to be suitable for use as a spread, has a firmness of 0.4 N or less. If the product is intended for another application, a relatively high firmness, in particular of up to about 1 N may be acceptable or even desirable.
  • a too low firmness may be undesired e.g. because the composition may melt if exposed to a slightly higher temperature than ambient temperature (e.g.
  • the firmness of a composition according to the invention at 15 °C is 0.05 N and typically at least about 0.10 N. Further, it has been found that many consumers appreciate a composition with a moderately high firmness from a sensorial perspective (e.g. mouthfeel).
  • the solid food composition has a firmness at 15 °C in the range of 0.12-0.30 N.
  • Such product has good spreadability in combination with satisfactory firmness, e.g. for use in a spread application.
  • Such solid food composition may for instance be obtained using dairy cream as the sole or major source of protein and fat, in which case a particular strong olfactory resemblance with butter is experienced.
  • the firmness is 0.12-0.26 N.
  • good results in terms of spreadability and sensorial appreciation have been obtained with a composition having a firmness of 0.15-0.26 N, in particular 0.15-0.20, also at a temperature below 15 °C, e.g. at about 4 °C.
  • the pH of the solid food composition is usually about neutral (pH 7.0) or less. Usually, the pH is at least about 4.0. Preferably the pH is in the range of 4.5-6.8. A more acidic composition tends to be more firm, at the same protein and fat composition.
  • Example 1 A spreadable dairy product with a buttery taste was prepared as follows.
  • a dairy cream (bovine) was stored at 4 °C. To this cream rennet was added at a temperature of 4 °C. Thereafter, calcium chloride was added (also at 4 °C).
  • the resultant fluid suspension comprising micellar casein and solid milk fat thus provided (step a) was divided over a plurality of containers which were placed in a storage room having a temperature of 40 °C for 2-4 hrs (step b). Some of the containers were removed from the storage room after 2 hours, others after 4 hours. Of these removed containers, some were placed in a refrigerated room at 4 °C and others in a refrigerated room at -2 °C. They were allowed to stand there overnight (step c). The next day the resultant products were evaluated.
  • the containers kept in the storage room at 40 °C for 2 hours and subsequently subjected to cooling at 4 °C contained a solid food composition which was spreadable at a temperature of 4 °C and higher, at least up to about 20 °C.
  • the containers that had been kept at 40 °C for 4 hours and/or that were stored at -2 °C did not contain a composition with a spreadable texture. Instead the suspensions in those containers remained fluid.
  • Bovine Cream 38 - 45 wt% fat, about 2 wt.% protein, of which about 80 wt. % micellar casein) (FrieslandCampma, Rijkevoort, Netherlands), Caprine Cream ( ⁇ 40 % fat) (Rouveen Kaasspecialiteiten, Rouveen, Netherlands), MCI80 liquid and powder (FrieslandCampma, Lochem, Netherlands), Kalase rennet (CSK, Leeuwarden,
  • cream was first concentrated (e.g. to provide a fluid suspension having a fat content of more than 45 wt.%) was first transferred to a rotary evaporator and a pump was started to bring the system under vacuum (-0.95 bar). Simultaneously, the sample was warmed to and kept between 40— 50 °C. After concentrating the cream from 46 % to 60 % dry matter, the evaporator was stopped to prevent phase separation. The cream was transferred to the cooling chamber and stored overnight at 5 °C.
  • a fluid suspension comprising solid fat in an aqueous phase was provided in accordance with step a) of a method according to the invention.
  • the cream was stored for at least 12 hours at 5 °C in a cooling chamber to provide the fluid suspension with a solid fat content of at least about 80 wt.% (step a) and then taken out of the cooling chamber.
  • MCI MCI enriched cream was mixed with regular cream (that had been stored at 5 °C overnight) in different ratios before further treatment to obtain a solid food composition according to the invention.
  • the cream was weighed and inoculated with Kalase to provide 60 IMCU/1) cream, unless specified otherwise. If included to the experimental design, CaCl2 was added at this stage.
  • the suspension was stirred to distribute the rennet and any other components.
  • Each sample was produced in quadruplicate by distributing the suspension over four 125 mL cups (i.e. 500 mL for each process variable). Then the cups comprising the fluid suspension comprising solid fat were sealed with an ILPRA termosaldatrici (Induquip, Wapenveld, Netherlands) and transferred to a water bath. The samples were warmed for 150 minutes at 35 °C, unless specified otherwise (step b).
  • CLSM Leica TCS SP5, Leica Microsystems Ltd.
  • the samples were stained with Nile Red and Fast Green to visualize the fat and protein respectively.
  • An Argon laser excitation wavelength of 488 nm
  • a Helium-neon (HeNe) laser (633 nm) were used.
  • Nile Red was detected between 575 and 625 nm and Fast Green between 640— 740 nm.
  • the lOx, 20x and 63x objective lenses were utilized for different magnifications and the images obtained had a resolution of 1024 x 1024.
  • the temperature of the cream upon cooling was recorded in order to study the effect of cooling rate.
  • An Ecograph T RSG35 (Endress & Hauser, Naarden, Netherlands) was used in combination with 4 PT100 probes. The probes were placed in the middle of the samples and the temperatures were tracked over time.
  • Particle size distributions were measured with a Mastersizer 2000 (Malvern, Worcestershire, England), combined with a Hydro 2000MU wet dispersion unit, using laser diffraction.
  • the refractive index for cream was set to 1.462, the absorption to 0.01 and the dispersant was water (RI 1.33).
  • the Sauter mean diameter (D 3,2) was calculated by the Malvern Software.
  • An MCR 302 rheometer (Anton Paar, Graz, Austria) was used to determine the viscosity of the obtained food compositions as a function of shear rate.
  • An MCR 302 rheometer was used with a concentric setup to determine the viscosity. Prior to the actual measurement, the samples were allowed to reach the starting temperature by remaining 5 minutes in the concentric cylinder. The rheometer temperature ramp was set to 5— 50 °C with a rate of 0.5 °C / minute. The strain was set to 0.01 and the frequency 1.000 Hz. The machine software calculated the complex viscosity from the measured data.
  • the temperature of the rheometer was set to 15 °C and the food composition to be evaluated was spooned to a plate (TEK P/MCl-80).
  • the shear stress linear ramp was set to 0 - 750 Pa in 90 seconds. The viscosity as function of shear stress was calculated and graphically shown by the machine software. All samples were measured in duplicate.
  • Sample pretreatment A square mould was filled with sample by pressing it in the food composition. After taking out the mould from the sample, redundant food composition was removed with a putty knife to obtain a smooth surface in the square mould. The square moulds with sample were put in a box and transferred to a water bath (15 °C). They remained in the water bath for 2— 3 hours to ensure a temperature of 15 °C and by that exclude any effect of temperature on the firmness of the food composition.
  • the firmness of the composition was measured with a wire cutter probe attached to a ⁇ - ⁇ 2 ⁇ (Stable Micro Systems, Godalming, England) with a load cell of 50 kg.
  • the trigger force was set to 0.04 N and the test speed 0.20 mm/s.
  • the total penetration distance of the probe through the sample was 18.0 mm.
  • the force (N) required to press through the sample between 7 and 14 mm penetration was averaged and gave the firmness of the composition.
  • step b) was carried out at 40 °C (till essentially all fat had melted) subsequent cooling did not result in a strong viscosity increase, and the obtained composition did not sufficiently solidify at 5 °C. It was concluded that for a suspension having this specific composition, the maximum temperature in step b) should be lower and/or duration of step b) should be shorter.
  • Casein micelles are not dissolved anymore and their effective size have increased after aggregation.
  • the CLSM image shows that fat granules and casein aggregates are well distributed throughout the composition The viscosity increase after aggregation of casein is thought to be a consequence of a highly packed system, causing the composition to be solid.
  • the firmness and spreadability (using viscosity when applying shear stress as a measure) of the food composition was measured as a function of fat content.
  • This calculated number represents the accumulated viscosity after applying shear stress, considering both the peak viscosity and the shear stress required to nullify the viscosity.
  • the force (i.e. firmness) and the surface under the curve (as a measure for resistance against spreading) are shown in Figure 3.
  • the dashed line represents the estimate interparticle space in ⁇ .
  • the firmness and spreadability increased strongly with an increasing fat content.
  • the surface under the curve decreased slightly when the fat volume fractions exceeded 0.5. This is because the peak viscosity is lower, even though the shear stress required to nullify the viscosity is higher.
  • Figure 4 shows the effect of milk fat content of bovine dairy cream (providing the fluid suspension in step a) of a method according to the invention) on the firmness of the obtained product (after treatment in step b) at 35 °C (for 150 min) and cooling to 5 °C in step c) ).
  • step c The effect of the temperature increase during step b) to a temperature in the range of 33 - 39 °C was studied with an interval of 2 °C using a water bath. The resulting force and area under the curve are shown in Figure 5. It can be concluded that for the tested compositions based on bovine cream, a holding temperature of 35 °C was optimal in providing firmness to the obtained solid food composition. Cooling rate (step c)
  • cooling rate can be used to adjust firmness of the solid product to be prepared.
  • a lower cooling rate generally contributes to an increased firmness.
  • micellar casein I Content of micellar casein I
  • casein aggregates significantly affects the firmness and spreading properties of the food composition.
  • step b) addition of MCI to cream, prior to step b) contributed to the firmness of the food composition, particularly in the range of 2.0 % to 2.5 % (w/w) protein (in addition to casein already present in the cream). At higher concentrations, only a small increase in firmness was observed.
  • micellar casein content was found particularly useful to provide a product with altered stress required to nullify viscosity, with a relatively low change in firmness.
  • Figure 7 shows the resulting firmness and resistance against spreading as a function of the rennet concentration. The firmness was only significantly affected at very low rennet concentrations (0— 8 IMCU / 1). Both the force and the area under the curve show a peak at -30 IMCU / 1).
  • the warming time (duration of step b) affects both the extent to which the fat crystals are molten and the ⁇ -casein hydrolysis (and thus casein aggregation). It is expected that after a certain time there is no effect when holding the cream at its warming temperature any longer. This point in time is reached after sufficient melting of fat crystals and sufficient ⁇ -casein hydrolysis.
  • caprine dairy differs from bovine dairy in some crucial aspects.
  • the ratio casein to whey protein is smaller in caprine dairy (7:3) than in bovine dairy.
  • Caprine dairy contains less as- casein than bovine dairy and it contains more as2 than asl-casein. Due to differences in casein proteins and micelle structure, the renetting time for caprine milk is shorter and the consistency of casein gels is usually weaker .
  • caprine cream After centrifugation, the fat content of caprine cream is more or less equal to the fat content of bovine cream, but caprine fat globules have a smaller average diameter (3.49 ⁇ ) than bovine cream (4.55 ⁇ ).
  • the fat globule size influences fat crystallization and probably rebodying.
  • Another relevant difference is the lack of agglutinin in caprine dairy, a component responsible for clustering (agglutination) and creaming of fat in bovine dairy. It is expected that agglutination of fat in bovine cream promotes partial coalescence through rebodying.
  • the fat globules are already clustered by agglutinin and as a result, protruding crystals may easily pierce surrounding fat globules.
  • caprine cream (42.79 % fat) was successfully used for the preparation of a solid composition according to the invention.
  • the firmness of the composition prepared from caprine cream was 0.152 N, which is about as firm as a composition prepared from bovine cream (42.77 % fat) , of which the firmness was 0.155 N.
  • the main difference (except from the source), was the warming temperature.
  • the melting range of caprine fat is different from bovine fat and the optimum warming temperature was found to be 25 °C. When warming to 35 °C, the resulting caprine Dream Cream was very soft.
  • Figure 8 shows the firmness of a food composition made from caprine cream after step c) prepared from raw cream, pasteurized cream or pasteurized cream with calcium (0.175 %). Warming the cream to 25 °C led to a significant higher firmness than warming it to 35 °C. Considering the fact that the product was still a solid after warming at 35 °C, indicates that not all fat crystals are molten. Another important result is that the pasteurized cream led to a significantly firmer product than the raw cream.
  • the different solid food compositions prepared from caprine cream were studied with CLSM.
  • the obtained images did not reveal major structural differences between the composition obtained from raw and pasteurized caprine cream.
  • Casein aggregation was achieved by adding rennet, but could also be achieved through acid coagulation.
  • texture analysis showed that when applying acid coagulation instead of rennet-induced coagulation the firmness was around 1.5 times higher.
  • the firmness for acid and rennet- induced coagulation were 0.209 N and 0.140 N respectively.
  • CLSM images showed a similar structure for both types of casein aggregation. No differences in syneresis were observed between rennet coagulated and acid coagulated product.
  • Example of method to obtain a solid food composition with particular good firmness, spreadability and olfactory appreciation (in terms such as mouthfeel and a butter-like taste), based on findings in Example 2
  • Cooling prior to warming >1 h at 5 °C (e.g. about 12 hours)
  • step b 150 min at 35 °C
  • step c Cooling after warming (step c) 12 h at 5 °C **

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Abstract

L'invention concerne un procédé de préparation d'une composition alimentaire comprenant de la caséine et de la matière grasse de lait, consistant à soumettre une suspension du type huile dans eau comprenant de la caséine micellaire et de la matière grasse de lait à un traitement coagulant la caséine et remodelant la matière grasse. La composition alimentaire obtenue est (à 20 °C) une suspension solide du type huile dans eau. L'invention concerne en outre une composition alimentaire laitière, laquelle composition est une suspension du type huile dans eau, comprenant de 1 à 6 % en poids de protéine laitière, ladite protéine laitière comprenant de la caséine coagulée; de 20 à 55 % en poids de matière grasse, dont 50 à 100 % en poids sont de la matière grasse de lait; de 40 à 79 % en poids d'eau; et de 0 à 10 % en poids d'autres ingrédients.
PCT/EP2018/074159 2017-09-08 2018-09-07 Substitut de beurre WO2019048620A1 (fr)

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US5916608A (en) * 1995-07-27 1999-06-29 Van Den Bergh Foods Company, Division Of Conopco, Inc. Dairy based spread and process of making
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CN110583793B (zh) * 2019-09-17 2022-09-09 光明乳业股份有限公司 一种低饱和脂肪酸的再制奶酪及其制备方法

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