AU2013258018B2

AU2013258018B2 - A composition comprising chlorophyllin as a green pigment

Info

Publication number: AU2013258018B2
Application number: AU2013258018A
Authority: AU
Inventors: Klaus Koehler; Lene Munch NIELSEN
Original assignee: Oterra AS
Current assignee: Oterra AS
Priority date: 2012-05-11
Filing date: 2013-05-08
Publication date: 2016-05-05
Anticipated expiration: 2033-05-08
Also published as: WO2013167644A1; AU2013258018A1; EP2846647A1

Abstract

A green coloring composition comprising copper chlorophyllin as a green pigment. It may be used in the manufacture of food and pharmaceutical products.

Description

WO 2013/167644 PCT/EP2013/059563 TITLE: A composition comprising chlorophyllin as a green pigment FIELD OF THE INVENTION 5 The present invention relates to a green coloring composition comprising cop per chlorophyllin as a green pigment. It may be used in the manufacture of food and pharmaceutical products. BACKGROUND ART 10 Copper chlorophyllin is today used commercially as a green pigment in differ ent food products. The commercially available acid stable (e.g. in soft drink) transparent natural 15 green color product of Chr. Hansen A/S, Denmark termed "C-10.OOOP-WS-AP" comprises following ingredients: Sodium copper chlorophyllin (E 141(ii)), pro pylene glycol (E 1520) (69%), polysorbate 80 (E 433) (23%) - see e.g. the publicly available product information. 20 When this natural green C-10.OOOP-WS-AP product is used in e.g. soft drinks (low pH around 3-4) a stable transparent green color is obtained. It is transparent due to the fact that the chlorophyllin (green color) particles are very small in the suspension - i.e. very small chlorophyllin (green color) particles dispersed in the low pH water phase (e.g. soft drink). 25 One may term this a solid-in-water dispersion - which, as known to the skilled person, is different from e.g. an oil-in-water emulsion. As known in the art Polysorbate 80 (Tween 80) is a detergent/emulsifier herein alternatively expressed dispersing agent. 30 As known in the art Polysorbate 80 (Tween 80) may be said to have an un wanted unpleasant taste. Another natural green color product of Chr. Hansen A/S, Denmark is termed CapColors@Green 100 and it may be characterized as made by milling in order to create sufficient small chlorophyllin (green color) particles.

WO 2013/167644 PCT/EP2013/059563 -2 According to the public available product information - for this product the col or will look more or less opaque (i.e. one may say that it is less transparent than the C-10.OOOP-WS-AP product discussed above). The CapColors@Green product does not comprise Polysorbate 80 and may 5 therefore be seen as a prior art solution to make a product without the un pleasant taste of Polysorbate 80 (Tween 80). The compound quillaja is a known detergent/emulsifier. 10 W02011/119290A1 and W02011/154407A1 describe use of quillaja as emulsi fier in an oil-in-water emulsion. Claim 14 of W02011/154407A1 relates to an oil-in-water emulsion comprising chlorophyll. As known in the art - chlorophyll is soluble in oil/fat and not in water at any 15 herein relevant pH range. As known in the art, the herein relevant copper chlorophyllin green pigment is not soluble in oil/fat. The two WO documents do not describe use of quillaja in a herein relevant sol id-in-water dispersion (such as e.g. a soft drink). 20 SUMMARY OF THE INVENTION The problem to be solved by the present invention is to provide a green color 25 ing composition, giving a green transparent color in acid applications, compris ing copper chlorophyllin as a green pigment, wherein the green coloring com position does not have a herein relevant unwanted unpleasant taste (i.e. is not comprising significant amounts of Polysorbate 80 (Tween 80)). 30 The solution is based on the fact that the present inventors has identified that a water-dispersible composition using quillaja as dispergent agent is very good in relation to use of copper chlorophyllin as a green pigment - see working ex amples herein for further details.

WO 2013/167644 PCT/EP2013/059563 -3 An advantage of quillaja is that it does not have a herein relevant unwanted unpleasant taste (i.e. like Polysorbate 80 (Tween 80)). As can be seen in reference Example 3 herein - for instance polyglycerol is 5 NOT working satisfactory for copper chlorophyllin - i.e. one may say that quil laja works surprisingly better. Polyglycerol and quillaja have both a relatively high Hydrophilic-lipophilic bal ance (HLB) value - however, even though Polyglycerol has a relatively high HLB value it is not working properly in the present context. 10 Accordingly, a first aspect of the invention relates to a water-dispersible green composition comprising from 0.5% to 70% (w/w on a water free basis) of cop per chlorophyllin as a green pigment and from 1.0% to 80% (w/w on a water free basis) of quillaja. 15 An example of a composition of the first aspect is shown in working Example 1 herein - wherein the composition comprises 8.2% (w/w on a water free basis) of copper chlorophyllin and 26.2% (w/w on a water free basis) of quillaja. The rest of the material/substance of the composition/suspension of Example 1 20 herein was Propylene glycol: 6 5.

6 % (w/w on a water free basis) and around 50-52% water. Preferably, the water-dispersible green composition of the first aspect compris es less than 9 0% (w/w) of water. 25 As known in the art - copper chlorophyllin is soluble in water at alkaline pH and relatively insoluble at lower pH ranges - such as at pH around pH 3, which is roughly the pH value of e.g. commercially relevant soft drink products. 30 The water-dispersible composition as described herein may advantageously be used for green coloring of a herein relevant edible, drinkable or pharmaceutical product - such as in particular a product with a herein relevant not alkaline pH value.

WO 2013/167644 PCT/EP2013/059563 -4 By using water-dispersible composition as described herein for green coloring it is possible to obtain a stable transparent green solid-in-water dispersion prod uct (e.g. a soft drink or a wine gum product) - see e.g. working Example 2 herein, where a stable transparent green soft drink product was made. 5 Accordingly, a second aspect of the invention relates to a transparent green solid-in-water dispersion product comprising copper chlorophyllin particles as a green pigment and quillaja as dispergent agent and wherein the pH of the dis persion is from pH 1 to pH 8 and wherein the ratio (w/w) of copper chlorophyl 10 lin and quillaja is a ratio from 0.01 to 10. A third aspect of the invention relates to a method for preparing the water dispersible composition of the first aspect, wherein method comprises the fol lowing steps: 15 (i): dissolving adequate amount of copper chlorophyllin in a solvent to get a solution; (ii): adding the solution of step (i) to a solution of quillaja under stirring to thereby obtain the water-dispersible composition of the first aspect. 20 A fourth aspect of the invention relates to a method for making a transparent green solid-in-water dispersion product of the second aspect, wherein the method comprises dispersing the water-dispersible composition of the first as pect into a water based product with a pH 1 to pH 8 to thereby obtain the transparent green solid-in-water dispersion product of the second aspect. 25 A fifth aspect of the invention relates use of the water-dispersible composition as described herein to green coloring of an edible, a drinkable or a pharmaceu tical product. 30 DEFINITIONS All definitions of herein relevant terms are in accordance of what would be un derstood by the skilled person in relation to the herein relevant technical con text.

WO 2013/167644 PCT/EP2013/059563 -5 The term "pigment" relates to a material that changes the color of light it re flects as the result of selective color absorption. This physical process differs from fluorescence, phosphorescence, and other forms of luminescence, in 5 which the material itself emits light. The term "green pigment" simply relates to a pigment that gives a green color. When used as a pigment as described herein copper chlorophyllin will always give a green color and the term "green" in relation to use of copper chlorophyl 10 lin as described herein may therefore be seen as merely descriptive - i.e. not a limiting term. The term "green coloring" in relation to the use of the water-dispersible com position as described herein simply relates to the fact that the copper chloro 15 phyllin pigment gives a green color. The term "solid-in-water dispersion" should be understood as the skilled per son would understand it in the present context. For instance, in relation to a transparent green solid-in-water dispersion product as discussed herein - cop 20 per chlorophyllin particles are solid particles dispersed in the water phase of the solid-in-water dispersion. Embodiment of the present invention is described below, by way of examples only. 25 DETAILED DESCRIPTION OF THE INVENTION Water-dispersible composition 30 Beside the copper chlorophyllin (as a green pigment) and the quillaja the wa ter-dispersible composition as described herein may of course comprise other herein relevant material/substances. For instance may the water-dispersible composition comprise another emulsifi er (dispergent agent) than quillaja.

WO 2013/167644 PCT/EP2013/059563 -6 As evident to the skilled person, when there herein is described relevant per centage (%) of e.g. copper chlorophyllin (as a green pigment) and e.g. quillaja the sum of such percentages can of course not exceed 100% in the water dispersible composition as described herein. 5 Copper chlorophyllin is as such a well known green pigment - it has the com mon E-number E141(ii) (see EU food additive legislation). The copper chlorophyllin may e.g. be potassium copper chlorophyllin or sodium 10 copper chlorophyllin. Quillaja is as such known to the skilled person. An example of a herein suitable quillaja product is a to 20% in water diluted quillaja product that has the common E-number E999 (see EU food additive 15 legislation) In working Example 1 herein the commercially available product Q-Naturale@ from National Starch, UK was used. The Merck Index, Twelfth Edition mentions examples of herein suitable quillaja product/sources - such as e.g. Merck Index number 8222 (Quillaja, from bark) 20 and Merck Index 8223 (Quillaja, Saponin). In the present context it may be preferred to have a relative concentrated wa ter-dispersible green composition as described herein - e.g. in order to have a concentrated color product, wherein one e.g. only has to add a few drops to 25 e.g. a soft drink product in order to get a soft drink with a herein relevant suit able green color. Accordingly, it may be preferred that the water-dispersible green composition as described herein comprises less than 70% (w/w) of water, more preferably 30 less than 50% (w/w) of water and even more preferably less than 40% (w/w) of water. Preferably, the water-dispersible composition comprises from 2% to 95% (w/w on a water free basis) of a solvent, such as e.g. propylene glycol as a solvent.

WO 2013/167644 PCT/EP2013/059563 -7 In working Example 1 herein a preferred composition comprising 65.6 % pro pylene glycol (w/w on a water free basis) as a solvent is described. Preferably, the water-dispersible composition comprises from 15% to 85% 5 (w/w on a water free basis) of a solvent, such as e.g. propylene glycol as a solvent. The water-dispersible composition may be a liquid composition, in particular wherein the liquid composition is a liquid solution. 10 The composition of working Example 1 herein is an example of a liquid solu tion. Alternatively, the water-dispersible composition may be a dry powder composi tion. 15 Preferably, the water-dispersible green composition as described herein com prising from 2% to 40% (w/w on a water free basis) of copper chlorophyllin as a green pigment and from 5% to 6 0% (w/w on a water free basis) of quillaja; more preferably the water-dispersible green composition as described herein 20 comprising from 3 % to 2 0% (w/w on a water free basis) of copper chlorophyl lin as a green pigment and from 15% to 3 5% (w/w on a water free basis) of quillaja. A transparent green solid-in-water dispersion 25 As discussed above - an example of a herein relevant transparent green solid in-water dispersion of the second aspect could e.g. be a soft drink or wine gum. 30 As discussed above - a herein relevant advantage of water-dispersible compo sition as described herein it that it may be used obtain a stable transparent green solid-in-water dispersion product (e.g. a soft drink or a wine gum prod uct) - see e.g. working Example 2 herein, where a stable transparent green soft drink product was made.

WO 2013/167644 PCT/EP2013/059563 Accordingly, as discussed above - a second aspect of the invention relates to a transparent green solid-in-water dispersion product comprising copper chloro phyllin particles as a green pigment and quillaja as dispergent agent and wherein the pH of the dispersion is from pH 1 to pH 8 and wherein the ratio 5 (w/w) of copper chlorophyllin and quillaja is a ratio from 0.01 to 10. Without being limited to theory - it is believed that quillaja works as disper gent agent in the sense that it stably disperses the copper chlorophyllin parti cles so there is not unwanted sedimentation of the copper chlorophyllin parti 10 cles. As known to the skilled person - when there is unwanted sedimentation of the copper chlorophyllin particles the herein relevant green color will be lost. Further - it is believed that quillaja work as a dispergent agent in the sense 15 that it is involved in getting copper chlorophyllin particles of a relatively small size. As known to the skilled person - if the copper chlorophyllin particles are too big in size then will the product (e.g. a soft drink) not be properly transparent. 20 A further advantage of such small particles is that they have very little tenden cy of sedimentation. In the present context - the skilled person knows whether a herein relevant product is properly transparent or not and this will generally depend on the 25 specific product of interest (e.g. if it is e.g. a soft drink or e.g. wine gum). The term "transparent" of the second aspect should be understood in this con text - i.e. as the skilled person will understand it in the present context. As discussed above - the transparency is related to the size of the copper chlo 30 rophyllin particles and this is related to the ratio (w/w) of copper chlorophyllin and quillaja in the transparent product of interest. As evident to the skilled person in the present context - if there is an indefi nitely small amount of quillaja present as compared to the amount of copper chlorophyllin then will the effect of the quillaja be very limited and one would WO 2013/167644 PCT/EP2013/059563 -9 then get e.g. too big size copper chlorophyllin particles (i.e. bad transparency) or sedimentation of the copper chlorophyllin (i.e. green color is lost). Preferably, the transparent green solid-in-water dispersion as described herein 5 is a dispersion, wherein the ratio (w/w) of copper chlorophyllin and quillaja is a ratio from 0.03 to 5; more preferably a ratio from 0.05 to 2 and even more preferably a ratio from 0.1 to 1. Economically quillaja may be seen as a production cost herein (it is not as such 10 giving the green color). Accordingly, overall one may say that it is herein preferred to use a minimum amount of quillaja - but still enough to get the herein relevant stable transpar ent green color. 15 Preferably, the transparent green solid-in-water dispersion as described herein is a dispersion, wherein the copper chlorophyllin particles are having an aver age particle diameter of less than 5 pm, more preferably the copper chloro phyllin particles are having an average particle diameter of less than 2 pm, even more preferably the copper chlorophyllin particles are having an average 20 particle diameter of less than 1 pm and most preferably the copper chlorophyl lin particles are having an average particle diameter of less than 200 nm. A transparent green solid-in-water dispersion as described herein may be a dispersion, wherein the pH of the dispersion is from pH 1 to pH 6 or wherein 25 the pH of the dispersion is from pH 1 to pH 5. As discussed above - the pH of a soft drink may be around pH 3. A transparent green solid-in-water dispersion may be a herein relevant edible, drinkable or pharmaceutical product. 30 Preferably, transparent green solid-in-water dispersion is a food product or a beverage product - preferably for human use. Preferred examples of edible or drinkable product may be a soft drink or wine gum.

WO 2013/167644 PCT/EP2013/059563 - 10 A method for preparing the water-dispersible composition As discussed above, the third aspect of the invention relates to a method for preparing the water-dispersible composition of the first aspect, wherein meth 5 od comprises the following steps: (i): dissolving adequate amount of copper chlorophyllin in a solvent to get a solution; (ii): adding the solution of step (i) to a solution of quillaja under stirring to thereby obtain the water-dispersible composition of the first aspect. 10 As evident to the skilled person one may make adequate adjustments of the method in order to get a specific water-dispersible composition of interest. A herein suitable solvent may propylene glycol - in working Example 1 herein 15 was used propylene glycol as solvent. Without being limited to theory - quillaja as such could maybe be used as a suitable solvent. Further, water at a suitable pH could also maybe be used as a suitable solvent. 20 Propylene glycol is liquid at room temperature - accordingly, if propylene gly col is used as a solvent one may directly get a liquid composition. As discussed above - an example of a herein suitable quillaja product is a to 25 20% in water diluted quillaja product - if such water containing quillaja prod uct is used one may directly get a liquid composition. Further, if one e.g. wants a dry powder composition the method may comprise the further step of drying. 30 A method for making a transparent green solid-in-water dispersion As discussed above, the fourth aspect of the invention relates to a method a method for making a transparent green solid-in-water dispersion product of the second aspect, wherein the method comprises dispersing the water- WO 2013/167644 PCT/EP2013/059563 - 11 dispersible composition of the first aspect into a water based product with a pH 1 to pH 8 to thereby obtain the transparent green solid-in-water dispersion product of the second aspect. 5 In the present context may this method be seen as routine work for the skilled person and it may therefore not be described in great details herein. Use of the water-dispersible composition 10 As discussed above, the fifth aspect of the invention relates to use of the wa ter-dispersible composition as described herein to green coloring of an edible, a drinkable or a pharmaceutical product. Essentially, this use may herein be seen as corresponding to know prior art 15 uses of water-dispersible compositions comprising herein relevant coloring pigments. Accordingly, it is herein not required in details to describe how such composi tions are used for coloring of a herein relevant edible or pharmaceutical prod uct - the skilled person knows how to use it in relation to obtainment of specif 20 ic objectives (e.g. degree of coloring) of interest. Preferably, the product is a food product or a beverage product - preferably for human use. 25 Preferred examples of edible or drinkable product may be a soft drink or wine gum. 30 WO 2013/167644 PCT/EP2013/059563 - 12 EXAMPLES EXAMPLE 1: In the laboratory a product according to the invention was produced: 5 Ingredient Amount grams /o w/w on a water free basis Quillaja 64 grams (20% pure - 26.2% Q-Naturale@ from Na- rest including water) tional Starch, UK => 12.8 grams Quillaja Propylene glycol 32 grams 65.6% Sodium copper chloro- 4 grams 8.2% phyllin The copper chlorophyllin was dissolved in the solvent propylene glycol - while stirring and heating to 600C. When the copper chlorophyllin had dissolved the solution was cooled to room 10 temperature and added to the quillaja solution under stirring. A dark green liquid solution was obtained. EXAMPLE 2: In the laboratory the product produced as described in Example 1 was tested 15 as follows. A few drops of the water water-dispersible green composition of example 1 were added to a standard soft drink medium with pH of 3. A nice transparent green color was obtained. 20 The soft drink medium corresponds to a standard commercially available soft drink media. The result was a transparent green solid-in-water soft drink dispersion that 25 was stable in the sense that it was still green and transparent and showed no sedimentation after two days storage at room temperature.

WO 2013/167644 PCT/EP2013/059563 - 13 EXAMPLE 3: This example is a comparative example using polyglycerol ester as a dispersing agent. In this example was used the same ingredients in approximately the 5 same amounts as in Example 1 - except polyglycerol ester had replaced the quillaja - i.e. a true comparative example. The comparative polyglycerol containing composition was tested as in Example 2. 10 The result was a soft drink dispersion that was not stable in the sense that af ter two days storage at room temperature there was a significant sedimenta tion of green pigment - i.e. the soft drink had lost its green color. 15 Accordingly, the results of this comparative example clearly demon strated that quillaja works significantly better than polyglycerol.

WO 2013/167644 PCT/EP2013/059563 - 14 REFERENCES 1: Publicly available product information - natural green color product of Chr. Hansen A/S, Denmark termed "C-10.OOOP-WS-AP" 5 2: Publicly available product information - natural green color product of Chr. Hansen A/S, Denmark is termed "CapColors@Green 100". 3: W02011/119290A1 10 4: W02011/154407A1 15

Claims

1. A transparent green solid-in-water dispersion product comprising copper chlorophyllin particles as a green pigment and quillaja as dispergent agent and wherein the pH of the dispersion is from pH 1 to pH 8 and wherein the ratio (w/w) of copper chlorophyllin and quillaja is a ratio from 0.01 to 10.

2. The transparent green solid-in-water dispersion product of claim 1, wherein the ratio (w/w) of copper chlorophyllin and quillaja is a ratio from 0.1 to 1.

3. The transparent green solid-in-water dispersion product of any one of claims 1 to 2, wherein the copper chlorophyllin particles are having an average particle diameter of less than 1 pm.

4. The transparent green solid-in-water dispersion product of any one of claims 1 to 3, wherein the pH of the dispersion is from pH 1 to pH 5.

5. The transparent green solid-in-water dispersion product of any one of claims 1 to 4, wherein the dispersion product is a food product or a beverage product.

6. The transparent green solid-in-water dispersion product of claim 5, wherein the product is a soft drink or wine gum. Chr. Hansen Natural Colors A/S Patent Attorneys for the Applicant/Nominated Person SPRUSON & FERGUSON (10385513_1) :GGG