GB2248170A - Beta-carotene emulsion composition - Google Patents

Abstract

A composition for coloring cheese curd without loss of colour in the cheese whey comprises beta-carotene, a fat, a caseinate and an aqueous solution of gelatin. A method of making the composition is also described.

Description

BETA-CAROTENE EMULSION COMPOSITION This invention is concerned with a beta-carotene emulsion composition useful for coloring the curd, without loss of color to the whey, in cheese production. The invention is also concerned with a method of using the novel beta-carotene composition.

In the preparation of natural cheeses, the dairy industry conventionally uses an annatto preparation to color the cheese curd.

Annatto is an orange-red extract prepared from the seeds of the Bixa orellana tree. The oil soluble carotenoid extract of the seeds is saponified to form a water soluble dicarboxylic acid, labile norbixin, used as the main component of the annatto preparations. This carboxylic acid is, however, pH sensitive and may turn pink if used in acidic foods.

The trees from which annatto is prepared are predominantly grown in Kenya. Because it is a natural product, the yearly production of annatto depends on environmental conditions and political stability, and its market price may fluctuate.

Because of the variables of annatto production, the discovery of a chemical compound to color food was desirable. Therefore, the use of betacarotene to color food, particularly cheese, has been researched. See Luck, H. South African Journal Dairv Technologv:5. No. 4, pp. 181-185 (1973); and Chapman, H. R. et al., Journal of the Societv of Dairv Technoloev.33, No. 4, pp. 162-164 (October 1980).

The use of beta-carotene to color cheese is advantageous over annatto in that the chemical compound may be more closely controlled than the natural product. Beta-carotene may be synthesized or extracted from natural sources. The price of beta-carotene is more stable as opposed to the fluctuating market price of annatto. Additionally, recently discovered health benefits of beta-carotene further promote the use of the substance over annatto.

Beta-carotene is a useful cheese coloring agent because it gives the cheese a color which appeals to the consumer, it does not produce off-flavors (odors, taste) during the ripening of the cheese and it is absorbed by the curd during cheese-making.

Beta-carotene preparations up until the present invention have not been successfully used because an appreciable amount of color was lost in the whey during the cheese making process. When preparations combining beta-carotene with gelatin were tried, loss of color in the whey was high (Luck, supra at page 184). Preparations of beta-carotene in combination with oil reportedly showed no loss of color in the whey (Luck, supra at page 185).

However, these results were observed in the lightly colored Gouda cheese and were not reproducible in more colored cheeses without an appreciable amount of whey color as discussed infra. The color of the cheese depends on the concentration of beta-carotene added during the cheese-making process so that a relatively small amount of beta-carotene would be used to color Gouda cheese as opposed to Cheddar cheese.

The object of the present invention is to overcome the loss of color to the whey by using a novel beta-carotene composition to color cheese products. In particular, natural colored cheeses, such as Cheddar, Colby, Gouda, Montery Jack and Leicester cheeses, may be colored by the novel preparation comprising an effective amount of beta-carotene for coloring cheese curd, an aqueous solution of gelatin, a caseinate and a fat. The beta-carotene composition is prepared as an emulsion and mixed with cheese-making substances to produce colored cheese, as desired.

Preferably, the composition according to the present invention includes as the gelatin component hydrolysed gelatin.

The ingredients are emulsified together and then added to the milk during the cheese-making process to color the cheese curd.

The novel composition may also include a plasticizer, an antioxidant, a surface active agent and a preservative.

The novel beta-carotene composition is made by preparing an aqueous solution of gelatin. Caseinate is then added to the gelatin solution. A fat is heated to an elevated temperature to form a hot oil solution or mixture. Betacarotene is added to the hot oil solution or mixture and dissolved therein to form an oil phase. The oil phase is emulsified into the aqueous gelatin solution containing caseinate to form the novel composition.

Listed below are the definitions of various terms used in this disclosure. These definitions apply throughout the specification unless otherwise stated.

The term "antioxidant" refers to a compound which inhibits oxidation of the fat and the beta-carotene of the novel composition. Examples of antioxidants include alpha-, gamma- and mixed tocopherol, ascorbyl palmitate, butylated hydroxyanisole (BIlA), butylated hydroxytoluene (BHT), tertiary butylated hydroxyquinone (TBHQ) and propyl gallate. The preferred antioxidants are alpha-tocopherol and ascorbyl palmitate. Antioxidants are described in Food Chemistrv, edited by Owen, R. Fennema, Department of Food Science, University of Wisconsin, Madison, WI pp. 198-205 (1985), herein incorporated by reference.

The term "fat" means a biomolecule made up of carbon, hydrogen and oxygen which is a glyceride of a fatty acid. Such fats may be derived from either an animal or vegetable source or synthesized. Fats which are liquid at room temperature (i.e. about 23"C) used in the subject invention are generally referred to as "oils". Examples of such liquid fats or oils include coconut oil, vegetable oil, peanut oil, palm oil, cottonseed oil, corn oil, safflower oil, fish oil, mono-, di- and triglycerides, acetylated monoglyceride and lecithin. Examples of fats which are solid at room temperature include butter, tallow, hydrogenated vegetable oil and lard. Fats are described in Food Chemistrv. supra, chapter 4, herein incorporated by reference.

The term "elevated temperature" refers to a temperature in a range of about 1200C to about 2300C, at which temperature the beta carotene can be dissolved in the fat during the process of preparing the novel composition of the present invention.

The term "plasticizer" refers to an agent which is useful for increasing the dispersibility of an emulsion in milk during the cheese-making process and preventing the hardening of the gelatin in the aqueous solution which is added to the oil phase in forming the novel composition. Examples of plasticizers include sugars (e.g. glucose, fructose and sucrose), invert sugars, maltodextrins and polyols. Preferred plasticizers include propylene glycol and sucrose. Plasticizers are described in Ward, A. G. and Courts, A.

(editors), The Science and Technology of Gelatin, pp. 261-263 (Academic Press, 1977) herein incorporated by reference.

The term "preservative" refers to an agent approved for use in food by a governmental agency such as the U.S. Food and Drug Agency to prevent microbial contamination in the novel composition. Examples of such preservatives include sorbates, benzoates and parabens. Preferred preservatives are propyl paraben, methyl paraben and sorbic acid.

Preservatives are described in Food Chemistrv. supra, pp. 644-653, herein incorporated by reference.

The term "surface active agent" refers to an agent which lowers a surface tension of a fat in the oil phase of the subject invention to maintain the oil droplets intact and prevent the separation of the aqueous phase from the oil phase of the novel composition. Such agents work by aligning along an interface between the oil and the aqueous phases or by adding a charge to the surface of the oil phase which causes the oil droplets in the phase to repel each other. Examples of such agents include mono- and di-glycerides, acetylated monoglyceride, lecithin, polyglycerol esters, polysorbates and free fatty acids. A preferred surface active agent is acetylated monoglyceride.

Surface active agents are described in Food Chemistrv, supra at pp. 169-175, and Friberg, S. Food Emulsions. The Swedish Institute for Surface Chemistry (Stockhold, Sweden, 1976) herein incorporated by reference.

According to the method of the present invention, beta-carotene, an aqueous solution of gelatin, a caseinate and a fat are combined as described below to form a beta-carotene preparation to color the curd portion of natural cheeses, without losing color to the whey or aqueous solution formed during the cheese-making process.

Cheeses which may be colored according to this invention include, for example, Cheddar, Colby, Gouda, Montery Jack and Leicester Cheese. It may be appreciated that any other natural cheese which is colored for sale to consumers may be prepared with the novel beta-carotene preparation.

Beta-carotene used in the subject invention may be obtained in crystal form or in a oil suspension form which may be commercially available. The following preparations of beta-carotene in oil suspensions useful in the invention may be obtained from Hoffmann-La Roche, Inc. of Nutley, New Jersey: PRODUCT OTTER INGREDIENTS 1. Beta Carotene 30% in Partially Hydrogenated Vegetable Oil Cottonseed and Soybean Oils 2. Beta Carotene 24% Hydrogenated Coconut Semi-Solid Suspension Oil 3. Beta Carotene 22% HSR Partially Hydrogenated in Vegetable Oil Cottonseed and Soybean Oils, Lecithin, BHA Ascorbyl Palmitate, Citric Acid A preferred form of beta-carotene is the crystal form without other ingredients added.

Beta-carotene is preferably combined with an aqueous solution of gelatin, a fat and a caseinate and preferably amounts to about 0.25 to about 15 percent (w/w) of the total composition. Especially preferred is a percentage of about 4 to about 7 (w/w) beta carotene to composition.

An aqueous solution of gelatin is prepared to produce the novel composition. Although either hydrolysed or unhydrolysed gelatin may be used, hydrolysed gelatin is prefered because it disperses more easily in the milk during cheese making. The gelatin preferably makes up about 10 to about 35 percent (w/w) of the total composition, especially about 12 to about 25 percent.

Examples of both hydrolysed and unhydrolysed gelatins commercially available include: Bloom Supplier type Strength *K & Low bloom gel - type A 100 ** Croda Low bloom gel 100 K & K Hydrolysed gel - type A 0 *** Dynagel Low bloom gel - type A 50 Dynagel Hydrolysed gel - type A 0 * Kind and Knox, Division of Knox Gelatin, Inc., Saddle Brook, NJ ** Croda, Inc. of New York, NY and *** Dynagel, Inc. of Calumet City, IL An especially preferred hydrolysed gelatin is of the acid type with a 0 bloom strength such as Sol-U-ProX gelatin manufactured by Dynagel of Calumet City, IL.

Gelatins are generally described in Ward, A. G. and Courts, A.

(editors), The Science and Technology of Gelatin (Academic Press 1977), herein incorporated by reference.

Preferred caseinates used in the composition include sodium caseinate, calcium caseinate or potassium caseinate. Especially preferred is sodium caseinate. Any commercially available preparation of caseinate useful in preparing the novel composition may be used.

A preferred range of caseinate in the composition is about 2 to about 10 percent (w/w) of the total composition and more preferably about 2 to about 5% (wlw).

As discussed below, during the cheese manufacturing process rennin or acid or both is added to milk to react with the casein in the milk protein to coagulate the milk. It is believed that the rennin also reacts with the caseinate of the novel composition causing the caseinate of the composition to coagulate along with the casein of the milk to therefore entrap the betacarrotene in the curd.

A fat is combined with the beta-carotene to form an oil phase. In the preferred embodiment a fat or oil is heated to an elevated temperature, preferably in a range of about 140"C to about 1600C. Oil may be preheated to save time in preparing the beta-carotene preparation and lower temperatures (i.e. below about 1600C) avoid substantial degradation of the beta-carotene when it is added to the heated oil.

Although any fat described above may be used by the skilled artisan, preferable fats include vegetable oil and coconut oil, such as the vegetable oil manufactured under the trademark Durkex 500 by Van Den Bergh, Foods of Lisle, Illinois. The fat is preferably used in a range of about 3 percent to about 30 percent (w/w) of the total composition, and more preferably about 3 to about 10 percent (w/w).

In a preferred embodiment, an antioxidant, a plasticizer, a surface active agent and a preservative may be added.

An antioxidant to prevent the oxidation of the fat and the beta-carotene may be added in a range of about 0.2 to about one (1) percent (w/w) of the total composition. Examples of such antioxidants are described above and preferred antioxidants include alpha-tocopherol and ascorbyl palmitate.

A plasticizer in a range of about 5 to about 40 percent (w/w) of the total composition is also preferably included. Of the plasticizers described above, preferred plasticizers are sugars and polyols, especially sucrose and propylene glycol, respectively.

A surface active agent is preferably added to lower the surface tension of an oil in the oil phase so that the oil and water phases will stay intermixed without separation of the described agents. A preferred surface active agent is acetylated monoglyceride manufactured under the trademark MyvacetB by Eastman Chemical Co. of Kingsport, TN. Such an agent is preferably used in a range of about 1 to about 20 percent (w/w) of the total composition.

To prevent microbial contamination a preservative, such as a sorbate, a benzoate or a paraben, may be added to the novel composition. Preferred preservatives include methyl paraben, propyl paraben and sorbic acid.

During the preparation of the novel composition the pH of the aqueous phase is preferably adjusted to about 7.0 to about 9.0 with, for example, a sodium hydroxide solution. More preferably, a 10-25 percent sodium hydroxide solution (w/w) is added to the aqueous phase to adjust it to a pH of about 7.2 to about 7.6.

The method according to the present invention for preparing the composition (which includes beta-carotene) comprises a) preparing an aqueous solution of gelatin and b) mixing a caseinate in the aqueous gelatin solution to form an aqueous phase. A fat, preferably coconut oil or vegetable oil, is heated to an elevated temperature, in particular to a temperature of about 1200C to about 230"C, to form a hot oil solution or mixture (step c) and d) beta-carotene (e.g. in the form of crystals) is added to the hot oil solution or mixture and dissolved therein to form an oil phase. Preferably, about 5 percent to about 7 percent (w/w) beta-carotene (e.g. crystals) are dissolved in the hot oil at an elevated temperature. The resulting oil phase containing the beta-carotene (crystals) is emulsified into the aqueous gelatin solution of step b) and preferably propylene glycol and water are added as needed to form the beta-carotene composition (step e).

In a preferred embodiment of the method step b) further comprises mixing a plasticizer and a preservative into the aqueous gelatine solution in the formation of the aqueous phase.

In cheese manufacturing, casein, fat, insoluble salts and some moisture of milk are reduced to a concentrated form by the action of rennin or acid or both. Pasturized milk is innoculated with a appropriate starter culture to convert lactose to lactic acid, which lowers the pH of the milk. The novel beta-carotene composition is added and dispersed throughout the milk.

When the correct pH is reached, i.e. from about 6.5 to about 6.8, the enzyme rennin is added to curdle the casein which precipitates and entraps as much as 90% of the milk fat. The amount of novel composition added to the milk depends on the colour of the cheese curd ultimately desired, and is within the skill of the cheese producer. As a guide, the range of novel composition added to milk is generally in the range from approximately 1:5,000 to approximately 1:40,000 (w/w) Later, during the cheese manufacturing process, the curd is separated from the whey, suitably in conventional manner. The novel beta-carotene emulsion colors the cheese the desired color (i.e. yellow to orange color for cheddar cheese) while the whey remains substantially uncolored or white.

Examples of beta-carotene compositions according to this invention are as follows: Example 1 Ingredients Amount (%) Hydrolysed gelatin 12.57 Sodium caseinate 2.50 Sucrose 10.50 Methyl paraben 0.35 Propyl paraben 0.09 Sorbic acid 0.22 Ascorbyl palmitate 0.55 Coconut oil 6.12 alpha-tocopherol 0.58 Beta-carotene crystals 5.50 Water 61.02 Total 100 percent Manufacturing Procedure A. Combine the hydrolysed gelatin with an equal amount of water. Heat to about 60"C to dissolve the gelatin and form a clear solution (aqueous phase).

B. Add the sodium caseinate, sucrose, methyl paraben, propyl paraben and sorbic acid with agitation to the clear solution of step A. Water may be added as needed to maintain flow of the clear solution.

C. Raise the pH of the aqueous phase to between 7.0 and 8.0 using a 20% sodium hydroxide solution as needed.

D. Heat the oil and alpha-tocopherol together to about 140"C to form an oil mixture.

E. Add the beta carotene crystals to the oil mixture of Step D and continue to heat until the beta-carotene crystals dissolve, preferable at about 1600C, to form an oil phase.

F. Emulsify the oil phase formed in step E with the aqueous phase of step C with homogenization, adding water as needed.

Example 2 Ingredients Amount (%) Hydrolysed gelatin 12.57 Propylene glycol 30.17 Sodium caseinate 5.03 Sucrose 10.06 Asorbyl palmitate 0.55 Fiitered water 27.15 Oil 3.67 Alpha-tocopherol 0.58 Acetylated monoglyceride 3.67 Beta-carotene crystals 5.54 20% Sodium hydroxide solution 1.01 Total 100 percent Manufactunne Procedure A. Hydrate the gelatin by preparing a solution of equal amounts water and propylene glycol to form a solution.

B. Heat the solution of step A in an oven at about 60"C until the gelatin in the solution dissolves.

C. Add the sodium caseinate, the sucrose and the ascorbyl palmitate to the warmed gelatin solution of Step B to form an aqueous solution.

D. Adjust the pH of the aqueous solution of Step C to about 7.2 to about 7.6 using a 20% sodium hydroxide solution.

E. Heat together the coconut oil, alpha-tocopherol and acetylated monoglyceride to approximately 1400C to form a heated oil mixture (oil phase).

F. Add beta carotene crystals to the oil phase of step E and heat the mixture to about 1600C until the beta carotene crystals are dissolved.

G. Emulsify the oil phase of step F into the aqueous phase of step D by adding propylene glycol and filtered water as needed.

Example 3 Ingredients Amount (%) Low bloom gelatin 25.00 Sodium caseinate 5.17 Sucrose 10.50 Methyl paraben 0.35 Propyl paraben 0.09 Sorbic acid 0.22 Ascorbyl palmitate 0.55 Vegetable oil 6.12 alpha-tocopherol 0.58 Beta-carotene crystals 5.50 Water 45.92 Total 100 percent Manufacturing Procedure A. Combine the low bloom gelatin with an equal amount of water. Heat to about 600C to dissolve the gelatin and form a clear solution (aqueous phase).

B. Add the sodium caseinate, sucrose, methyl paraben propyl paraben and sorbic acid with agitation to the clear solution of step A Water may be added as needed to maintain flow of the clear solution.

C. Raise the pH of the aqueous phase to between 7.0 and 8.0 using a 20% sodium hydroxide solution as needed.

D. Heat the oil and alpha-tocopherol together to about 140"C to form an oil mixture.

E. Add the beta carotene crystals to the oil mixture of Step D and continue to heat until the beta-carotene crystals dissolve, preferably at about 1600C, to form an oil phase.

F. Emulsify the oil phase formed in step E with the aqueous phase of step C with homogenization, adding water as needed.

The beta-carotene compositions described in Examples 1, 2 and 3 were individually added during three cheese making processes. Whey was separated from the curd colored by the novel formulations. The color of the whey samples were evaluated using a Hunterlab Labscan II colorimeter manufactured by Hunter Associates of Reston, Va. A value designated the b* value (measure of yellowness) was used to quantify the amount of color present in each whey sample. The lower the b* value, the less color in the whey. A b* value of less than 30 corresponds to a visual observation of uncolored whey. It was found that each of the described formulations produced whey with a b* value less than 30.

The novel composition in Example 1 was compared to two different commercially available "water-soluble" beta-carotene compositions, namely, Dry Beta carotene beadlets, Type 2.4S and Dry Beta carotene 1% CWS. Dry Beta carotene beadlets, Type 2.4S include hydrogenated coconut oil, gelatin, sucrose, starch, BHA, BHT, methyl and propyl paraben, sodium benzoate and potassium sorbate. The beadlets are manufactured by Hoffinaun-La Roche of Nutley, NJ. Dry beta carotene 1.0% CWS includes dextrin, gum acacia, vegetable oil, sucrose, sodium ascorbate and dl-alpha-tocopherol and is made by Hoffinann-La Roche. In Luck, H. supra (1973 S. Afr. J. Dairy Tech.) Dry Beta carotene beadlets, Type 2.4S were evaluated and it was concluded that there was practically no loss of color to the whey.

The whey from three cheese making processes using the novel composition of Example a, the Dry Beta carotene 1% CWS and the Dry Beta carotene beadlets, Type 2.4S were evaluated for color using the Hunterlab Lab scan II colorimeter and by analytical assay of beta-carotene. The b* value for the whey from cheese made with the Dry Beta carotene, Type 2.45 Beadlets or Dry Beta carotene 1.0% CWS were 58.85 and 88.87 respectively.

The b* value for the whey from cheese colored with the novel composition was 22.00. Visually, the whey from the cheese colored with the novel formulation appeared uncolored while those from cheese colored with the other beta carotene preparations appeared yellow or orange. The whey samples were analytically assayed for beta-carotene with the following results: Beta-carotene assay Beta-carotene colorant in whev Dry beta-carotene, Type 2.4S 5.02 parts per million Dry beta-carotene 1% CWS 11.2 parts per million Novel composition of Example 2 0.34 parts per million Therefore, it was observed that the novel composition did not visibly color the whey and "no measurable amount" of beta-carotene was quantified.

The phrase "no measurable amount" is defined as less than 0.35 ppm of beta-carotene in the whey. In contrast, the type 2.4S beadlets used by Luck, suDra. produced visible whey color and quantitatively produced about fifteen (15) times more beta-carotene in the whey than the novel composition as assayed above in the whey.

Claims (19)

We Claim:

1. A composition for coloring cheese curd comprising an effective amount of beta-carotene to color cheese curd, an aqueous solution of gelatin, a caseinate and a fat.

2. The composition according to claim 1 wherein the effective amount of beta-carotene is about 0.25 to about 15 percent weight per weight of beta carotene to total composition, the amount of fat is about 3 to about 30 percent weight per weight of fat to total composition, the amount of gelatin is about 10 to about 35 percent weight per weight of gelatin to total composition and the amount of caseinate is about 2 to about 10 percent weight per weight of caseinate to total composition.

3. The composition according to claim 2 wherein the amounts are about 4 to about 7 percent (w/w) beta-carotene, about 3 to about 10 percent (w/w) fat, about 12 to about 25 percent (w/w) gelatin, and about 2 to about 5 percent (w/w) caseinate of the total composition.

4. The composition according to any preceding claim further comprising a plasticizer, an antioxidant, a preservative and a surface active agent.

5. The composition according to any preceding claim wherein the caseinate is sodium caseinate, potassium caseinate or calcium caseinate.

6. The composition according to any preceding claim wherein the fat is an oil, a mono-, di- or triglyceride, an acetylated monoglyceride, a lecithin, a butter, a tallow, a hydrogenated vegetable oil or a lard.

7. The composition according to claim 6 wherein the oil is coconut oil, vegetable oil, peanut oil, palm oil, cottonseed oil, corn oil, safflower oil or fish oil.

8. The composition according to claim 4 wherein the plasticizer is a sugar, an invert sugar, a maltodextrin or a polyol.

9. The composition according to claim 4 wherein the antioxidant is ascorbyl palmitate, alpha-tocopherol, gamma-tocopherol, mixed tocopherol, butylated hydroxyanisole, butylated hydroxytoluene, tertiary butylated hydroxyquinone or propyl gallate.

10. The composition according to claim 4 wherein the surface active agent is an acetylated monoglyceride, a mono- or di-glyceride, lecithin, a polyglycerol ester, a polysorbate or a free fatty acid.

11. The composition according to claim 4 wherein the preservative is a sorbate, a benzoate or a paraben.

12. A method for preparing a composition for coloring cheese curd without substantially coloring cheese whey comprising: a) preparing an aqueous solution of gelatin; b) mixing a caseinate in the aqueous gelatin solution to form an aqueous phase; c) heating a fat to a temperature of about 1200C to about 230"C to form a hot oil solution or mixture; d) adding beta-carotene to the hot oil solution or mixture and dissolving it to form an oil phase; e) emulsifing the oil phase into the aqueous phase of step b to form the composition.

13. The method according to claim 12 wherein step b further comprises mixing a plasticizer and a preservative into the aqueous gelatin solution in the formation of the aqueous phase.

14. The method according to claim 13 wherein step b further comprises: adjusting the pH of the aqueous phase from about 7.0 to about 9.0 by adding a sodium hydroxide solution to the aqueous phase.

15. The method according to any one of claims 12 to 14 wherein the step a comprises mixing about 10 to about 35 percent gelatin weight per weight of the gelatin to the composition with substantially equal amounts of propylene glycol and water to form the aqueous solution of gelatin.

16. The use of a composition according to any one of claims 1 to 11 for coloring cheese curd.

17. A composition for coloring cheese curd whenever prepared by a method according to any one of claims 12 to 15.

18. A composition according to claim 1, substantially as described herein with reference to any one of Examples 1 to 3.

19. A method according to claim 12, substantially as described herein with reference to any one of Examples 1 to 3.