FR2974976A1 - Ice block comprises water, polyol, water soluble coloring agents, a colored part, a colorless part, a colorless body, a colored envelope containing polyol and coloring agents, and a colored body containing polyol and coloring agents - Google Patents

Abstract

Ice block comprises water, polyol having 3-5C in a concentration of 0.1-4 wt.%, and water soluble coloring agents having a concentration of 0.5-100 mg/kg. Independent claims are included for: (1) a colorant additive in the form of aqueous solution for producing an ice block comprising applying an additive, in dilution ratio, in water, where the additive comprises water soluble coloring agents and polyol having 3-5C; (2) an ice block tray made of plastic material containing the additive; and (3) a process for producing an ice block comprising diluting the additive in water at a dilution ratio of 2-150, preferably 10.

Description

Additive for the production of colored ice cubes, colored ice cubes containing this additive and method of manufacture

The present invention relates to ice cubes or ice that are colored by adding a particular coloring additive.

The additive intended to color ice cubes according to the invention is advantageously in liquid form. It solubilizes quickly in water and allows to obtain ice cubes of homogeneous color.

It is known to use adjuvants such as ethanol, glycerin, sugar or xanthan gum to stabilize the dispersion of a dye. However, the Applicant has discovered that only the addition of a particular polyol in a precise concentration makes it possible to improve the dispersion of the dye in the ice cubes without significantly changing the melting rate of the ice cubes. This polyol also has the advantage of not altering the taste and smell of ice cubes.

The present invention thus has for its first object a dye additive for coloring ice cubes. This additive is an aqueous solution containing a dye and a polyol. The word "ice cube" in the sense of the present invention refers to pieces of ice that can have different sizes and shapes. Examples of icicles are pieces of ice obtained by pouring water into a mold placed in the freezer. The word ice cube within the meaning of the invention also refers to crushed ice, sliced ice, broken ice, sculpture ice and other forms of ice.

The coloring additive of the invention is in the form of an aqueous solution for the manufacture of ice cubes by applying a dilution ratio of said additive in water, said additive containing a water-soluble dye and a polyol, the polyol being chosen among the polyols having 3 to 5 carbon atoms, - the concentration of the polyol in the additive and the dilution ratio of the additive in the water being such that the ice cubes are intended to contain from 0.1 to 4% by weight, preferably from 0.5 to 1.5% by weight of polyol relative to the weight of ice cubes.

The present invention also relates to the use of this additive dye to prepare ice cubes, as well as ice cubes containing this additive.

The ice cubes contain water, a polyol having 3 to 5 carbon atoms in a concentration ranging from 0.1 to 4% by weight based on the weight of ice cubes, and one or more water-soluble dyes in a concentration ranging from 0.5 to 400 mg per kilogram of ice cubes. The additive according to the invention contains a polyol, i.e. a carbon compound comprising at least two -OH groups. The polyol comprises from 3 to 5 carbon atoms.

This compound makes it possible to improve the dispersion of the colorant (s) in the additive so that the color of the ice cubes is more homogeneous. The polyol has the advantage, in comparison with other compounds which also improves the dispersion of dyes, not to bring any odor or taste to the drink in which the ice cubes are placed and not to cause the icicles to melt in the drink too fast.

The Applicant has found that other polyols which are not in accordance with the invention, such as xanthan gum or sugar, do not make it possible to improve the homogeneity of the color in ice cubes. By using sugar in particular, ice cubes are fat on the surface and heterogeneous; we also observe the deposition of white grains at the bottom of the glass of water when the ice cubes have melted. The Applicant has also found that ethanol makes it possible to obtain well-frozen homogeneous colored ice cubes, but that they melt much too quickly. The ice cubes of the invention are therefore preferably devoid of ethanol, or contain a very small amount of ethanol, preferably less than 0.1% by weight relative to the weight of the ice cubes.

The polyol advantageously represents between 0.1 and 4% by weight, preferably between 0.5 and 1.5% by weight of the weight of the ice cubes, more preferably between 0.8 and 1.2% by weight of the ice cubes. Indeed, when the polyol concentration is less than 0.5%, the dye tends to remain on the surface of the ice cube so that the color is heterogeneous. When the polyol content exceeds 4%, it has been observed that the ice cubes tend to stick to each other and melt quickly. The polyol will be incorporated in the additive at a concentration inversely proportional to the dilution ratio of the additive in the water.

The polyol is for example chosen from monopropylene glycol, glycerol (also called glycerin) and mixtures thereof.

The additive of the present invention has many other advantages. The coloring of ice cubes is stable over time: for example the color of the ice cubes does not vary during their conservation. Ice cubes do not stain or color the drink very little. If the ice cubes made with the additive of the invention are used in a clear and opaque drink such as milk, the coloration of the ice cube is very visible, and the milk is hardly colored when the ice cubes are melted. With the additive according to the invention, the colors of the ice cubes are bright and deep.

Colored spots, possibly left on fabrics by the ice containing the additive, can also be easily removed by a simple washing.

The Applicant has selected dyes, determined their concentration and optimized the size of the ice cubes so as to obtain ice cubes which are colored in the mass, whose color is always perceived when they are put into a drink, and which do not stain or do not color the beverage once they have melted. The additive according to the present invention makes it possible to use very small amounts of dyes while obtaining a satisfactory color intensity, so that the quantity of dye ingested by the consumer with the beverage is limited and the cost price is reduced.

The dyes are water soluble. They may be chosen from compounds comprising at least two aromatic rings, at least two nitrogen atoms and at least two sulphonate groups.

The dye is, for example, chosen from N-ethyl-N- [4 - [[4- [ethyl [(3-sulfophenyl) methyl] amino] phenyl] (2-sulphophenyl) methylene] -2,5-cyclohexadiene. Sodium 1-ylidene] -3-sulfo-benzenemethanaminium, sodium 1- (1-naphthylazo) -2-hydroxynaphthalene-4 ', 6,8-trisulfonate, 4,5-dihydro-5-oxo-1- Sodium 4- (4-sulfophenyl) -4- [2- (4-sulfophenyl) diazenyl] -1H-pyrazole-3-carboxylate, and mixtures thereof. These dyes have the advantage of giving ice cubes in bright colors. Furthermore, the amount needed to color the ice in the mass satisfactorily is low enough to ensure frequent food use. A blue dye is preferably a disodium salt of triphenyl methane of the chemical formula C37H34N2Na2O9S3: This dye has a CAS number 3844-45-9 and the chemical name N-ethyl-N- [4 - [[4- [ethyl] Sodium (3-sulfophenyl) methyl] amino] phenyl] (2-sulfophenyl) methylene] -2,5-cyclohexadienylidene] -3-sulfo-benzenemethanaminium.

The following codes have been assigned to regulate its use in food products: E 133 (in Europe), FD & C Blue No. 1 (in the USA), I Blue 1 (in Japan), and CI Food Blue 2 - Cat.1 (in China). This dye is commercially available under many references such as Acid Blue 9; Brilliant Blue FCF; Dolkwal Brilliant Blue; Duasyn Acid Blue AE 02; Hexacol Brilliant Blue A; Puricolor Blue ABL 9; Sicovit Brilliant Blue 85E133; Unicert Blue 05601-J; and Usacert Blue No.

A red dye is preferably a trisodium salt of a monoazo compound of the chemical formula C20H11N2Na3O10S3: This dye has a CAS number 2611-82-7 and a chemical name of 1- (1-naphthylazo) -2-25 hydroxynaphthalene. 4 ', 6,8-trisulfonate sodium. It has been approved in many countries for food use under the following codes: E124 (code laughs H ,, o; 5 European), I Red 102 (Japanese code), CI Food Red 7 - Cati. (Chinese food code). It can be found commercially under many references such as Cochineal Red A; Acid Red 18; Ponceau 4R; Scarlet 3R; New Coccine. Another red dye may be cochineal red or carmic acid of chemical formula C22H20013: OH OH OH

It carries the E120 food code in Europe and the C.I. Natural Red 4 code in the United States. Its CAS number is 1390-65-4.

A yellow dye is preferably a trisodium salt of a monoazo compound, of chemical formula C16H9N4Na309S2: This dye has for CAS number 1934-21-0 and for chemical name, 4,5-dihydro-5-oxo-1- (4-sulfophenyl) -4- [2- (4-sulfophenyl) diazenyl] -1H-pyrazole-3-carboxylate sodium. It has been approved in many countries for food use: E102 (European code 25), FD & C Yellow No. 5 (American code), I Yellow 4 (Japanese code), and CI Food Yellow 4 - Cat.1 (Chinese code) ). It can be found commercially under many references such as Acid Yellow; 1310 Yellow; 1409 Yellow; AizenTartrazine; Amacid Yellow; Basovit Yellow Calcocid Yellow; Canacert Tartrazine; Cogilor Yellow; Eurocert Tartrazine; Unicert Yellow 08005-J. These yellow, blue and red dyes can be mixed to create other colors. For example, a range of three to ten bottles of additives may be proposed in order to provide the user with ready-to-use colors. The amount of dye (s) in the additive is preferably selected such that the amount of dye (s) in the ice cube is between 0.5 and 400 mg per kilogram of ice, for example between 0.5 and 15. mg per kilogram of ice cube. The dye concentration in the additive and the dilution ratio of the additive are preferably such that the ice cubes are intended to contain between 0.5 and 400 mg of dye per kilogram of ice cubes.

The Applicant has indeed found that at concentrations of less than 0.5 mg per kilogram of ice, the color of the ice cube in the mass obtained with these dyes is not sufficient. The icing of the ice cube in the mass can be observed when the ice cubes are still in the freezing tank or when they have been demolded. At lower concentrations, it also becomes difficult to perceive the color of ice cubes once they have been put into a glass of water or drink. The Applicant has also determined that at concentrations greater than 400 mg per kilogram of ice, the coloring of the drink by the ice cubes becomes noticeable and can become unsightly. The amount of the dye contained in the additive according to the invention thus makes it possible to reach a compromise between the intensity of the color of the icicle observed in the drink before it melts, and the absence of pronounced coloration of the drink. wherein the ice cube is fully melted.

When the color is obtained with only one of the dyes described above, the amount of dye is preferably between 1 and 50 mg per kilogram of ice cube. According to one embodiment, the amount of dye is between 1 and 2 mg per kilogram of ice cube; it ranges, for example, from 1.4 to 1.6 mg per kilogram of ice cube. When the dyes are used as a mixture, the total dye content can be raised to between 4 and 225 mg per kilogram of ice cube, for example between 4 and 9 mg per kilogram of ice cube.

The dye may also be selected from heat-sensitive dyes, which emit a color at a temperature below 0 ° C, and are colorless at a temperature above 0 ° C.

The coloring additive according to the invention may be in the form of single-use doses, for example from 10 ml to 10 liters, which the user dilutes with water, preferably tap water. For example, a 50 ml dose of additive will be added to 500 ml with tap water, when the recommended dilution ratio is 10. The recommended dilution ratio will be adapted according to size, shape and the color of the ice cubes that we want to prepare. It can range from 2 to 150, for example be of the order of 10. The additive will preferably be free of preservatives.

The additive can be sold in the form of a range comprising several flasks, each of the flasks containing a different color additive. This range makes it possible to prepare ice cubes of different colors or to create new colors. The subject of the invention is also a range of coloring additives comprising at least two coloring additives according to the preceding description, in which the additives have different colors.

To prepare the additive, the ingredients are introduced into a closed vessel, equipped with a stirring system. The manufacturing, storage and packaging equipment must be perfectly clean and dry. In the tank are introduced water, polyol and dye. The water used to prepare the additive is preferably demineralized and free of chlorine. In one embodiment, the additive consists of the dye (s), the polyol and demineralized water. In order to facilitate the dilution of the dye and the preparation of the additive, a 0.1% by weight solution of a dye in demineralised water is preferably prepared, a defined amount being then mixed with the polyol and rest of the water. Stirring is maintained until homogenization. The additive is then packaged under a sterile atmosphere. The invention also relates to ice cubes containing water, a polyol having 3 to 5 carbon atoms in a concentration ranging from 0.1 to 4% by weight relative to the weight of ice cube, and a water-soluble dye. a concentration ranging from 0.5 to 400 mg per kilogram of ice cube. The ice cubes according to the invention may have various shapes. They generally have a mass of between 10 and 20 grams; the biggest ones can reach 25 grams. The ice cubes containing the additive of the invention are preferably used at a rate of 1 to 2 ice cubes per 100 ml of beverage, when the beverage is already colored and its color is not to be changed by melting the ice cubes.

The ice cubes may consist of a single portion homogeneously colored. They may be monoblock in the sense that they are prepared from a single colored aqueous solution, and that all their mass is colored.

The coloring additive according to the present invention also makes it possible to manufacture colored ice cubes comprising at least two parts whose color is different. The ice cubes may also comprise two parts, a colored part and a colorless part.

The ice cubes may for example consist of two parts, preferably a core and an envelope; in this case, we are talking about two-layer ice cubes. The heart can be colored while the envelope can be colorless. By colorless in the sense of the invention is meant that does not contain colored additive. In this embodiment, the colorless envelope advantageously allows not to leave traces on the fingers when taking the ice cube.

In another embodiment, the core is colorless and the envelope is colored and contains the polyol and the dye (s). Making colored bilayer ice cubes makes it possible to concentrate the dye in the envelope with an equivalent amount of dye and to obtain ice cubes that are more colorful than monolayer ice cubes. Color-coated bilayer ice cubes make it possible to use a smaller amount of dye than that used to prepare monolayer ice cubes while achieving the same color intensity, but also to significantly reduce the eventual coloration of the final drink, if this is the case. proves necessary. This may be the case for the realization of certain shades. The colored envelope will preferably be devoid of ethanol, so as not to accelerate the melting of the ice cube.

The thickness of the colored outer layer will preferably be between 1 and 10 mm. The thickness will preferably be uniform over the entire surface of the ice cube. It is for example of the order of 2 to 3 mm. The Applicant has in fact discovered that the increase of the outer layer of the ice cube beyond 2 mm does not improve the intensity of the color of the latter. If the ice cube is prepared with a dye or a mixture of dyestuff in such a quantity that the beverage tends to color when the ice cube is melted, the thickness of the unstained layer may be increased so as to delay the appearance of color in the drink.

Ice cubes may include a cavity in which pieces of fruit or flowers are inserted.

To prepare the ice cubes, the additive according to the present invention will preferably be diluted in water at room temperature, preferably in mineralized water such as tap water.

To prepare bilayer ice cubes according to the present invention, ice cubes are produced in a first mold (heart mold) which will form the core of the bilayer ice cube. A second mold (envelope mold) whose cavities have a larger dimension is provided to pour the water and form the envelope. According to one variant, the water will be colored. For the purposes of the present invention, the term "colored water" refers to water in which the dye additive has been diluted.

According to a first embodiment, the water is poured into the mold "envelope" so as to glaze only the bottom and to prepare a first portion of the envelope. The heart ice cubes are prepared and then demolded to be placed on the icy bottom which has been prepared in the shell mold; he is careful to center the hearts in the cavities of the envelope mold. The rest of the water is poured to form the sides and the top layer, then iced.

According to a second embodiment, the heart ice cubes are demolded and transferred to the second mold, taking care to center the hearts. The cavities of the second mold have pins that allow colored water or not to wrap the heart in one step. During all these steps the water will preferably be at a temperature of the order of 5 ° C so as not to cause melting of already frozen parts.

The ice cube mold used to make two-layer ice cubes may have the form reproduced in Figure 1. In the left-hand section, the internal ice cubes made of water alone or colored water will be made first. These ice cubes will then be tilted to the right and kept centered with respect to the cavities, and water alone or colored will be poured into the cavities to form the outer layer.

According to one embodiment of the invention, the bilayer ice cubes have a core whose volume is greater than the volume of the outer layer. This type of ice will be used when it is desired to avoid the coloration of the final drink after the melting ice cubes. In this case, the thickness of the outer layer of the ice cube will preferably be set between 2 and 3 mm and the amount of dye between 1 and 2 mg per kilogram of ice cubes.

In another variant, the volume of the outer layer is greater than that of the heart, so as to intensify the color of the ice cube, without increasing the amount of dye that would be used to prepare a monobloc ice cube. In this same variant, the amount of dye incorporated in the outer layer may be less than that which would be used to prepare a one-piece ice cube, in order to obtain the same final color with a reduced amount of dye.

In this case, the thickness of the outer layer of the ice cube will preferably be set between 3 and 5 mm and the amount of dye between 2 and 6 mg per kilogram of ice cubes.

The subject of the invention is also a process for the preparation of ice cubes, which consists in diluting the additive described above in water at a dilution ratio ranging from 2 to 150, preferably of the order of 10. recommended dilution will be adapted according to the size, shape and color of the ice cubes that one wishes to prepare. It can range from 2 to 150, for example be of the order of 10. The additive can be diluted in one step or in several steps. To facilitate the dilution of the additive, it is possible, if necessary, to dilute the additive to 0.1% by weight of the dye (s) in water, preferably in demineralized water, and to carry out a second dilution. to obtain the desired concentration of dye (s).

Ice cubes can be made in conventional professional machines with manual or automatic feed. Traditional ice trays can also be used. Ice machines usually have a direct and continuous connection to the running water supply. A food grade tub to hold the colored water will be placed between the ice maker and the water supply. The tank can be connected to the incoming water inlet and is connected to the ice machine at the outlet. It can include if necessary a stirrer. The bowl includes a manual opening for pouring the colored additive. It also has a connection for filling with city water. In a variant, the mixture of the colored additive in the tap water can be provided by a static mixer located between the city water supply and the tank. The tank is advantageously graded to control the amount of colored additive poured and the amount of dilution water added. The ice cubes may be prepared according to one of the methods described in WO 00/17589 and US Pat. No. 6,513,337.

The solidification temperature of the ice cubes is preferably between -5 ° C and -18 ° C.

During the preparation of the ice cubes, especially in the dilution water or in the molds, it is possible to add aromas or pieces of plants such as fruits or flowers (small berries, fruit zest, petal). Vitamins or food supplements (trace elements, plant extracts, mineral salts) can also be added to ice cubes at concentrations compatible with the color and transparency of ice cubes.

The present invention also relates to plastic ice packs containing an additive as described above. These bags are advantageously equipped with communicating compartments that are filled with water to prepare ice cubes.

These sachets may be offered for sale in the form of a kit also containing one or more bottles of color additive.

In another variant, the pouches may be sold pre-filled with the additive so that the user does not need to handle and dose the additive. Just add the water usually used, then put the bags in the freezer after mixing. Finally, the bags can be offered for sale pre-filled with colored water. To prepare the ice cubes, simply put the bag in the freezer, the tightness of the bag to avoid the use of preservative. The sachets may be sold in batches containing the same color additive, or in batches comprising several colors of different additives. The pouches may be in accordance with the teachings of EP 1 369 649. The plastic bags will preferably be colorless to better control the color of prepared ice.

The present invention is illustrated by the following examples. EXAMPLE 1 The additives of the following composition were prepared: Weight DEMINERALIZED WATER Purified water 89.9973 GLYCERIN Glycerol or [422 Brenntag 10.00 Dyestuff See below Sensient Cosmetic 0 00268 Technologies LCW 'J Technologies COMMERCIAL NAME FOOD NAME SUPPLIERS% The dye is either Unicert® Blue 05601-J, Ponceau 4R® 80% or Unicert® Yellow 08005-J, all supplied by LCW. COMMERCIAL NAME FOOD NAME SUPPLIERS% by weight DEMINERALIZED WATER Purified water 89.9964 GLYCERIN Glycerol or E422 Brenntag 10.00 UNICERT® BLUE 05601-J E133 Sensient Cosmetic 0.0018 Technologies UNICERT® YELLOW 08005- E102 Sensient Cosmetic 0.0018 These color additives are diluted 10 times with tap water (they are added a volume of water equal to 9 times their volume) to prepare one-piece ice cubes of dimensions 2.5 x 10 2.5 x 2.5 cm or 15.625 cm3 . They are placed in the freezer at -15 ° C for 6 hours. The ice cubes are of a homogeneous color, and do not color 100 ml of water when they melt.

These coloring additives can also be used to prepare bilayer ice cubes having the following dimensions: Total dimensions of the ice cube: 2.5 x 2.5 x 2.5 cm or 15.625 cm3 Dimensions of the internal ice cube: 2.0 x 2.0 x 2,0 cm or 8 cm3 Two ice cubes thus prepared and put in a glass of water of 100 ml do not color the drink.

These coloring additives may also be used to prepare bilayer ice cubes having the following dimensions: Total dimensions of the ice cube: 2.5 × 2.5 × 2.5 cm or 15.625 cm 3 Dimensions of the inner ice cube: 1.7 × 1.7 × 1 , 7 cm or 4.913 cm35 The ice cubes thus prepared have a more contrasting color than the bilayer ice cubes previously obtained.

EXAMPLE 2 13.77 g ice cubes, of dimensions different from those of Example 1: 3 cm × 2 cm × 2.55 cm, are prepared in a translucent pan, by varying the amount of dye. The coloring additives are diluted in variable proportions (see table below) with tap water to prepare one-piece ice cubes of the required size. They are placed in the freezer at -10 ° C for 8 hours. The dye is either Unicert® Blue 05601-J, Ponceau 4R® 80% or Unicert® Yellow 08005-J, all supplied by LCW. Amount of Appearance of ice cubes Appearance of 2 ice cubes of Appearance of dye in mg in the tank 13.77 g in 100 ml final solutions in 2 ice cubes of city water after melting ice cubes 0.009 Ice cubes very little Icicles are very few Solutions very slightly colored for the 3 colored and do not stand out colored not dyes 0.018 0.045 Icicles well colored The color of the ice cubes Solution little for the 3 dyes is visible in the colored water 0.066 Colored solution15

Claims (14)

REVENDICATIONS1. Icicles containing water, a polyol having 3 to 5 carbon atoms in a concentration of 0.1 to 4% by weight based on the weight of ice cubes, and one or more water-soluble dyes a concentration ranging from 0.5 to 400 mg per kilogram of ice cubes. 2. Ice cubes according to the preceding claim, characterized in that they are monoblock in that they are prepared from a single colored aqueous solution, and that all their mass is colored. 3. Ice cubes according to claim 1, characterized in that they comprise two parts, a colored part and a colorless part. 4. Ice cubes according to the preceding claim, characterized in that they comprise a colorless core, and a colored envelope containing the polyol and the dye (s). 5. Ice cubes according to claim 3, characterized in that they comprise a colored core containing the polyol and the dye, and a colorless envelope. 6. Colorant additive in the form of an aqueous solution intended to be used for the manufacture of ice cubes by applying a dilution ratio of said additive in water, said additive containing a water-soluble dye and a polyol, the polyol being chosen from polyols having of 3 to 5 carbon atoms, - the concentration of the polyol in the additive and the degree of dilution of the additive being such that the ice cubes are intended to contain from 0.1 to 4% by weight of polyol relative to the weight ice cubes. 7. Additive according to the preceding claim, characterized in that the polyol is monopropylene glycol, glycerol or a mixture thereof. 8. Additive according to claim 6 or 7, characterized in that the concentration of the polyol in the additive and the dilution ratio of the additive in water are such that the ice cubes are intended to contain from 0.5 to 1, 5% by weight of polyol relative to the weight of ice cubes. 9. Additive according to one of claims 6 to 8, characterized in that the dye concentration in the additive and the dilution ratio of the additive are such that the ice cubes are intended to contain between 0.5 and 400 mg of dye per kilogram of ice cubes. 10. Additive according to one of claims 6 to 9, characterized in that it consists of the dye or dyes, polyol and demineralized water. 11. Range of coloring additives comprising at least two coloring additives according to one of claims 6 to 10, wherein the additives have different colors. 12. Plastic ice bags containing an additive according to one of claims 6 to 10. 13. A method of preparing ice cubes which comprises diluting the additive according to one of claims 6 to 10 in water at a dilution ratio ranging from 2 to 150, preferably of the order of 10. 14. Use of the additive according to one of claims 6 to 10 for preparing ice cubes.