PL236931B1 - Natural dye based on vegetable carbon in the form of a paste, and method of its production - Google Patents

Description

Description of the invention

The subject of the invention is a recipe and a comprehensive technology for the production of carbon paste as a natural dye based on vegetable carbon for coloring food.

The concept of the invention is based on micronized bamboo vegetable carbon with an average particle size of <1 gm (d10), which is a component of a carbon paste based on: high molecular weight modified amphiphilic starch OSA type (FLO-MAX ™ 2110 corn starch preparation) with the addition of xanthan gum ( 0.1%) as a thickener and suspending agent as well as water without the addition of glycerol. Micronization of bamboo charcoal guarantees effective suspension of particles in the matrix of pastes and / or food and effective dyeing as a black dye. The physical properties of pastes, the density (at 1120 kg / m ³⁾ and viscosity (at 750 cps) for easy and aplikowalność dozowalność in industrial practice.

The taste and the color that stimulates the appetite have always been one of the key factors determining the choice of a given food product (Spence, C. (2015). On the psychological impact of food color. Flavor, 4 (1), 21). The color emphasizes the taste. This is the first element by which the consumer recognizes a food product. The process of tasting a product begins with its selection on the store shelf, and this largely depends on the color. Food without color would be monotonous. Consumers perceive non-colored food differently and experience different emotions and sensations while eating (Burrows, JD (2009). Palette of our palates: a brief history of food coloring and its regulation. Comprehensive Reviews in Food Science and Food Safety, 8 (4), 394-408).

In the food industry, the natural dye E 153 VEGETABLE CARBON (Vegetable Black Number according to Color Index 77266 Number according to EINECS 231-153-3) is mainly used for dyeing and shading colors in sugar industry (Bechtold, T., & Mussak, R. (Eds.) . (2009). Handbook of natural colorants. John Wiley & Sons., Lehto, S., Buchweitz, M., Klimm, A., Straβburger, R., Bechtold, C., & Ulberth, F. (2017). Comparison of food color regulations in the EU and the US: a review of current provisions. Food Additives & Contaminants: Part A, 34 (3), 335-355.). Recent applications include: - for the production of black ice cream - for the coloring of sugar masses, creams and coatings for cakes, muffins, cakes for baking - for the production of sweets. Activated is used to clarify wines, juices, vinegar, discolor preparations and solvents, remove fragrances and impurities.

Vegetable carbon E 153 (Commission Regulation (EU) No 231/2012 of 9 March 2012 laying down specifications for food additives listed in Annexes II and III to Regulation (EC) No 1333/2008 of the European Parliament and of the Council) is black, odorless powder, resistant to light, heat, acids and bases, to physical and chemical factors (Rutkowski, A., Gwiazda, S., & Dąbrowski, K. (2003). Compendium of food additives. Hortimex.). Contains: not less than 95% carbon on an anhydrous and ash-free basis, not more than 12% humidity (loss on drying 120 ° C, 4 hours), not more than 4.0% ash, polycyclic aromatic hydrocarbons Benzo (a) pyrene less than 50 g / kg in the extract (1 g of product and 10 g of pure cyclohexane). Insoluble in water and organic solvents.

Natural dye E 153 VEGETABLE CARBON is commercially available in the form of sticky pastes with a dye content of 4-10% (not more than 20%), usually based on glucose syrup, but also other carriers, because it is a powdery powder itself, with particles usually smaller than 5 gm, and in this form a material very difficult to handle and apply (Wrolstad, RE, & Culver, CA (2012). Alternatives to those artificial FD&C food colorants. Annual review of food science and technology, 3, 59-77., Houghton, JD, & Hendry, GAF (2012). Natural food colorants. Springer Science & Business Media). Thanks to the enormous potential in the field of sourcing and processing of raw materials around the world, the offer of vegetable carbon coloring components in the form of powder formulations is consistently developed.

The basic starting materials for the preparation of the inventive paste in the form of a stable carbon paste with high dyeing strength were modified OSA starch and xanthan gum - functional carriers having specific properties of viscosity, stabilizing and suspending particles.

Modified starch of the OSA type, i.e. the sodium salt of starch octenyl succinate (octenyl sodium starch succinate) in the list of food additives is marked with the symbol E 1450. It acts as a stabilizer, thickener, binder, carrier and emulsifier. According to the Commission Directive 2010/69 / EU of 22 October 2010, the Scientific Committee for Food established the Acceptable Daily Intake (ADI) as "not specified" for the stabilizer E 1450, therefore this additive does not pose a risk to the health of consumers.

PL 236 931 B1

Starch is a polysaccharide, the building unit of which is a-D-glucose molecule. Native starch is hydrophilic in nature, therefore it does not show surface properties (Murύa-Pagola B., Beristain-Guevara CI, Martinez-Bustos F. (2009). Preparation of starch derivatives using reactive extrusion and evaluation of modified starches as shell materials for encapsulation of flavoring agents by spray drying. J. Food Eng. 91 (3), 380-386.). However, it is possible to impart these properties by chemical modification (Taggart, P., & Mitchell, J. R. (2009). Starch. In Handbook of Hydrocolloids (Second Edition) (pp. 108-141.)). As a result of the esterification of the hydroxyl groups of the starch with a hydrophobic substituent, it acquires an amphiphilic character. One of the most frequently used modifications of this type is esterification of starch with octenylsuccinic acid anhydride in an alkaline environment (Magnusson E., Nilsson L. (2010). Interactions between hydrophobically modified starch and egg yolk proteins in solution and emulsions, Food Hydrocoil. 25 (4), pp. 764-772., Nilsson L., Bergenstahl B. (2007). Adsorption of hydrophobically modified anionic starch at oppositely charged oil / water interfaces. J. Colloid Interface Sci. 308 (2), 508-513.). The derivative obtained in this way is called starch octenyl succinate (OSA). The substituent may be attached to the 2, 3 and 6 carbons of the glucose molecule in an amount not exceeding 3% on s.s. (degree of substitution D.S. ~ 0.02). This degree of substitution is typical for commercial preparations, as increasing it would not improve the surface properties of starch (Magnusson E., Nilsson L. (2010). Interactions between hydrophobically modified starch and egg yolk proteins in solution and emulsions, Food Hydrocoll. 25 (4 ), pp. 764-772 .; Nilsson L., Bergenstahl B. (2007). Adsorption of hydrophobically modified anionic starch at oppositely charged oil / water interfaces. J. Colloid Interface Sci. 308 (2), 508-513; Shogren RL, Viswanathan A., Felker F., Gross RA (2000) Distribution of octenyl succinate groups in octenyl succinic anhydride modified waxy maize starch, "Starch / Starke", 52 (6-7), pp. 196-204. ). OSA starch preparations in aqueous solutions are almost colorless and tasteless. They do not modify the natural taste and color of the product (Tesch S., Gerhards Ch., Schubert H. (2002). Stabilization of emulsions by OSA starches. J. Food Eng. 54 (2), 167-174.). Moreover, starch is a polymer that has a glass transition temperature in the range of 151 to 243 ° C, so it can be exposed to the high temperatures used in the drying process and does not undergo glass transition.

The attachment of an anionic octenylsuccinate group to the starch chain also gives it ionic character, thanks to which it gains the ability to electrostatically stabilize dispersion systems, mainly oil-in-water emulsions (Nilsson L., Bergenstahl B. (2007). Adsorption of hydrophobically modified anionie starch at oppositely charged oil / water interfaces. J. Colloid Interface Sci. 308 (2), 508-513.). OSA amphiphilic starch can adsorb at the interface and spatially stabilize the dispersion system. The steric hindrances created by the branching of the polymer prevent the particles of the dispersed phase from approaching and aggregating (Tesch S., Gerhards Ch., Schubert H. (2002). Stabilization of emulsions by OSA starches. J. Food Eng. 54 (2), 167- 174.). Modig et al. (2006) claim that a significant increase in the spatial stabilization of the emulsion occurs even at a low concentration of starch. Moreover, this polymer increases the viscosity of the continuous phase of the system, which additionally stabilizes the system. Starch octenyl succinate acts as both a surfactant and a texture modifying stabilizer for the continuous phase (Tesch S., Gerhards Ch., Schubert H. (2002). Stabilization of emulsions by OSA starches. J. Food Eng. 54 (2), 167-174.) . Yusoff and Murray (Yusoff A., Murray BS (2011). Modified starch granules as particle-stabilizers of oil-in-water emulsions. Food Hydrocoil. 25 (1), 42-55.) Proved that OSA starch can also effectively stabilize the o / w emulsion using the Pickering mechanism, which consists in adsorption at the phase boundary of solid particles with a diameter smaller than the diameter of the inner phase droplet.

Highly functional preparations of modified starches of the OSA type are particularly effective in microencapsulating flavors, lipids and lyophilic substances and in stabilizing beverages and dressings (Shogren RL, Viswanathan A., Felker F., Gross RA (2000). Distribution of octenyl succinate groups in octenyl succinic anhydride modified waxy maize starch, "Starch / Starke", 52 (6-7), pp. 196-204., Domian et al. 2013). They are an alternative to other natural hydrocolloids such as gum arabic or sodium caseinate. Starch octenylsuccinate meets all the requirements for carrier materials used for microencapsulation by spray drying (Pegg and Shahid 2008, Krishnan et al. 2005, Murua-Pagola et al. 2009, Dłużewska et al. 2006, Drusch et al. 2006, Loksuwan 2007, Serfert) et al. 2009, Domian et al. 2015a, 2018, Soottitantawat et al. 2005). In addition to emulsifying and stabilizing properties, it also has the ability to form films. As a result of modification, it also becomes relatively soluble in water (Bai, Y.,

PL 236 931 B1 & Shi, Y. C. (2011). Structure and preparation of octenyl succinic esters of granular starch, microporous starch and soluble maltodextrin. Carbohydrate Polymers, 83 (2), 520-527.).

Aqueous solutions of long polymers of OSA starch are characterized by higher viscosity compared to solutions of other modified starches. Thirathumthavorn and Charoenrein (Thirathumthavorn D., Charoenrein S. (2002). Thermal and pasting properties of native and acid-treated starches derivatized by 1-octenyl succinic anhydride, Carbohydr. Polym. 66 (2), pp. 258-265.) argue that this is due to the association of hydrophobic chains and the formation of amylose complexes with hydrophobic OSA substituents.

There are many preparations of OSA starch on the market with different trade names, which differ in the botanical origin of the starch, molecular weight, degree of polymerization or the degree of substitution with octenyl succinic anhydride groups (Shogren RL, Viswanathan A., Felker F., Gross RA (2000 Distribution of octenyl succinate groups in octenyl succinic anhydride modified waxy maize starch, "Starch / Starke", 52 (6-7), pp. 196-204., Walkowski and Lewandowicz 2004, Prochaska et al. 2007). Thus, they can show various functional properties in multi-phase food systems (Górecka 2004, Shube et al. 2003, Taherian et al. 2006, Yan-Li et al. 2010). It was assumed that high molecular weight OSA preparations based on additionally physically modified, retrograded or dextrinated starches may be particularly effective in stabilizing dispersed systems with a high proportion of solid particles, such as carbon pastes with suspended particles.

The essence of the invention is a natural dye based on vegetable carbon in the form of a paste characterized by the fact that it contains micronized vegetable carbon from bamboo with an average particle size <1 µm (dw) in the amount of 10% - 20% by weight, high molecular weight starch octenyl succinate sodium in the amount of 2 % - 8% by weight and addition of a mixture of xanthan and acacia gum in the amount of 0.1% - 0.5% by weight.

Preferably, the density of the paste is 1,080 - 1.250 kg / m ³ (25 ° C) and a viscosity of 500-2000 cP (25 ° C).

Another object of the invention is a method of industrial preparation of a natural dye based on vegetable carbon in the form of a paste, characterized by the following steps:

a) preparing a liquid base by mixing high molecular weight starch sodium octenyl succinate with water and a mixture of xanthan and acacia gum,

b) micronising the coal to a mean particle size <1 µm (d10); and c) combining the intermediates in a) and b) into a paste.

The present invention is illustrated in detail in the following Examples.

P r z k ł a d 1

Product Characteristics:

CARBON PASTE E153 - A paste intended for coloring food

Ingredients: Water, starch, vegetable carbon, xanthan gum, acacia gum, sodium benzoate, potassium sorbate

Application: confectionery, bakery industry, production of jellies, dragées, ice cream

Characteristics: Homogeneous, water-dispersible suspension

Physical and chemical properties:

Appearance: homogeneous, slightly thick liquid

Odor: no foreign smells

Taste: none

Density: 1120 kg / m ³ (25 ° C)

Viscosity: 742 mPas (25 ° C)

P r z k ł a d 2

The composition of the vegetable dye paste:

micronized bamboo vegetable carbon with an average particle size of <1 µm (d10) - 10% high molecular weight starch octenylsuccinate sodium 5% mixture of xanthan and acacia gum 0.2% demineralized water 84.8%

P r z k ł a d 3

The composition of the vegetable dye paste:

micronized bamboo vegetable carbon with an average particle size of <1 μm (d10) - 12% high molecular weight starch octenyl succinate 8%

PL 236 931 B1 mixture of xanthan and acacia gum 0.1% demineralized water 79.9%

P r z k ł a d 4

The composition of the vegetable dye paste:

micronized bamboo vegetable carbon with an average particle size <1 gm (d10) - 12% high molecular weight starch octenylsuccinate sodium 2% mixture of xanthan and acacia gum 0.5% demineralized water 85.5%

P r z k ł a d 5

The composition of the vegetable dye paste:

micronized bamboo vegetable carbon with an average particle size <1 gm (d10) - 20% high molecular starch sodium octenyl succinate 3% mixture of xanthan and acacia gum 0.3% demineralized water 76.7%

P r z k ł a d 6

A method of producing selected forms of vegetable carbon dyes

The production technology consists of 3 stages:

- preparation of a liquid base,

- micronization of carbon and

- the process of combining semi-finished products into a paste.

Stage 1. An accurately weighed portion of FLO-MAX ™ 2110 starch (Ingredion, USA) should be hydrated in water at a temperature in the range of 18-25 ° C using a BMX 15S mixer (Biomix, Poland), adjusting the mixing speed so that the sample does not become damaged. excessive aeration (in the range of 200-500 rpm). After the starch is hydrated, add the Thixogum ™ gum blend (Nexira, France) in small portions to the clear solution, stirring continuously until the solids are fully hydrated. Set aside prepared in this way for about 15 minutes.

Stage 2. Prepare the charcoal for micronization. A source of compressed air should be connected to the microniser, e.g. MC-JETMILL MC2 (Dec, China). Coal should be fed through the feeder, keeping the feed rate constant, so that the particles migrate freely to the jet mill. A working pressure of 12 bar should be used for the process. In order to obtain the raw material with the smallest particles, the raw material should be removed from the filter surface every 5 minutes.

Stage 3. In the next stage, micronized carbon should be added to the prepared base in small portions, and then the whole thing should be thoroughly mixed using a BMX 15S mixer (Biomix, Poland). Air released during mixing should be removed with a ME1C vacuum pump.

FLO -MAX ™ 2110 starch (Ingredion, USA) - modified OSA starch (E1450 Sodium starch octenyl succinate) is obtained from corn kernels for use as a stabilizer, emulsifier, carrier, thickener and binder. It is characterized by a viscosity of 2.0 - 3.5 [cP], a dry weight of 90 [%] and a pH of 2.5 - 4.5.

Shanghai Coal (Hainuo Coal Industry, China) - vegetable coal obtained from bamboo.

Thixogum ™ - (Nexira, France) blend of natural hydrocolloids, ie xanthan gum and acacia gum in a 45:55 ratio.

The dye according to the invention is used to color foodstuffs for the production of cookies, ice cream, muffins and jelly beans. The dye according to the invention in the form of a paste gives a good coloring effect and a stable black color of the product in various technological operations such as freezing, baking or gelling.

Claims (3)

Patent claims 1. Natural vegetable carbon-based dye in paste form, characterized by containing micronized vegetable carbon from bamboo with an average particle size <1 gm (dw) in the amount of 10% - 20% by weight, high molecular weight starch sodium octenyl succinate in the amount of 2% - 8% by weight and addition of a mixture of xanthan and acacia gum in the amount of 0.1% - 0.5% by weight. 6 PL 236 931 B1 2. The dye according to claim 1 1, characterized in that the density of the paste is 1,080 - 1.250 kg / m ³ (25 ° C) and a viscosity of 500 - 2,000 cps (25 ° C). 3. Industrial method for obtaining a natural dye based on vegetable carbon in the form of a paste, characterized by the following steps: a) preparing a liquid base by mixing high molecular weight starch sodium octenyl succinate with water and a mixture of xanthan and acacia gum, b) micronizing the carbon to a mean particle size <1 gm (d10) and c) combining the intermediates from a) and b) to form a paste.