WO2015004275A1

WO2015004275A1 - Color composition comprising carmine pigment and ferrous ions

Info

Publication number: WO2015004275A1
Application number: PCT/EP2014/064946
Authority: WO
Inventors: Charlotte SY
Original assignee: Chr. Hansen A/S
Priority date: 2013-07-11
Filing date: 2014-07-11
Publication date: 2015-01-15

Abstract

The present invention relates to a color composition, which is an aqueous composition comprising a source of carmine pigment and a source of ferrous (Fe²⁺) ions. Also, the present invention relates to the use of the above compositions as food colorants, and to the food products produced containing the present composition.

Description

COLOR COMPOSITION COMPRISING CARMINE PIGMENT AND FERROUS IONS

FIELD OF INVENTION The present invention relates to the technical field of natural colorants, especially to food-grade carmines which can be obtained from insect extracts, and further relates to the use of these colorants for food coloring. BACKGROUND

Colorants containing natural coloring substances are commonly used in the manufacture of a wide range of products, such as food products, pharmaceuticals, painting colors and cosmetics. However, increasingly strict requirements must be fulfilled in order to allow natural colorants to be accepted as commercial coloring agents, especially in the fields of food products, pharmaceuticals, and cosmetics. One requirement of colorants is that they must be stable under common use conditions. For many food applications, this means that a colorant must be thermally stable against heat exposure which may occur during the food preparation process, for example during baking, food pasteurization, and also on any further heating by the consumer prior to consumption. Furthermore, the colorants must exhibit sufficient photostability, i.e. they must be stable on exposure to light over the lifetime of the colored (food) product without substantial color change or disappearance (fading) .

In addition, coloring agents used in food applications must gain regulatory approval for their use, which may impose restrictions on the types of food that the coloring agents can be used with, or the maximum amount which is permitted in food. Recently, new regulations on food colorants and colors containing aluminum have been introduced limiting the amount of aluminum permitted. As a result, much research currently addresses the problem of decreasing the loadings of aluminum used in colorants.

It is also required that colorants are stable against chemical interaction with other compounds in the environment of food. Furthermore, as many food products have a pH in the acidic range, colorants must be stable and effective as colorants in media having a low pH. In addition, the colorant itself may not have a strong taste and/or odor.

Carminic acid is naturally produced by scale insects (like cochineal scale or Polish cochineal. For food coloring, it is obtained by extraction from the powdered bodies of the cochineal Dactylopius coccus. Treatment of aqueous solutions of carminic acid with aluminum precipitates the carmine, and delivers carmine lake, a well-known coloring agent. Process conditions and the optional addition of calcium salts enable providing colors in the red to purple color range. It has found wide application in the coloring of food products such as yoghurt and fruit juices, and has found further application in the coloring of cosmetics.

Despite the known utility of natural food colorants including carmine lake colorants, there exists a desire to develop a greater diversity of color tones suitable for commercial colorants, especially for coloring foods such as dairy, fruit products, and confectionary. Also, there is a general interest in producing colorants with lower loadings of aluminum, and furthermore in replacing the commonly used red acid stable carmines containing ammonium. Colorants having a bluish color tone are particularly desirable.

SUMMARY OF THE INVENTION

In view of the foregoing, the problem addressed by the present invention is the provision of a new natural carmine colorant, the color of which has a new, bluish shift compared to the known red-purple carmine colors. Furthermore, the colorant of the present invention must be suitable for application as food coloring, and be at least as stable to heat and light as the known carmine food colorants, and be colored in the acidic pH ranges commonly encountered in food application. Preferably, the colorant should (i) be free of off-tastes or off-odors which would make it unsuitable for use in food coloring applications, (ii) contain a limited amount of aluminum, and (iii) be suitable for replacing the presently used red acid stable carmines containing ammonium.

As a result of the inventors' comprehensive research undertaken in an attempt to solve the above problem, it has been discovered that such a desirable colorant can be obtained by the provision of aqueous compositions comprising solubilized carmine lakes and a source of ferrous (Fe²⁺) ions.

Furthermore, the present invention provides for the use of the above composition as a food colorant, specifically as a food colorant for fruit, dairy, confectionary, and bakery or prepared food products. Preferred embodiments of the present invention are outlined in the following description and/or identified in the appended dependent claims.

DETAILED DISCLOSURE OF THE INVENTION

Carminic acid (I) is extracted from the powdered bodies of the

(I) The carmine lake pigment is subsequently formed by treatment of an aqueous carminic acid solution with metallic salts in order to precipitate the colored complex formed of the carminic acid and the metal salt. The specifications of carmine lakes for food applications involve that aluminum compounds must be used to precipitate carminic acid, the most widely used being aluminum oxides. Several other metal ions can be used in addition to aluminum during the precipitation of carmine, it is known to influence the color of the resultant lake; carmine aluminum lakes are purple, while carmine aluminum/calcium lakes are shades of red.

EP1669414 describes a method of preparing carmine aluminum/calcium lake, which is free of potential allergenic cochineal insect proteins.

Carmine lakes are insoluble colorants in most solvents including water. When the lakes are dispersed into water and the pH is increased to about 11 or 12 (with sodium hydroxide, potassium hydroxide, etc.), the lake (aluminum salt with/without calcium fixed on a substrate) is irreversibly ruptured, thus releasing the aluminum salt of carminic acid (forming a chelate complex with calcium ions, if they were present in the lake) .

Solubilized carmine aluminum lake is the aluminum salt of carminic acid forming a complex with 2 molecules of carminic acid (II) and solubilized carmine aluminum/calcium lake is the aluminum salt of carminic acid forming a complex with 4 molecules of carminic acid and quelating calcium ions (III) .

( I D ( I I I )

These complex molecules induce pink to purple solutions at pH above 3.5-4 and sediment at lower pH, due to their high molecular weight and lower solubility in acidic conditions.

Accordingly, as known to the person skilled in the art (see e.g WO2012/131057 directed to a food coloring composition comprising a dispersion of carmine lake blended with solubilized carmine lake) , a solubilized carmine lake is a carmine lake in a solution where the pH has been raised to around 12, in order to fully solubilize the carmine lake, and then decreased but kept above 3.5-4. US 2013047349 discloses a hair dye, which comprises a combination of (1) a first agent, which may be carminic acid, and will react with iron to develop color, and (2) a second agent containing an iron salt. From this, the skilled person may learn that combination of carminic acid and iron salts leads to colored compounds.

Widely used carmine lakes include, as commercially available examples and without being restricted thereto, the CP-50 carmine aluminum lake obtainable from Chr . Hansen A/S (Denmark), which contains around 50% carminic acid and 2.8-3.4% aluminum and formulated as powder with maltodextrin . Further carmine lakes are the carmine aluminum/calcium lake, such as CT-100, CT-200, CTR/C and CHR lakes obtainable from Chr. Hansen A/S, which contain around 60% carminic acid, 4-8% calcium and 1.0-1.6% aluminum. These compositions are also formulated as powders with maltodextrin . As the present inventors have found out, a color composition possessing the desired characteristics of having a bluish-shift to the color, high stability to heat and light, and free of off-tastes when used as a food colorant in appropriate matrixes, can be obtained by providing aqueous compositions comprising carmine lake and a source of ferrous (Fe²⁺) ions. The carmine lake may comprise at least one of a carmine aluminum lake and a carmine aluminum/calcium lake. In a preferred embodiment, the composition comprises both a carmine aluminum lake and a carmine aluminum/calcium lake.

Furthermore, the color composition of the present invention preferably contains a carmine lake comprising of 45-65 wt.-% carminic acid, and 1.0-3.4 wt.-% aluminum. In other preferred embodiments, the composition contains carmine lake comprising either 45-55 wt.-% carminic acid, and 2.8-3.4 wt.-% aluminum, or 55-65 wt.-% carminic acid, 4-8 wt.-% calcium and 1.0-1.6 wt.-% aluminum. The color composition can also be defined in terms of the content of the carmine lake in units of the free carminic acid, which is in the range of 2-10 wt.-% based on the composition, preferably, 3-8 wt.-%, more preferably 4-6 wt.-%, and most preferably 4.2-4.8 wt.-%.

The inventors have found that compositions comprising a range of (carmine aluminum lake) : (carmine aluminum/calcium lake) weight ratios can be useful embodiments of the invention. Accordingly, the weight ratio of the carmine aluminum lake to the carmine aluminum/calcium lake is preferably in the range of 23/77 to 83/17, and more preferably 44/56 to 64/36. It was furthermore discovered that working embodiments of the composition can be made from a wide range of sources of ferrous ions. Preferably, the source was selected from at least one of ferrous gluconate, ferrous lactate, ferrous carbonate, ferrous sulfate, ferrous acetate and ferrous chloride, preferably ferrous gluconate and/or ferrous lactate, and more preferably ferrous gluconate. These investigations also revealed that the total amount of ferrous ions present in the composition is preferably in the range of 0.1-5 mol, preferably 1-3 mol, and more preferably 1.5-2.5 mol, and especially 2 mol, per mol of carminic acid present in the composition.

The inventors have also found that in a preferred embodiment, the aqueous color composition of the invention may also comprise a base, preferably an inorganic base, more preferably an alkali and/or alkaline earth hydroxide, and most preferably sodium hydroxide. As a result, the pH of the favored compositions is preferably in the range of 8-13, preferably 9- 12, and more preferably 10.5-11.5. Without wishing to be bound by any particular theory, it is believed that basic pH interrupts the interaction between the ferrous ions and the carmine, with the result that the bluish shade of the present application only becomes visible at slightly acidic and neutral pH, and therefore cannot be seen in the claimed compositions. As most food products have a pH in the range pH 3-7, addition of the composition to foodstuffs inevitably brings the composition into the correct pH range for the color to be visible(See e.g. Example 4).

Various additives may be added to the composition in order to further enhance or preserve its appearance and taste in foods. Accordingly, the composition may further comprise a humectant/stabilizer, which is preferably selected from propylene glycol, propan-1 , 2-diol or glycerol, the most preferable of which is propylene glycol. The composition may further comprise at least one adjuvant to improve the longevity, processability and ease of use of the composition. The adjuvant is preferably selected from stabilizers such as polysorbate-80, thickeners such as carboxymethyl cellulose, methyl cellulose or vegetal gums and fatty acids such as palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid. While the composition of the present invention can be combined with alternative colorants to deliver coloring agents with different shades, the composition is preferably used as the sole colorant component in a carmine/ferrous ions source system.

The present invention also includes embodiments combining some or all of the above-described features. Accordingly, the invention claims compositions consisting of carmine lake (solubilized) ; a source of ferrous (Fe^- ⁺ ) ions; and optionally one or more or all of the bases selected from inorganic bases, or more preferably alkali and/or alkaline earth hydroxide, and most preferably sodium hydroxide; a humectant which is preferably selected from propylene glycol, propan-1 , 2-diol or glycerol, and more preferably propylene glycol; any of the adjuvants selected from stabilizers, thickeners and fatty acids; and water.

A particularly favored such embodiment comprises

3.0-8.0 wt.-% of carmine aluminum lake

3.0-8.0 wt.-% of carmine aluminum/calcium lake

0.5-2.0 wt.-% in units of Fe^ ^" , of a source of ferrous

(Fe2+) ions,

40-60 wt.-% of polypropylene glycol,

0.5-5.0 wt.-% of a base selected from inorganic bases, or more preferably alkali and/or alkaline earth hydroxides, and most preferably sodium hydroxide

1-10 wt.-% in total, of any of the adjuvants selected from stabilizers, thickeners and fatty acids, and

water to sum up to 100 wt.-% As discussed above, coloring agents used in food applications must gain regulatory approval for their use, which may restrict the types of food that the coloring agents can be used with, or the maximum amount which is permitted in food. Accordingly, a preferable embodiment of the present invention is one in which all of the components are approved for use in foods. It is also noted that this innovation is in line with new regulations on food colorants and colors containing aluminum, since it contains a limited amount of aluminum (<0.25 % Al, w/w) . Furthermore, it has been found that this product can be used to substitute the red acid stable carmines, which are currently not considered as suitable colorants in foodstuffs because they contain a citroammonical salt of carminic acid (4-aminocarminic acid, formed by the combination of carminic acid and ammonium salts) that does not fit European specifications of carminic acid and carmines (E120, E121) and is not mentioned in the specifications of directive 2008/128/EC.

The present invention also includes the use of the present composition in the coloring of foods, preferably dairy products, fruit preparations, confectionary products, and prepared food (like bakery products) . The resultant colored food products are also encompassed by the invention. For this reason, it is noted that the composition is stable to the various heating processes commonly employed in the preparation of foodstuffs, such as pasteurization and baking. It has furthermore been observed that the bluish shade of the present composition disappears for a while on heating, only to reappear after a few hours. Without wishing to be bound by any particular theory, it is thought that the loss of color on heating may be due to the rupture of weak interactions between carminic acid and ferrous iron, which return on cooling, accompanied by the bluish shade.

BRIEF DESCRIPTION OF THE FIGURES Photographs showing various embodiments of the present invention in pH 5.5 deionized water. Figure la shows ratios of carminic acid coming from an aluminum carmine lake (CP-50) to carminic acid coming from an aluminum/calcium carmine lake (CHR) varying from (left to right) 80:20, 60:40, 50:50, 40:60 and 20:80, with 1.2% Fe²⁺ for 4.5 carminic acid. Figure 2a depicts ratios of carminic acid coming from an aluminum carmine lake (CP-50) to carminic acid coming from an aluminum/calcium carmine lake (CHR) varying from (left to right) 80:20, 60:40, 50:50, 40:60 and 20:80, with 0.9% Fe2+ for 4.5% carminic acid.

Photographs showing various embodiments of the present invention in semi-skimmed milk. Figure 2a shows ratios of carminic acid coming from an aluminum carmine lake (CP-50) to carminic acid coming from an aluminum/calcium carmine lake (CHR) varying from (left to right) 80:20, 60:40, 50:50, 40:60 and 20:80, with 1.2% Fe2+ for 4.5% carminic acid. Figure 2b depicts ratios of carminic acid coming from an aluminum carmine lake (CP-50) to carminic acid coming from an aluminum/calcium carmine lake (CHR) varying from (left to right) 80:20, 60:40, 50:50, 40:60 and 20:80, with 0.9% Fe2+ for 4.5% carminic acid.

Photographs showing various embodiments of the present invention in yogurts with acid slurry after heat- treatment, compared to embodiments lacking iron ions. Figure 3a shows a set of matrices with different shades, colored with the same composition of the present invention, containing 4.5% carminic acid (40% from aluminum carmine lake CP-50 and 60% from aluminum/calcium lake CHR) and 1.2% ferrous iron, and not submitted to heat-treatment. Figure 3b depicts a set of water fondants with different shades, colored with the same composition of the present invention (at dosage 0.05 g /40 g) , containing 4.5% carminic acid (40% from alumiminium carmine lake CP-50 and 60% from aluminum/calcium lake CHR) and 1.2% ferrous iron, before heat-treatment. Figure 3c illustrates a set of water fondants with different shades, colored with the same composition of the present invention (at dosage 0.05 g /40 g) , containing 4.5% carminic acid (40% from aluminum carmine lake CP-50 and 60% from an aluminum/calcium lake CHR) and 1.2% ferrous iron, after heat-treatment.

Photographs showing a set of various shades obtained with the present invention, depending on the matrix nature, pH and heat-treatment. Figure 4a shows yoghurts with carminic acid or each one of the CP-50, CT-100, CT-200, CTR/C or CHR carmine lakes, without ferrous iron, after pasteurization of the colored slurries and 24h stabilization of the yoghurts. Figure 4b depicts yoghurts with carminic acid or each one of the CP-50, CT-100, CT-200, CTR/C or CHR carmine lakes, with 1.5% ferrous iron for 4.5% carminic acid, after pasteurization of the colored slurries and 24h stabilization of the yoghurts

Photographs of the use of the present invention in neutral pH confectionery products. Figure 5a shows foams at two different dosages of an aluminum carmine lake (CP-50) with iron, at 1.5% Fe²⁺ for 4.5~6 carminic acid in the color bulk. Figure 5b depicts foam at low dosage of an aluminum/calcium carmine lake (CHR) with iron, at 1.5% Fe2+ for 4.5% carminic acid in the color bulk .

Fig. 6 Photographs of the use of composition in bakery products. Figure 6a shows bakery with an aluminum carmine lake (CP-50) and iron, at 1.5% Fe for 4.5% carminic acid in the color bulk. Figure 6b depicts bakery with an aluminum/calcium carmine lake (CHR) and iron, at 1.5% Fe2+ for 4.5% carminic acid in the color bulk .

Photographs showing comparison between the present invention and a control color containing red acid stable aluminum carmine in yoghurt

Photographs showing comparison between the present invention and a control color containing red acid stable carminic acid in confectionary

Photograps showing a set of various shades obtained with the present invention, depending on the presence of ferrous iron in the carmine color. Figure 9a shows aqueous solutions (pH 6.0-6.5 in deionized water) coloried with carminic acid or each one of the solubilized carmine lakes, CP-50 (aluminum carmine lake), CT-100, CT-200, CTR/C or CHR (aluminum/calcium carmine lakes), without ferrous iron. Figure 9b depicts aqueous solutions (pH 6.0-6.5 in deionized water) colored with carminic acid or each one of the solutbilized carmine lakes, CP-50 (aluminum carmine lake), CT-100, CT-200, CTR/C or CHR (aluminum/calcium carmine lakes), with 1.5% ferrous iron in the colorant for 4.5% carminic acid.

EXAMPLES

Example 1

Preparation of a colorant of the invention

As an illustrative example, the procedure for the preparation of a colorant of the invention is given. The color is formulated at 25°C, by mixing two building blocks. The first building block contains an aluminum carmine lake (CP- 50: 50% laked carmine, 3.13% aluminum, maltodextrin) , an aluminum/calcium carmine lake (CHR: 60% laked carmine, 1.45% aluminum, 7.5% calcium, maltodextrin), propylene glycol, water and NaOH. Carmine is totally soluble in this building block. The second building block contains ferrous gluconate, water and NaOH. Ferrous gluconate is also soluble in this building block. The final bulk is at pH 10-12, with a turbidity value (at 0.05 wt.-% in water) under 10 Nephelometric Turbidity Units (NTU) and contains 4.5% carminic acid.

Example 2

Dilution of the composition bulks in pH 5.5 deionized water

A range of solutions of compositions of the present invention were made up in pH 5.5 deionized water at 0.05 wt.-%. As shown in Figure 1, the weight ratio of carminic acid coming from the aluminum carmine lake CP-50, to carminic acid coming from the aluminum/calcium carmine lake CHR in the composition was varied from 80:20 to 60:40 to 50:50 to 40:60 to 20:80 while maintaining the weight ratio of Fe²⁺ to carminic acid at 1.2:4.5. A second experiment is also depicted in Figure 1, which differs only in that the weight ratio of Fe²⁺ to carminic acid was 0.9:4.5.

The samples in Figure 1 were also subjected to colorimetric analysis according to the CIELAB L*C*h* color system to measure the lightness (L*), chroma (C*) and hue (h*) of solutions of the claimed compositions in deionized water at pH 5.5.

Colorimetric measurements were performed in 25cm² Iwaki plastic flasks using Spectraflash 650 (Datacolor) in transmission mode under D65 lOdeg illuminant. Turbidity at 0.05 wt . ~6 was measured on a VWR turbidimeter. DE*2000 is an indicator for the total color variation, which includes the changes all of L*, C* and h* values and illustrates the total color difference. High values indicate large differences.

As can be clearly seen both in Figure 1 and the colorimetric measurements in Table 1, changing the ratio of aluminum carmine lake CP-50 to the aluminum/calcium carmine lake CHR in the composition leads to a significant change in the chroma and hue of the resultant solution. Meanwhile, changing the ratio of Fe²⁺ to carminic acid from 1.2:4.5 to 0.9:4.5 appears to have a moderate impact on the chroma and hue in water solutions (slightly brighter and less bluish) .

Table 1

Specifications of original

composition

Turbidity Colorimetry in

CA Ratio ¹> at 0.05 deionized water

Brix

pH aw wt.-% in pH = = 5. 5, 0.05%

(°bx)

water

(NTU)

L C* h*

80/20

35 ±5 337 ±5

1.2% Fe²⁺

60/40

1 40 ±5 343 ±5 .2% Fe²⁺

50/50

42 ±5 345 ±5

1.2% Fe²⁺

40/60

46 ±5 348 ±5

1.2% Fe²⁺

20/80

0 . 600- 48 ±5 352 ±5 .2% Fe²⁺

10 - 12 0 . 7 99 45 - 60 < 10 55 - 60

80/20

37 ±5 334 ±5

0.9% Fe²⁺

60/40

42 ±5 339 ±5

0.9% Fe²⁺

50/50

42 ±5 341 ±5

0.9% Fe²⁺

40/60

42 ±5 344 ±5

0.9% Fe²⁺

20/80

46 ±5 34 9 ±5

0.9% Fe²⁺

1) [carminic acid from Al-carmine] / [carminic acid from Al/Ca- carmine]

Example 3

Dilution of the composition bulks in semi-skimmed milk.

A range of solutions of compositions of the present invention were made up in semi-skimmed milk at a dosage allowing a Lightness (L* value) of 65. As shown in Figure 2, the weight ratio of carminic acid coming from the aluminum carmine lake CP-50 to carminic acid coming from the aluminum/calcium carmine lake CHR in the composition was varied from 80:20 to 60:40 to 50:50 to 40:60 to 20:80 while maintaining the weight ratio of Fe²⁺ to carminic acid as 1.2:4.5. A second experiment is also depicted in Figure 2, which differs only in that the weight ratio of Fe²⁺ to carminic acid was 0.9:4.5.

The samples depicted in Figure 2 were also subjected to colorimetric analysis to measure the lightness (L*), chroma (C*) and hue (h*) of solutions of the claimed compositions in semi-skimmed milk.

As can be clearly seen in Figure 2 and in the colorimetric measurements in Table 2, changing the ratio of aluminum carmine lake CP-50 to the aluminum/calcium carmine lake CHR in the composition leads to a clear change in the intensity and hue of the resultant solution. Meanwhile, changing the weight ratio of Fe²⁺ to carminic acid from 1.2:4.5 to 0.9:4.5 has a moderate impact of the chroma (slightly more bright) and does not appear to have a significant impact on the hue of the solutions.

Table 2

1) [carminic acid from Al-carmine] / [carminic acid from Al/Ca- carmine ]

Example 4

Final shades of a composition used in matrixes with different pH and natures, and in water fondants at increasing pH, before and after heat-treatment A set of matrixes (pH 3 drink, pH 3.8 slurry, pH 4.2 slurry, yoghurt, deionized water, milk, tap water) and a set of water fondants at pH 1, 3, 5, 7 and 9 were prepared with a composition of the present invention containing 4.5 ~6 carminic acid (at 40% from aluminum carmine and 60% from aluminum/calcium carmine) and 1.2% ferrous iron (from ferrous gluconate) dissolved in propylene glycol and water with 11% NaOH. The water fondants were then pasteurized at 90°C for 5 min, cooled down and left to stabilize for 24 h. As shown in Figure 3, these experiments demonstrate that the final shade obtained with the present invention in food applications depends on the matrix nature, on the pH and on the heat-treatment applied during the process of the colored food. Example 5

Final shades in yoghurts with acid slurry after heat-treatment

A set of yoghurts were prepared with and without ferrous iron, and containing either carminic acid, or various carmine aluminum, and carmine aluminum/calcium lakes (Figure 4) . The weight ratio of Fe²⁺ to carminic acid was 1.5:4.5 in all of the compositions containing ferrous iron, and the lakes employed were aluminum and aluminum-calcium carmine (CP-50, CT-100, CT- 200, CTR/C and CHR obtainable from Chr . Hansen A/S, Denmark) as defined above. The compositions were employed in an acidic slurry (pH 3.8) at a dosage permitting to have 50 mg/kg carminic acid in final yoghurt The slurry mixture was then pasteurized (90°C / 5 min) , cooled down and added to plain yoghurts . As is evident from analysis of Figure 4, the addition of ferrous ions to the composition leads to a significant improvement in the bluish aspect of the color of yoghurts, that is revealed after heat-treatment (pasteurization of the colored slurry) and stabilization (24h waiting after mixing the cooled slurry with yoghurt) .

Example 6

Use of composition in neutral pH confectionery products:

Confectionary foams at pH 6-7 were prepared at 60°C containing compositions of the present invention, as shown in Figure 5. Confectionary foam (I) contains 0.08 wt.-% of a composition comprising carmine aluminum lake CP-50 with a weight ratio of Fe²⁺ to carminic acid of 1.5:4.5. Confectionary foam (II) only differs from (I) in that it contains 0.046% of the composition of the present invention, while confectionary product (III) only differs from (II) in that it comprises carmine aluminum/calcium lake CHR with Fe²⁺.

As shown in Figure 5, these experiments demonstrate that the color of the resultant confectionary products is dependent on the carmine lake employed. Example 7

Use of composition in bakery products

Bakery products at pH 5-6 were prepared containing compositions of the present invention, comprising carmine aluminum, and carmine aluminum/calcium lakes with ferrous iron. The color compositions were mixed with the batters which were then baked for 21-24 min at 180°C. Bakery product (I) contains 0.20 wt.-% of a composition comprising carmine aluminum lake CP-50 with a weight ratio of Fe²⁺ to carminic acid of 1.5:4.5. Bakery product (II) only differs from (I) in that it contains carmine aluminum/calcium lake CHR with Fe²⁺, instead of carmine aluminum lake CP-50.

As shown in Figure 6, these experiments demonstrate that the color of the resultant baked items are dependent on the carmine lake employed, and furthermore that the color composition is stable to the heat of the baking process.

Example 8 Replacement of a control aluminum-carmine color containing 7% red acid stable carmine in yoghurt: colorimetry

Yoghurts were prepared containing 34.5 mg/kg and 60 mg/kg carminic acid from a composition of the present invention. The color composition was 4.5 % carminic acid (at 40% from aluminum carmine and 60% from aluminum/calcium carmine) and 1.2% ferrous iron (from ferrous gluconate) dissolved in propylene glycol and water with 11% NaOH. And they were compared to yoghurts containing 30 mg/kg and 60mg/kg carminic acid from the prior art red acid stable control aluminum carmine color.

The colors were employed in acidic slurry (pH 3.8) at a dosage permitting to have the appropriate wt.-% of carminic acid in final yoghurt. The slurry mixtures were then pasteurized (90°C / 5 min and cooling down) and added to plain yoghurts.

As is clear from Figure 7, the present invention is a good replacer of the red acid stable control aluminum-carmine color in yoghurt products with low to high dosages of carminic acid (different color intensities) : DE*2000 around 1.6 show that the global difference of shade between the two products is acceptable. Furthermore, this replacement might require a slight dosage adjustment (overdosage of the present invention compared to the control color, especially at low dosages) to obtain an acceptable DE*2000 (under 2.0) .

Example 9

Replacement of a control carminic acid color containing 5% red acid stable carmine in confectionary: stability to light

Confectionary foam was prepared containing 20 mg/kg carminic acid from a composition of the present invention. The color composition was 4.5 % carminic acid (at 50% from aluminum carmine and 50% from aluminum/calcium carmine) and 1.5% ferrous iron (from ferrous lactate) dissolved in propylene glycol and water with 12% NaOH. And they were compared to confectionary foams containing 20 mg/kg carminic acid from the prior art red acid stable control carminic acid color As is clear from Figure 8, the present invention is a good replacer of the red acid stable control carminic acid color in confectionary products, because the confectionary comprising the control carminic acid loses its color more rapidly on exposure to light than the confectionary comprising the composition of the present invention.

Example 10 Preparation of colorants of the invention.

As an illustrative example, the procedure for the preparation of diverse colorants of the invention is given. The color is formulated at 25°C, by mixing two building blocks. The first building block contains carminic acid, or an aluminum carmine lake (for instance CP-50: 50% laked carmine, 3.13% aluminum, maltodextrin) , or an aluminum/calcium carmine lake (for instance CT-100: 60% laked carmine, 1.1% aluminum, 7.5% calcium, maltodextrin; or CT-200: 55% laked carmine, 1.3% aluminum, 7.0% calcium, maltodextrin; or CTR: 60% laked carmine, 1.2% aluminum, 7.2% calcium, maltodextrin; or CHR: 60% laked carmine, 1.45% aluminum, 7.5% calcium, maltodextrin), mixed with propylene glycol, water and NaOH. Carmine (or carminic acid) is totally soluble in this building block. The second building block contains ferrous gluconate, water and NaOH. Ferrous gluconate is also soluble in this building block. The final bulk is at pH 10-12, with a turbidity value (at 0.05 wt.-% in water) under 10 Nephelometric Turbidity Units (NTU) and contains 4.5% carminic acid plus 1.5% ferrous iron. Figure 9b shows the shades obtained by the dilution of such colorants in deionized water at pH 6.5. To compare, similar colors were prepared without ferrous gluconate and figure 9a highlights that the shades obtained in the absence of ferrous iron are significantly less bluish.

Moreover, it can be seen that the presence of ferrous iron has a bigger impact on the shift of shade to bluish with carminic acid than with solubilized carmine lakes, and with solubilized aluminum carmine lake (CP-50) than with solubilized alumnum/calcium carmine lakes (CT-100, CT-200, CTR/C or CHR) . Indeed, the effect of ferrous iron is greater when more sites are free on the carminic acid molecules to chelate ions.

Claims

1. Color composition, which is an aqueous composition

comprising carmine lake and a source of ferrous (Fe^- ⁺ ) ions, wherein the carmine lake comprises (i) a carmine aluminum lake and/or (ii) a carmine aluminum/calcium lake.

2. The color composition of claim 1, wherein the carmine lake contains 45-65 wt.-% carminic acid, 1.0-3.4 wt.-% aluminum and 0.0-8 wt.-% calcium.

3. The color composition of claim 2, wherein the carmine lake contains

(i) 45-55 wt.-% carminic acid and 2.8-3.4 wt.-% aluminum, and/or

(ii) 55-65 wt.-% carminic acid, 4-8 wt.-% calcium and 1.0- 1.6 wt.-% aluminum.

4. The color composition of any of claims 1-3, wherein the

weight ratio of the carmine aluminum lake (i) to the carmine aluminum/calcium lake (ii) is in the range of 23/77 to

83/17, and preferably 44/56 to 64/36.

5. The color composition of any of claims 1-4, wherein the

source of ferrous ions is at least one selected from ferrous gluconate, ferrous lactate, ferrous carbonate, ferrous sulfate, ferrous acetate and ferrous chloride, preferably ferrous gluconate and/or ferrous lactate, and more

preferably ferrous gluconate.

6. The color composition of any of claims 1-5, which further comprises a base, preferably an inorganic base, more

preferably an alkali and/or alkaline earth hydroxide, and most preferably sodium hydroxide.

The color composition of any of claims 1-6, which further comprises a humectant/stabilizer, preferably propylene glycol, propan-1 , 2-diol or glycerol, and more preferably propylene glycol.

8. The color composition of any of claims 1-7, which has a pH in the range of 8-13, preferably 9-12, and more preferably

10.5-11.5.

9. The color composition of any of claims 1-8, wherein the

content of carmine lake, in units of free carminic acid, is in the range of 2-10 wt.-% based on the composition, preferably, 3-8 wt.-%, more preferably 4-6 wt.-%, and most preferably 4.2-4.8 wt.-%.

10. The color composition of any of claims 1-9, wherein the

amount of ferrous ions is in the range of 0.1-5 mol, preferably 1-3 mol, and more preferably 1.5-2.5 mol

(especially 2 mol) , per mol of carminic acid present in the composition .

11. The color composition of any of claims 1-10, which further comprises at least one selected from stabilizers, thickeners and fatty acids .

12. The color composition of any of claims 1-11, wherein the

carmine is the sole pigment.

13. The color composition of any of claims 1-12, which consists of solubilized carmine lake, a source of ferrous (Fe2+) ions, and optionally one or more or all of a base as defined in claim 6, a humectant/stabilizer as defined in claim 7, and any of the adjuvants as defined in claim 11, and water.

14. The color composition of any of claims 1-13, which comprises or consists of

3.0-8.0 wt.-% of carmine aluminum lake

3.0-8.0 wt.-% of carmine aluminum/calcium lake

0.5-2.0 wt.-% in units of Fe^ ^" , of a source of ferrous

(Fe2+) ions,

40-60 wt.-% of polypropylene glycol,

0.5-5.0 wt.-% of a base as defined in claim 7

1-10 wt.-% in total, of any of the adjuvants as defined in claim 11, and

water to sum up to 100 wt.-%.

The use of the color composition of claim 14 for coloring foods, preferably dairy products, fruit preparations, confectionary products or prepared food (like bakery products) .

A food product, preferably a dairy product, a fruit

preparation, a confectionary product or a prepared food (like bakery product) , comprising the color composition of claim 14.