Colored particles
20220401341 · 2022-12-22
Inventors
- Jens-Michael Hilmer (Holzminden, DE)
- Sergej Elenschleger (Holzminden, DE)
- Rita Lages (Bodenwerder, DE)
- Ingo Reiss (Holzminden, DE)
Cpc classification
C08L3/02
CHEMISTRY; METALLURGY
International classification
Abstract
The present invention relates to color particles from an extrudate, the production thereof, color particles produced by the process and the use of the color particles for the production of foodstuffs, beverages, cosmetics, in particular oral hygiene products, pharmaceuticals and consumer articles, in particular washing and cleaning agents in liquid, gel-like or powdery form, animal food or animal care products and foods, beverages, cosmetics, in particular oral hygiene products, pharmaceuticals, consumer goods, in particular detergents and cleaning agents in liquid, gel-like or powdery form, animal food or animal care products comprising the color particles.
Claims
1. Color particles comprising or consisting of an extrudate from an extrusion process, wherein the extrudate comprises: a carbohydrate matrix comprising a starch having an amylopectin content of at least 80% and at least one viscosity modifying component; at least one emulsifier; and water.
2. Color particles, according to claim 1, wherein the starch has an amylopectin content of at least 90%.
3. Color particles, according to claim 1, wherein the starch is selected from potato starch or rice starch or a combination thereof; and/or wherein the starch has a viscosity of from 10 mPa.Math.s to 50,000 mPa.Math.s, measured as a 10% solution in water at 90° C. using a viscometer.
4. Color particles, according to claim 1, wherein the at least one viscosity-modifying ingredient is a water-soluble compound selected from one or more in the group of mono, di and trisaccharides, sugar alcohols, dextrins or maltodextrins, and mixtures of the aforementioned compounds.
5. Color particles, according to claim 1, wherein the sugar alcohol is selected from one or more in the group of sorbitol, mannitol, isomalt, lactitol, xylitol, threitol, erythritol, arabinol, arabitol, adontol, alditol, ducitol, iditol and mixtures of the aforementioned sugar alcohols.
6. Color particles, according to claim 1, wherein the ratio of starch having an amylopectin content of at least 80% to the viscosity modifying ingredient ranges from 99:1 to 50:50.
7. Color particles, according to claim 1, wherein the at least one emulsifier is selected from one or more in the group of: monoglycerides, diglycerides, deca-glycerol dipalmitate, hexa-glycerol distearate, polyglycerol esters, sulfoacetates, lecithin, polysorbates and mixtures of the aforementioned emulsifiers.
8. Color particles, according to claim 1, wherein the at least one colorant is selected from one or more in the group of oil-soluble colorants and pigment colorants: E141, E153, E160, E160a, E160b, E160c, E171, E172, CI11680, CI12085, CI12490, CI13015, CI15850, CI16185, CI18965, CI19140, CI42045, CI42051, CI42090, CI45350, CI45410, CI47005, CI59040, CI60725, CI61565 CI61570, CI74160, CI74260, CI77007, CI77019, CI77266, CI73360, CI77492, CI77499, CI77891 and mixtures of the abovementioned colorants or pigment colorants.
9. Color particles, according to claim 1, comprising: 50 to 98% by weight of a carbohydrate matrix of a starch having an amylopectin content of at least 80% and at least one viscosity modifying component; 0.1 to 5% by weight of at least one emulsifier; and 1 to 30% by weight of water; based on the total weight of the color particle.
10. Color particle, according to claim 1, wherein the water content is 1 to 30% by weight, based on the total weight of the color particle.
11. Color particles, according to claim 1, wherein the particles have a particle diameter in a range from 0.2 to 5 mm, and/or a length in a range from 0.1 to 10 mm.
12. A method of making a color particle comprising: providing a combination of a carbohydrate matrix comprising a starch having an amylopectin content of at least 80% and at least one viscosity modifying component; preparing a mixture of the combination obtained from step (i) and at least one emulsifier, water to obtain a suspension or gel; extruding the suspension or gel to obtain an extrudate; and comminuting the extrudate to obtain a color particle.
13. The process for producing the color particle according to claim 12, wherein the extrusion of the emulsion is carried out at a temperature in the range of 70 to 150° C. and/or at a pressure of 1 to 60 bar and/or the torque occurring in the extruder during extrusion is in the range of 30-60%, based on the max. torque of the extruder.
14. Color particles obtainable by the method of claim 12.
15. (canceled)
16. A foodstuff, beverage, cosmetic, oral hygiene, pharmaceutical, consumer article, detergent, cleaning agent pet food, or pet care product comprising color particles according to claim 1.
17. The product of claim 16, wherein the food product is selected from the group of: instant beverage powders, tea, soup or sauce powders, bakery products, chewy candies, confectionery, dairy products; the cosmetic product is selected from the group of oral care products, chewing gums, toothpaste, oral gels, chewable tablets, shampoo, shower gel, exfoliating products, creams, and lotions; and the cleaning product is selected from the group of dishwashing detergents, liquid soaps, liquid washing emulsions, and soaps.
18. Colored particles, according to claim 1, further comprising at least one colorant.
19. Colored particles, according to claim 1, further comprising at least one flavoring substance.
20. Colored particles, according to claim 1, further comprising at least one or odiferous, aroma or scent substance.
Description
DESCRIPTION OF THE FIGURES
[0041]
DETAILED DESCRIPTION OF THE INVENTION
[0042] In a first aspect, the present invention relates to color particles comprising or consisting of an extrudate from an extrusion process, wherein the extrudate comprises or consists of: [0043] a carbohydrate matrix comprising or consisting of a starch having an amylopectin content of at least 80% and at least one viscosity modifying component; [0044] at least one/one emulsifier; [0045] water; and [0046] optionally at least one colorant and/or at least one flavoring or odiferous substance or at least one aroma or scent.
[0047] The color particles according to the invention comprise or consist of an extrudate. This extrudate is prepared from a mixture or combination of a carbohydrate matrix comprising or consisting of a starch with an amylopectin content of at least 80% and at least one viscosity modifying component. The two aforementioned components of the carbohydrate matrix form the body of the color particles and are also carriers for other, optional components that can be added to the color particles.
[0048] Starch is a polysaccharide with the formula (C6 Hio 05)n, which consists of α-D-glucose-units linked by glycosidic bonds. The macromolecule is therefore classified as a carbohydrate. Starch is one of the most important reserve substances in plant cells.
[0049] Particularly rich in starch, and therefore used for the extraction of isolated starch, are: [0050] Corn [0051] Wheat [0052] Rice [0053] Potatoes [0054] Cassava (Tapioca)
[0055] Starch consists mostly of [0056] 1-30% amylose, linear chains with helical (screw) structure linked only α-1,4-glycosidically; and [0057] 70-99% amylopectin, highly branched structures, with α-1,6-glycosidic and α-1,4-glycosidic linkages. Starch amylopectin is branched with about one α-1,6-glycosidic linkage per about 30 α-1,4-glycosidic linkages.
[0058] The proportions of amylose and amylopectin differ depending on the starch source.
[0059] Table 1 below shows the composition of starches (amylose content) and their solubility (from “Lehrbuch der Lebensmittelchemie”, ed.: Belitz, Grosch, Schieberle, 5th completely revised edition, 2001, Springer Publisher):
TABLE-US-00001 TABLE 1 Amylose content Solubility at 80° C. Strength (%) (%) Wheat 26-31 2.59 Rye 28 Barley 22-29 Corn 28 Wax corn 0-1 Oats 27 Rice 14-32 Potato 23 31.0 Cassava 17
[0060] Due to the different composition, the above-mentioned starches have different physical and chemical properties.
[0061] Starch is used in a variety of ways, either as native or modified starch. Modified starches are starch products obtained by physical, chemical or enzymatic processes that meet increased technological requirements. The grain structure and other essential properties are retained after modification.
[0062] Modified starches are used in the food industry because, compared to natural starch, they have better [0063] Heat stability [0064] Acid stability [0065] Shear stability, as well as [0066] freezing and thawing behavior
[0067] However, such strengths require procedural pretreatment.
[0068] In the context of the present invention and the following description, the term “starch” is understood to include both native starch(es) and modified starch(es), i.e., starch products obtained by physical, chemical or enzymatic processes, from different starch sources.
[0069] Surprisingly, it has now been found that a starch with an amylopectin content of at least 80% is particularly well suited for producing color particles with high producibility by extrusion processes, which are stable over a longer storage time, especially in an aqueous matrix, i.e., do not bleed out or dissolve, are not perceived as a disturbing foreign body when used, and, in addition, have a clean colored, including white, matrix.
[0070] According to the invention, a starch having an amylopectin content of at least 80% is preferably used for the production of the color particles according to the invention.
[0071] In a preferred embodiment of the color particles according to the invention, the starch having an amylopectin content of at least 80% is selected from the group consisting of rice starch, potato starch and combinations of the two mentioned starches.
[0072] Most preferred is starch with an amylopectin content of at least 90%.
[0073] The most suitable is amylopectin potato starch for the formation of the carbohydrate matrix. Amylopectin potato starch is based on natural breeding and has an amylopectin content of at least 95% and contains virtually no amylose. Such an amylopectin potato starch is commercially available, for example, under the name “Eliane™ Gel 100”. Amylopectin potato starch is characterized by high purity, particular process stability and very high viscosity.
[0074] In a preferred embodiment, the starch has a viscosity of 10 mPa.Math.s to 50.000 mPa.Math.s, preferably a viscosity of 20 mPa.Math.s to 30.000 mPa.Math.s, measured as a 10% solution in water at 90° C. using a rheometer (Anton Paar Rheometer MCR302, cone-plate system, cone type CP-50-1 at a constant shear rate of 5 sec.sup.−1).
[0075] Most preferred for the preparation of the color particles according to the present invention are starches from potatoes and rice having a viscosity of 10 mPa.Math.s to 50.000 mPa.Math.s, preferably a viscosity of 20 mPa.Math.s to 30.000 mPa.Math.s, measured as a 10% solution in water at 90° C. using a rheometer (Anton Paar Rheometer MCR302, cone-plate system, cone type CP-50-1 at a constant shear rate of 5 sec.sup.1).
[0076] In addition, the amylopectin potato starch has the following properties: [0077] smooth and glossy appearance, high clarity and creamy texture; [0078] high viscosity, high elasticity and high water-binding capacity; [0079] processable at low temperatures; [0080] neutral in taste and odor and good flavor acceptance; [0081] high temperature stability and resistance to shear forces.
[0082] Amylopectin potato starch has been used primarily as a thickener or in dry applications, for example in instant products such as soups and sauces, but not in an aqueous matrix, such as in toothpastes, dairy products, especially yogurt, or cleaning agents.
[0083] The starches used according to the invention have melting points above 170° C., preferably above 180° C. The carbohydrate polymers used have glass transition temperatures above 70° C., preferably above 80° C., in particular preferably above 90° C. (glass transition temperatures determined by differential scanning calorimetry (DSC 200 F3 Netzsch)).
[0084] The further at least one viscosity-modifying constituent of the carbohydrate matrix of the color particles according to the invention is a water-soluble compound selected from the group consisting of sugars, sugar alcohols, dextrins or maltodextrins, and mixtures of the aforementioned compounds.
[0085] Particularly suitable and preferred sugars are mono, di and trisaccharides, which in turn are selected from the group consisting of, for example, arabinose, xylose, fructose, galactose, glucose, mannose, sorbose, lactose, maltose, sucrose or maltotriose.
[0086] Sugar alcohols as a water-soluble compound are particularly preferred in the production of the color particles according to the invention.
[0087] The sugar alcohol used according to the invention is preferably selected from the group consisting of sorbitol, mannitol, isomalt, lactitol, xylitol, threitol, erythritol, arabinol, arabitol, adontol, alditol, ducitol, iditol and mixtures of the aforementioned sugar alcohols.
[0088] Particularly preferably, sorbitol is used to prepare the carbohydrate matrix.
[0089] If isomers of the previously mentioned compounds exist, either the pure isomers or any mixtures thereof can be used.
[0090] The water-soluble compounds facilitate granulation at the perforated nozzles. On the other hand, the water-soluble compounds act advantageously as humectants to prevent the color particles of the invention from drying out. The compounds interact with the starch contained, which means that the starch retains its water-binding capacity for longer and the color particles therefore dry out less quickly.
[0091] The amount of the carbohydrate matrix comprising or consisting of a starch having an amylopectin content of at least 80% and at least one viscosity modifying ingredient is from 50% to 98% by weight based on the total weight of the color particle. Preferably, the carbohydrate matrix is present in the color particle in an amount of from 60 to 98% by weight and most preferably in an amount of from 80 to 98% by weight, based on the total weight of the color particle.
[0092] In another preferred embodiment according to the first aspect of the present invention, the ratio of starch having an amylopectin content of at least 80% to the viscosity modifying ingredient ranges from 99:1 to 50:50.
[0093] The color particle according to the invention further comprises an emulsifier as a further component. Advantageously, a small amount of at least one emulsifier is incorporated in order to increase the solubility or the emulsifiability or the suspendability of the constituents when preparing the color particle according to the invention. The addition of the at least one emulsifier also simultaneously increases the stability of the suspension or gel obtained. In addition, the at least one emulsifier in the carbohydrate matrix improves the transport of the material melt during extrusion, reduces the adhesion of the material melt to the walls of the extruder, and improves the flow of material through the dies of the extruder.
[0094] Suitable and preferred emulsifiers are emulsifiers selected from the group consisting of monoglycerides, diglycerides, deca-glycerol dipalmitate, hexa-glycerol distearate, polyglycerol esters, sulfoacetates, lecithin, polysorbates and mixtures of said emulsifiers.
[0095] Monoglycerides, diglycerides or lecithin are particularly preferred emulsifiers.
[0096] The at least one emulsifier is added to the color particle according to the invention in an amount of 0.1 to 5% by weight, based on the total weight of the color particle. Preferably, the emulsifier is present in the color particle in an amount of 0.2 to 4 wt. % and most preferably in an amount of 0.5 to 3 wt. %, based on the total weight of the color particle.
[0097] As a further component, the color particles according to the invention comprise water, which is necessary to be able to produce a viscous mixture in the form of a suspension or a gel from the above-mentioned components. Depending on the starting ingredients, in particular the starch used, a suspension or gel is formed after mixing together the ingredients of the color particles according to the invention and after adding the emulsifier. When the starch slurry is heated or warmed up, a gel is preferably formed.
[0098] In addition, the water content ensures that this mixture is still flowable enough to be dispensed through small openings at acceptable temperatures of <130° C. and not too high extrusion pressure of <60 bar.
[0099] Typically, the water content of the color particles according to the invention is 1 to 30% by weight, based on the total weight of the color particle.
[0100] A water content that is too low makes processing difficult due to the high viscosity of the compound, so that flow through small openings is no longer possible. A water content that is too high, on the other hand, results in a compound that is too soft and cannot be processed via extrusion or can only be processed very poorly.
[0101] Preferably, the water content of the color particles according to the invention is 1 to 20% by weight, even more preferably 5 to 15% by weight, but most preferably 30% by weight, based on the total weight of the color particle.
[0102] The color particles according to the invention may optionally contain, in addition to the above-mentioned ingredients, one or more further (customary) active ingredients or functional ingredients, which make up the sum to 100% by weight in the color particles according to the invention.
[0103] Compared to other starches, for example corn starch, the carbohydrate matrix advantageously has a pure white color, which already makes it suitable as such as color particles, for example as color particles in toothpastes, gels, dairy products, for example yogurt, or cleaning agents.
[0104] For optical purposes, at least one further colorant may optionally be added to the color particle according to the invention. The at least one colorant is a colorant or pigment colorant selected from the group consisting of: E100, E101, E102, E104, E110, E120, E122, E123, E124, E127, E128, E129, E131, E132, E133, E141, E141(i), E141(ii), E142, E150a, E150b, E150c, E150d, E151, E153, E155, E160, E160a, E160b, E160c, E161b, E163, E171, E172, E174, E175 and mixtures of the above colorants or pigment colorants.
[0105] Other colorants or pigment colorants used and added to the color particles according to the invention are titanium dioxide E171 C.I. 77891, pearlescent pigment silver AA, gold E175, blue C.I. 74160, iron oxide red E172 C.I. 77491, pearlescent pigment gold BB, vegetable carbon E153 C.I. 77268:1, red C.I. 73360, green C.I. 74260, iron oxide black E172 C.I. 77499 or mixtures of the above colorants and pigment colorants.
[0106] Particularly preferred are oil-soluble colorants and pigment colorants selected from the group consisting of: E141, E153, E160, E 160a, E 160b, E 160c, E171, E172, CI11680, CI12085, CI12490, CI13015, CI15850, CI16185, CI18965, CI19140, CI42045, CI42051, CI42090, CI45350, CI45410, CI47005, CI59040, CI60725, CI61565 CI61570, CI74160, CI74260, CI77007, CI77019, CI77266, CI73360, CI77492, CI77499, CI77891 and mixtures of the abovementioned colorants or pigment colorants.
[0107] The foregoing lists are illustrative and not intended to be exhaustive.
[0108] The previously mentioned colorants are in particular oil-soluble colorants and pigment colorants approved for food, beverages, oral care products and cosmetics. Water-soluble colorants are less suitable because they tend to bleed out in an aqueous matrix, for example in a toothpaste, a gel, a dairy product, preferably a yogurt, or a cleaning product.
[0109] The at least one colorant is added to the color particle of the invention in an amount of 0.001 to 10% by weight, based on the total weight of the color particle. Preferably, the at least one colorant is included in the color particle in an amount of 0.01 to 2 wt % and most preferably in an amount of 0.1 to 1 wt %, based on the total weight of the color particle.
[0110] The color particles according to the invention optionally contain as a further component at least one flavoring or at least one aroma, i.e., two, three, four, five or even far more aroma components in a sensory effective amount, or at least one further odiferous substance or at least one scent or two, three, four, five or even far more odiferous substance components in a sensory effective amount. The terms “flavoring” and “aroma” or “odiferous substance” and “scent” are used in the context of the present application equally next to each other and are therefore dependent on the intended use, namely flavoring on the one hand or fragrancing or perfuming on the other hand.
[0111] The term “sensory effective amount” in the context of the present application means that the flavoring or aroma or odiferous substance or scent is used in such a sufficient amount that the resulting product, in operation or in use, reveals the sensory properties of the flavoring or aroma or odiferous substance or scent.
[0112] Typically, flavoring or odiferous compounds are not used in binary or ternary blends, but as components of sophisticated complex blends that may contain two, three, four, five, ten, or preferably even a much higher number of flavoring or odiferous compounds, in some cases in very small amounts, to give a particularly rounded flavor profile.
[0113] In a preferred further development of the present invention, the color particles therefore optionally contain any desired number of further flavoring or odiferous compounds selected from the group formed by: (1) hydrocarbons; (2) aliphatic alcohols; (3) aliphatic aldehydes and their acetals; (4) aliphatic ketones and their oximes; (5) aliphatic sulfur-containing compounds; (6) aliphatic nitriles; (7) esters of aliphatic carboxylic acids; (8) acyclic terpene alcohols; (9) acyclic terpene aldehydes and ketones; (10) cyclic terpene alcohols; (11) cyclic terpene aldehydes and ketones; (12) cyclic alcohols; (13) cycloaliphatic alcohols; (14) cyclic and cycloaliphatic ethers; (15) cyclic and macrocyclic ketones; (16) cycloaliphatic aldehydes; (17) cycloaliphatic ketones; (18) esters of cyclic alcohols; (19) esters of cycloaliphatic alcohols; (20) esters of cycloaliphatic carboxylic acids; (21) araliphatic alcohols; (22) esters of araliphatic alcohols and aliphatic carboxylic acids; (23) araliphatic ethers; (24) aromatic and araliphatic aldehydes; (25) aromatic and araliphatic ketones; (26) aromatic and araliphatic carboxylic acids and esters thereof; (27) nitrogen-containing aromatic compounds; (28) phenols, phenyl ethers and phenyl esters; (29) heterocyclic compounds; (30) lactones; and mixtures thereof.
[0114] The selection of flavorings or odiferous substances is very comprehensive in this respect; corresponding substances with which the color particles according to the invention can be advantageously combined can be found, for example, in “S. Arctander, Perfume and Flavor Chemicals, Volumes I and II, Montclair, N.J., 1969, self-published” or “H. Surburg and J. Panten, Common Fragrance and Flavor Materials, 6th edition, Wiley-VCH, Weinheim, 2016”.
[0115] In detail, the following may be mentioned:
[0116] Extracts from natural raw materials: This group represents essential oils, concretes, absolutes, resins, resinoids, balsams, tinctures such as Ambergris tincture; Amyris oil; Angelica seed oil; Angelica root oil; Anise oil; Valerian oil; Basil oil; Tree moss absolute; Bay oil; Mugwort oil; Benzoeresin; Bergamot oil; Beeswax absolute; Birch tar oil; Bitter almond oil; Savory oil; Bucco leaf oil; Cabreuva oil; Cade oil; Calmus oil; Camphor oil; Cananga oil; Cardamom oil; Cascarilla oil; Cassia oil; Cassie-absolute; Castoreum-absolute; Cedar leaf oil; Cedarwood oil; Cistus oil; Citronella oil; Citron oil; Copaiva balsam; Copaiva balsam oil; Coriander oil; Costus root oil; Cumin oil; Cypress oil; Davana oil; Dill herb oil; Dill seed oil; Eau de brouts absolute; Oak moss absolute; Elemi oil; Tarragon oil; Eucalyptus citriodora oil; Eucalyptus oil; Fennel oil; Spruce needle oil; Galbanum oil; Galbanum resin; Geranium oil; Grapefruit oil; Guaiac wood oil; Gurjun balsam; Gurjun balsam oil; Helichrysum absolute; Helichrysum oil; Ginger oil; Iris root absolute; Iris root oil; Jasmine absolute; Calamus oil; Chamomile oil blue; Chamomile oil Roman; Carrot seed oil; Cascarilla oil; Pine needle oil; Curly mint oil; Caraway seed oil; Labdanum oil; Labdanum absolute; Labdanum resin; Lavandin absolute; Lavandin oil; Lavender absolute; Lavender oil; Lemongrass oil; Lovage oil; Lime oil distilled; Lime oil pressed; Linaloe oil; Litsea cubeba oil; Bay leaf oil; Mace oil; Marjoram oil; Mandarin oil; Masso bark oil; Mimosa absolute; Musk grain oil; Musk tincture; Muscat oil; Myrrh absolute; Myrrh oil; Myrtle oil; Clove leaf oil; Clove flower oil; Neroli oil; Olibanum absolute; Olibanum oil; Opopanax oil; Orange flower absolute; Orange oil; Origanum oil; Palmarosa oil; Patchouli oil; Perilla oil; Perubalsam oil; Parsley leaf oil; Parsley seed oil; Petitgrain oil; Peppermint oil; Pepper oil; Allspice oil; Pine oil; Poley oil; Rose absolute; Rosewood oil; Rose oil; Rosemary oil; Sage oil Dalmatian; Sage oil Spanish; Sandalwood oil; Celery seed oil; Spicy lavender oil; Star anise oil; Styrax oil; Tagetes oil; Fir needle oil; Tea tree oil; Turpentine oil; Thyme oil; Tolu balsam; Tonka absolute; Tuberose absolute; Vanilla extract; Violet leaf absolute; Verbena oil; Vetiver oil; Juniper berry oil; Wine yeast oil; Wormwood oil; Wintergreen oil; Ylang oil; Hyssop oil; Civet absolute; Cinnamon leaf oil; Cinnamon bark oil, and fractions thereof, or ingredients isolated therefrom.
[0117] Individual odiferous substances and flavorings: Individual odiferous substances and flavorings can be divided into a variety of classes, namely:
[0118] hydrocarbons, such as 3-carene; α-pinene; β-pinene; α-terpinene; γ-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; farnesene; limonene; longifolene; myrcene; ocimene; valencene; (E,Z)-1,3,5-undecatriene; styrene; diphenylmethane;
[0119] aliphatic alcohols such as hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2-methyl-2-heptanol; 2-methyl-2-octanol; (E)-2-hexenol; (E) and (Z)-3-hexenol; 1-octen-3-ol; mixture of 3,4,5,6,6-pentamethyl-3/4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methyleneheptan-2-ol; (E,Z)-2,6-nonadienol; 3,7-dimethyl-7-methoxyoctan-2-ol; 9-decenol; 10-undecenol; 4-methyl-3-decen-5-ol;
[0120] aliphatic aldehydes and their acetals such as hexanal; heptanal; octanal; nonanal; decanal; undecanal; dodecanal; tridecanal; 2-methyloctanal; 2-methylnonanal; (E)-2-hexenal; (Z)-4-heptenal; 2,6-dimethyl-5-heptenal; 10-undecenal; (E)-4-decenal; 2-dodecenal;2,6,10-trimethyl-9-undecenal; 2,6,10-trimethyl-5,9-undecadienal; heptanal diethyl acetal; 1,1-dimethoxy-2,2,5-trimethyl-4-hexene; citronellyloxyacetaldehyde; 1-(1-methoxy-propoxy)-(E/Z)-3-hexene;
[0121] aliphatic ketones and their oximes such as 2-heptanone; 2-octanone; 3-octanone; 2-nonanone; 5-methyl-3-heptanone; 5-methyl-3-heptanonoxime; 2,4,4,7-tetramethyl-6-octen-3-one; 6-methyl-5-hepten-2-one;
[0122] aliphatic sulfur-containing compounds such as 3-methylthiohexanol; 3-methylthiohexyl acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylthiohexyl acetate; 1-menthen-8-thiol;
[0123] aliphatic nitriles such as 2-nonenoic acid nitrile; 2-undecenoic acid nitrile; 2-tridecenoic acid nitrile; 3,12-tridecadienoic acid nitrile; 3,7-dimethyl-2,6-octadienoic acid nitrile; 3,7-dimethyl-6-octenoic acid nitrile;
[0124] esters of aliphatic carboxylic acids such as (E) and (Z)-3-hexenyl formate; ethyl acetoacetate; isoamyl acetate; hexyl acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate; (E)-2-hexenyl acetate; (E) and (Z)-3-hexenyl acetate; octyl acetate; 3-octyl acetate; 1-octen-3-yl acetate; ethyl butyrate; butyl butyrate; isoamyl butyrate; hexyl butyrate; (E) and (Z)-3-hexenyl isobutyrate; hexyl crotonate; ethyl isovalerate; ethyl 2-methylpentanoate; ethyl hexanoate; allyl hexanoate; ethyl heptanoate; allyl heptanoate; ethyl octanoate; ethyl (E,Z)-2,4-decadienoate; methyl 2-octinate; methyl 2-noninate; allyl 2-isoamyloxyacetate; methyl 3,7-dimethyl-2,6-octadienoate;4-methyl-2-pentyl crotonate;
[0125] acyclic terpene alcohols such as citronellol; geraniol; nerol; linalool; lavadulol; nerolidol; farnesol; tetrahydrolinalool; tetrahydrogeraniol; 2,6-dimethyl-7-octen-2-ol; 2,6-dimethyloctan-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-5,7-octadien-2-ol; 2,6-dimethyl-3,5-octadien-2-ol; 3,7-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl-1,5,7-octatrien-3-ol; 2,6-dimethyl-2,5,7-octatrien-1-ol; and their formates, acetates, propionates, isobutyrates, butyrates, isovalerianates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2-butenoates;
[0126] acyclic terpene aldehydes and ketones such as geranial; neral; citronellal; 7-hydroxy-3,7-dimethyloctanal; 7-methoxy-3,7-dimethyloctanal; 2,6,10-trimethyl-9-undecenal; geranylacetone; and the dimethyl and diethylacetals of geranial, neral, 7-hydroxy-3,7-dimethyloctanal;
[0127] cyclic terpene alcohols such as menthol; isopulegol; alpha-terpineol; terpinenol-4; menthan-8-ol; menthan-1-ol; menthan-7-ol; borneol; isoborneol; linalool oxide; nopol; cedrol; ambrinol; vetiverol; guaiaol; and their formates, acetates, propionates, isobutyrates, butyrates, isovalerianates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2-butenoates;
[0128] cyclic terpene aldehydes and ketones such as menthone; isomenthone; 8-mercaptomenthan-3-one; carvone; camphor; fenchone; alpha-ionone; beta-ionone; alpha-n-methylionone; beta-n-methylionone; alpha-isomethylionone; beta-isomethylionone; alpha-irone; alpha-damascone; beta-damascone; beta-damascenone; delta-damascone; gamma-damascone; 1-(2,4,4-trimethyl-2-cyclohexen-1-yl)-2-buten-1-on; 1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-methanonaphthalen-8(5H)-on; 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal; nootkatone; dihydronootkatone; 4,6,8-megastigmatrien-3-one; alpha-sinensal; beta-sinensal; acetylated cedarwood oil (methylcedrylketone);
[0129] cyclic alcohols such as 4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; 3-isocamphylcyclohexanol; 2,6,9-trimethyl-Z2,Z5,E9-cyclododecatrien-1-ol; 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol;
[0130] cycloaliphatic alcohols such as alpha,3,3-trimethylcyclohexyl-methanol;1-(4-isopropylcyclohexyl)ethanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)butanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-pentan-2-ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 1-(2,2,6-trimethylcyclohexyl)pentan-3-ol; 1-(2,2,6-trimethylcyclohexyl)hexan-3-ol;
[0131] cyclic and cycloaliphatic ethers such as cineol; cedryl methyl ether; cyclododecyl methyl ether; 1,1-dimethoxycyclododecane; (ethoxymethoxy)cyclodo-decane; alpha-cedrene epoxide; 3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan; 3a-ethyl-6,6,9a-trimethyldodecahydronaphtho[2,1-b]furan; 1,5,9-trimethyl-13-oxabicyclo[10.1.0]trideca-4,8-diene; rose oxide; 2-(2,4-dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1-methylpropyl)-1,3-dioxane;
[0132] cyclic and macrocyclic ketones such as 4-tert.butylcyclohexanone; 2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclo-pentanone; 2-hydroxy-3-methyl-2-cyclopenten-1-one; 3-methyl-cis-2-penten-1-yl-2-cyclopenten-1-one; 3-methyl-2-pentyl-2-cyclopenten-1-one; 3-methyl-4-cyclopenta-decenone; 3-methyl-5-cyclopentadecenone; 3-methylcyclopentadecanone; 4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone; 4-tert.-pentylcyclohexanone; 5-cyclohexadecen-1-one; 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone; 8-cyclohexadecen-1-one; 9-cycloheptadecen-1-one; cyclopentadecanone; cyclohexa-decanone;
[0133] cycloaliphatic aldehydes such as 2,4-dimethyl-3-cyclohexenecarbaldehyde; 2-methyl-4-(2,2,6-trimethyl-cyclohexen-1-yl)-2-butenal; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarbaldehyde; 4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarbaldehyde;
[0134] cycloaliphatic ketones such as 1-(3,3-dimethylcyclohexyl)-4-penten-1-on; 2,2-dimethyl-1-(2,4-dimethyl-3-cyclohexen-1-yl)-1-propanon; 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-on; 2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-2-naphthalenyl methyl ketone; methyl 2,6,10-trimethyl 2,5,9-cyclododecatrienyl ketone; tert.-butyl-(2,4-dimethyl-3-cyclohexen-1-yl)ketone;
[0135] esters of cyclic alcohols such as 2-tert-butyl cyclohexyl acetate; 4-tert-butyl cyclohexyl acetate; 2-tert-pentyl cyclohexyl acetate; 4-tert-pentyl cyclohexyl acetate; 3,3,5-trimethyl cyclohexyl acetate; decahydro-2-naphthyl acetate; 2-cyclopentyl cyclopentyl crotonate; 3-pentyl tetrahydro-2H-pyran-4-yl acetate; decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5, respectively 6-indenyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5, or 6-indenyl propionate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5, or 6-indenyl isobutyrate; 4,7-methanooctahydro-5, or 6-indenyl acetate;
[0136] esters of cycloaliphatic alcohols such as 1-cyclohexylethyl crotonate;
[0137] esters of cycloaliphatic carboxylic acids such as allyl 3-cyclohexyl propionate; allyl cyclohexyloxy acetate; cis and trans-methyl dihydrojasmonate; cis and trans-methyl jasmonate; methyl 2-hexyl-3-oxocyclopentane carboxylate; ethyl-2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate; ethyl-2,3,6,6-tetramethyl-2-cyclohexenecarboxylate; ethyl 2-methyl-1,3-dioxolane-2-acetate;
[0138] araliphatic alcohols such as benzyl alcohol; 1-phenylethyl alcohol; 2-phenylethyl alcohol; 3-phenyl propanol; 2-phenyl propanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenyl propanol; 2,2-dimethyl-3-(3-methylphenyl)propanol; 1,1-dimethyl-2-phenylethyl alcohol; 1,1-dimethyl-3-phenylpropanol; 1-ethyl-1-methyl-3-phenylpropanol; 2-methyl-5-phenylpentanol; 3-methyl-5-phenylpentanol; 3-phenyl-2-propen-1-ol; 4-methoxybenzyl alcohol; 1-(4-isopropylphenyl)ethanol;
[0139] esters of araliphatic alcohols and aliphatic carboxylic acids such as benzyl acetate; benzyl propionate; benzyl isobutyrate; benzyl isovalerate; 2-phenylethyl acetate; 2-phenylethyl propionate; 2-phenylethyl isobutyrate; 2-phenylethyl isovalerate; 1-phenylethyl acetate; alpha-trichloromethyl benzyl acetate; alpha,alpha-dimethylphenyl ethyl acetate; alpha,alpha-dimethylphenyl ethyl butyrate; cinnamyl acetate; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate;
[0140] araliphatic ethers such as 2-phenylethyl methyl ether; 2-phenylethyl isoamyl ether; 2-phenylethyl 1-ethoxyethyl ether; phenylacetaldehyde dimethyl acetal; phenylacetaldehyde dimethyl acetal; hydratropaaldehyde dimethyl acetal; phenylacetaldehyde glycerol acetal; 2,4,6-trimethyl-4-phenyl-1,3-dioxane; 4,4a,5,9b-tetrahydroindeno[1,2-d]-m-dioxin; 4,4a,5,9b-tetrahydro-2,4-dimethylindeno[1,2-d]-m-dioxin;
[0141] aromatic and araliphatic aldehydes such as benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; hydratropaaldehyde; 4-methylbenzaldehyde; 4-methylphenylacetaldehyde; 3-(4-ethylphenyl)-2,2-dimethylpropanal; 2-methyl-3-(4-isopropylphenyl)propanal; 2-methyl-3-(4-tert.-butylphenyl)propanal; 2-methyl-3-(4-isobutylphenyl)propanal; 3-(4-tert.-butylphenyl)propanal; cinnamaldehyde; alpha-butylcinnamaldehyde; alpha-amylcinnamaldehyde; alpha-hexylcinnamaldehyde; 3-methyl-5-phenylpentanal; 4-methoxybenzaldehyde; 4-hydroxy-3-methoxybenzaldehyde; 4-hydroxy-3-ethoxybenzaldehyde; 3,4-methylenedioxybenzaldehyde; 3,4-dimethoxybenzaldehyde; 2-methyl-3-(4-methoxyphenyl)propanal; 2-methyl-3-(4-methylenedioxyphenyl)propanal;
[0142] aromatic and araliphatic ketones such as acetophenone; 4-methylacetophenone; 4-methoxyacetophenone; 4-tert.butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone; 4-(4-hydroxyphenyl)-2-butanone; 1-(2-naphthalenyl)ethanone; 2-benzofuranylethanone; (3-methyl-2-benzofuranyl)ethanone; benzophenone; 1,1,2,3,6-hexamethyl-5-indanylmethyl ketone; 6-tert.butyl-1,1-dimethyl-4-indanyl methyl ketone; 1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methylethyl)-1H-5-indenyl]ethanone; 5′,6′,7′,8′-tetrahydro-3′,5′, 5′,6′,8′,8′-hexamethyl-2-acetonaphthone;
[0143] aromatic and araliphatic carboxylic acids and their esters such as benzoic acid; phenylacetic acid; methyl benzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methyl phenyl acetate; ethyl phenyl acetate; geranyl phenyl acetate; phenyl ethyl phenyl acetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; phenyl ethyl cinnamate; cinnamyl cinnamate; allyl phenoxy acetate; methyl salicylate; isoamyl salicylate; hexyl salicylate; cyclohexyl salicylate; cis-3-hexenyl salicylate; benzyl salicylate; phenyl ethyl salicylate; methyl 2,4-dihydroxy-3,6-dimethylbenzoate; ethyl 3-phenyl glycidate; ethyl 3-methyl-3-phenyl glycidate;
[0144] nitrogen-containing aromatic compounds such as 2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert.butylacetophenone; cinnamic acid nitrile; 3-methyl-5-phenyl-2-pentenoic acid nitrile; 3-methyl-5-phenylpentanoic acid nitrile; methyl anthranilate; methyl-N-methyl anthranilate; Schiff'sche bases of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3-(4-tert.-butylphenyl)propanal or 2,4-dimethyl-3-cyclohexenecarbaldehyde; 6-isopropylquinoline; 6-isobutylquinoline; 6-sec-butylquinoline;2-(3-phenylpropyl)pyridine; indole; scatole; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazine;
[0145] phenols, phenyl ethers and phenyl esters such as tarragol; anethole; eugenol; eugenyl methyl ether; isoeugenol; isoeugenyl methyl ether; thymol; carvacrol; diphenyl ether; beta-naphthyl methyl ether; beta-naphthyl ethyl ether; beta-naphthyl isobutyl ether; 1,4-dimethoxybenzene; eugenyl acetate; 2-methoxy-4-methylphenol; 2-ethoxy-5-(1-propenyl)phenol; p-cresylphenyl acetate;
[0146] heterocyclic compounds such as 2,5-dimethyl-4-hydroxy-2H-furan-3-one; 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one; 3-hydroxy-2-methyl-4H-pyran-4-one; 2-ethyl-3-hydroxy-4H-pyran-4-one;
[0147] lactones such as 1,4-octanolide; 3-methyl-1,4-octanolide; 1,4-nonanolide; 1,4-decanolide; 8-decene-1,4-olide; 1,4-undecanolide; 1,4-dodecanolide; 1,5-decanolide; 1,5-dodecanolide;4-methyl-1,4-decanolide; 1,15-pentadecanolide; cis and trans-11-pentadecene-1,15-olide; cis and trans-12-pentadecene-1,15-olide; 1,16-hexadecanolide; 9-hexadecene-1,16-olide; 10-oxa-1,16-hexadecanolide; 11-oxa-1,16-hexadecanolide; 12-oxa-1,16-hexadecanolide; ethylene-1,12-dodecanedioate; ethylene-1,13-tridecanedioate; coumarin; 2,3-dihydrocoumarin; octahydrocoumarin;
[0148] as well as any mixtures of the aforementioned flavoring or odiferous substances.
[0149] Flavorings or odiferous substances or aromas can be used in liquid form undiluted or diluted with a solvent for aromatization. Suitable and preferred solvents for this purpose are in particular ethanol, glycerol, vegetable oil, triglycerides, 1,2-propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate and triacetin.
[0150] Such flavoring or odiferous substance mixtures contain up to 99% by weight, preferably about 5% to about 70% by weight, in particular about 10% to about 50% by weight and particularly preferably about 15% to about 25% by weight of said solvents.
[0151] In a preferred alternative, the flavoring or odiferous substance mixtures comprise synthetic or natural, preferably tasteless and odorless carrier substances, in particular carrier oils, which contain the flavoring or odiferous substances in highly concentrated form and optionally solvents and/or excipients.
[0152] For some applications, it is also advantageous to adsorb the flavoring or odiferous substance mixtures to a carrier that provides both a fine distribution of the flavorings or odiferous substances contained therein in the product and a controlled release upon application. Such carriers can be porous inorganic materials such as light sulfate, silica gels, zeolites, gypsums, clays, clay granules, aerated concrete, etc., or organic materials such as woods, cellulose-based materials, sugars, dextrins (e.g., maltodextrin) or cyclodextrins.
[0153] In an alternative preferred embodiment, the flavoring or odiferous substance mixtures are in microencapsulated or spray-dried form or are present as inclusion complexes or as extrusion products to be added in this form to the flavored product.
[0154] The microencapsulation of the flavoring or odiferous substance compositions can be carried out, for example, by the so-called coacervation process using capsule materials, e.g., made of soft gelatin. The spray-dried scent, aroma or odiferous substance compositions can be prepared, for example, by spray-drying an emulsion or dispersion containing the flavoring or odiferous substance mixture according to the invention, wherein modified starches, proteins, dextrin and vegetable gums can preferably be used as carriers. Inclusion complexes can be prepared, for example, by incorporating dispersions of a flavoring or odiferous substance blend and cyclodextrins or urea derivatives into a suitable solvent, such as water. Extrusion products can be obtained by fusing a flavoring or odiferous substance blend with a suitable waxy material and by extrusion followed by solidification, optionally in a suitable solvent, e.g., isopropanol.
[0155] If necessary, the properties of flavoring or odiferous substance mixture preparations modified in this way can be further optimized by so-called “coating” with suitable materials with a view to more targeted scent release.
[0156] The color particles according to the invention have a flavoring, aroma or odiferous substance or scent content of from 0.01 to 25% by weight, preferably from 0.1 to 15% by weight, more preferably from 0.2 to 10% by weight, based on the total weight of the color particle.
[0157] Optionally, the color particles according to the invention comprise further active ingredients or functional ingredients selected from the group consisting of: preservatives, antioxidants, UV filters, vitamins, acidity regulators, sweeteners, stabilizers, thickeners, gelling agents, anticaking agents, and other ingredients commonly used and approved in the food, cosmetics and pharmaceutical industries.
[0158] In a particularly preferred variant of the first aspect, the color particles according to the invention have the following composition: [0159] 50 to 98% by weight of a carbohydrate matrix of a starch having an amylopectin content of at least 80% and at least one viscosity modifying component; [0160] 0.1 to 5% by weight of at least one emulsifier; [0161] 1 to 30% by weight of water; and [0162] optionally 0.001 to 10% by weight of at least one colorant; [0163] optionally 0.01 to 25% by weight of at least one flavoring or odiferous substance or at least one aroma or scent;
based on the total weight of the color particle.
[0164] The color particles according to the invention typically have a glass transition temperature in the range of 10 to 90° C., preferably in the range of 20 to 75° C., particularly preferably in the range of 20 to 60° C. The glass transition temperatures were determined by means of differential scanning calorimetry (DSC 200 F3 Netzsch).
[0165] The color particles according to the first aspect of the present invention preferably have a cylindrical or spherical geometry and a narrow particle size profile. They typically have a diameter of from 0.2 to 5 mm, preferably from 0.3 to 3.0 mm, and more preferably from 0.5 to 2.0 mm, and/or a length of from 0.1 to 10 mm, preferably from 0.2 to 3.0 mm, and more preferably from 0.3 to 1.5 mm. The aforementioned sizes thus preferably lie in the range of 0.1 to 1.5 mm in which particles are optically perceived.
[0166] As a comparison of the color particles according to the invention produced from rice or potato starch with color particles produced from corn, wheat or tapioca starch shows, the color particles according to the invention are characterized by good producibility in the extruder as well as good storage stability over a longer period of time. Even in a moist matrix, the color particles according to the invention do not bleed out or dissolve. Due to these properties, the color particles according to the invention are particularly suitable for improving the optical appearance of gel-based preparations, such as toothpastes or skin care products, cleaning products or dairy products, such as yogurt, or for imparting texture thereto, especially over the shelf life of such products.
[0167] The color particles of the invention are also readily friable in water, which makes them eminently suitable for the intended applications, for example in toothpastes, dairy products such as yogurt or cleaning products. The good stability and friability of the color particles in water is a measure of the fact that the color particles are not perceived as annoying or as rough when used. In addition, the color particles of the invention have a clean colored, including white, matrix.
[0168] The effects described above are illustrated by the results in Tables 2 and 3 below.
[0169] A further advantage of the color particles according to the invention is an optionally high loadability with flavorings or odiferous substances or aromas or scents, extracts or active ingredients as well as a maximum retention of flavorings or odiferous substances or aromas or scents, or extracts or active ingredients during their storage or over the shelf life of the end products.
[0170] The second object of the present invention is a method for producing a color particle, comprising the steps of: [0171] (i) providing a combination of a carbohydrate matrix comprising or consisting of a starch having an amylopectin content of at least 80% and at least one viscosity modifying component; [0172] (ii) preparation of a mixture of the combination obtained from step (i) and at least one emulsifier, water and optionally at least one colorant and/or at least one flavoring or odiferous substance and/or at least one aroma or scent to obtain a suspension or gel; [0173] (iii) extrusion of the suspension or gel to obtain an extrudate; [0174] (iv) comminution of the extrudate to obtain a color particle; and [0175] (v) optional drying of the color particle.
[0176] The color particles according to the invention are produced by extrusion in an extruder. After mixing and dispersing or suspending the components of the color particles according to the invention, the highly viscous mixture, i.e., the suspension or gel, is continuously pressed or extruded through the die(s) of the extruder and comminuted in a subsequent step.
[0177] The preferred extruder type used is a twin-screw extruder, although other known extruder types can also be used. Preferably, a twin-screw extruder is used for mixing the components of the color particle according to the invention, which can be equipped with several temperature zones so that the temperature during mixing and extrusion can be controlled in a targeted manner.
[0178] In a first step of the process according to the invention, a combination of the carbohydrate matrix ingredient and a viscosity modifying ingredient is provided and mixed in the extruder.
[0179] The carbohydrate matrix comprises a starch with an amylopectin content of at least 80%. The starch used with an amylopectin content of at least 80% can be used directly and without further pretreatment.
[0180] The term “starch” includes both native starch(es) and modified starch(es), i.e., starch products obtained by physical, chemical or enzymatic processes, from different starch sources.
[0181] In a preferred embodiment of the process according to the invention, the starch having an amylopectin content of at least 80% is selected from the group consisting of rice starch, potato starch and combinations of the two mentioned starches.
[0182] Most preferred is starch with an amylopectin content of at least 90%.
[0183] The most suitable is amylopectin potato starch for the formation of the carbohydrate matrix. Amylopectin potato starch is based on natural breeding and has an amylopectin content of at least 95% and contains virtually no amylose. Such an amylopectin potato starch is commercially available, for example, under the name “Eliane™ Gel 100”. Amylopectin potato starch is characterized by high purity, particular process stability and very high viscosity.
[0184] In a preferred embodiment, the starch has a viscosity of 10 mPa.Math.s to 50.000 mPa.Math.s, preferably a viscosity of 20 mPa.Math.s to 30.000 mPa.Math.s, measured as a 10% solution in water at 90° C. using a rheometer (Anton Paar Rheometer MCR302, cone-plate system, cone type CP-50-1 at a constant shear rate of 5 sec.sup.−1).
[0185] Most preferred for the preparation of the color particles according to the present invention are starches from potatoes and rice having a viscosity of 10 mPa.Math.s to 50.000 mPa.Math.s, preferably a viscosity of 20 mPa.Math.s to 30.000 mPa.Math.s, measured as a 10% solution in water at 90° C. using a rheometer (Anton Paar Rheometer MCR302, cone-plate system, cone type CP-50-1 at a constant shear rate of 5 sec.sup.1).
[0186] The viscosity modifying component lowers the softening point of the matrix: The higher its proportion in the mixture, the easier it is to extrude the carbohydrate matrix. Furthermore, this ingredient facilitates granulation at the perforated die.
[0187] In the second step of the process according to the invention, the further components of the color particles according to the invention, such as emulsifier, water and optionally colorant, flavoring and/or odiferous substance or aroma and/or scent, are continuously fed to the extruder in the dosages described above.
[0188] Alternatively, the two steps (first step and second step) can also be combined. For this purpose, all components are mixed beforehand and then continuously fed to the extruder.
[0189] The at least one emulsifier causes the carbohydrate matrix and the other components of the color particles to emulsify, suspend or form a gel-like structure with each other. The emulsifier also promotes transport of the materials during extrusion, reduces adhesion to the walls of the extruder, and improves transport of the mixture through the dies of the extruder.
[0190] The addition of water causes a lowering of the glass transition temperature, and the plasticizing effect of water favors the thermoplastic extrusion of the carbohydrate matrix. During the extrusion of starch, the shear forces destroy the starch granules, and water can penetrate the starch molecules more quickly and trigger gelatinization. Extrusion with water produces a thermoplastically deformable mixture in the extruder that exhibits pronounced viscoelasticity.
[0191] In an alternative variant of the process according to the present invention, all components of the color particles, i.e. carbohydrate matrix comprising or consisting of a starch with an amylopectin content of at least 80%, at least one viscosity modifying component, an emulsifier, water and optionally at least one colorant and/or at least one flavoring or odiferous substance and/or at least one aroma or scent are provided and mixed in one process step to obtain a highly viscous mixture.
[0192] With regard to the constituents of the color particles, their preferred or alternative embodiments, their mixing and quantity ratios and their advantageous effects, reference is made to the above detailed description in connection with the color particles according to the invention, which is equally valid for the process according to the invention in accordance with the second aspect of the invention, so that it is unnecessary to repeat it.
[0193] After completion of the mixing and dispersing or suspending of the components of the color particles according to the invention in the process according to the invention, a highly viscous mixture is present in the form of a suspension or gel, which is extruded in a further step, thereby obtaining an extrudate.
[0194] The extrudate is continuously pressed through the die(s) of the extruder. As a result, strands are formed downstream of the die opening. The diameter of the strands and thus the diameter of the color particles finally obtained is controlled via the die diameter. A minimum pressure of 1 bar must be built up in front of the nozzle to ensure uniform discharge without pulsing. The ideal pressure range is between 1 and 60 bar, preferably from 4 to 50 bar and particularly preferably from 5 to 45 bar.
[0195] Particularly good producibility in the extruder is achieved when starch with an amylopectin content of more than 90%, in particular pure amylopectin potato starch, is used in the process according to the invention to form the carbohydrate matrix. The amylopectin potato starch with more than 95% amylopectin content contains practically no amylose. Such an amylopectin potato starch is commercially available, for example, under the name “Eliane™ Gel 100”.
[0196] Since the viscosity of the suspension or gel has an influence on the stability of the color particles during application, in the process according to the present invention, in order to achieve the best possible stability of the color particles, a starch is used which has a viscosity of 10 to 50.000 mPa.Math.s, measured as a 10% solution in water at 90° C.
[0197] Preferably, a twin-screw or twin-shaft extruder is used for mixing the components of the color particle according to the invention, which can be equipped with several temperature zones so that the temperature during mixing and extrusion can be specifically controlled. The viscosity of the mixture is also controlled by heating the extruder housing and the frictional heat of the screw rotations.
[0198] Mixing of the components of the color particle according to the invention and/or extrusion of the suspension or gel is carried out at an elevated temperature. The increased temperature affects the viscosity of the suspension or gel, which is thereby lowered. This makes it easier to force the suspension or gel through the die plate of the extruder. Preferably, mixing of the components of the color particle according to the invention and/or extrusion of the suspension or gel is carried out at a temperature in the range from 70 to 150° C., preferably from 75 to 130° C. and particularly preferably from 80 to 120° C.
[0199] The torque occurring in the extruder during extrusion (measured in % of the max. torque or the total torque of the extruder) represents a measure of the producibility. If the torque is in the range of 30-60%, the color particles can be produced well i.e., uniform particles are produced during granulation at the head of the extruder and the extrusion runs for several hours without technical malfunction. A Leistritz ZSE 18MAXX twin-screw extruder was used for the experiments in the present invention. According to the manufacturer, this has a total screw torque of 71 Nm.
[0200] A suitable screw configuration controls the degree of filling and the residence time in the extruder. The screw speed can be used to control the degree of filling, the mixing efficiency, the frictional heat generated and the material pressure.
[0201] To form the strands after opening, the extruded compound is cooled.
[0202] The strands can be comminuted by means of a cold or hot die cutting process. Advantageously, the strands are comminuted while still in the solidification phase by head pelletizing or a hot die cutting process. For this purpose, a head pelletizer, which may be gas-tight, with rotating cutting knives is preferably used, which takes place directly at the outlet of the extruder. A (stepless) speed control of the head pelletizer allows the particle length to be adjusted as a function of the solids throughput.
[0203] Depending on the moisture content, the color particles thus obtained are still dried if necessary.
[0204] The bulk density of the color particles according to the invention is 500-1,000 g/l; particularly preferably, the bulk density is 600-900 g/l.
[0205] In a further, third aspect, the present invention relates to color particles comprising or consisting of a carbohydrate matrix comprising or consisting of a starch having an amylopectin content of at least 80% and at least one viscosity modifying ingredient, at least one emulsifier, water, and optionally at least one colorant and/or at least one flavoring or odiferous substance or at least one aroma or scent obtainable by the process according to the invention.
[0206] Preferably, the process is carried out with a starch containing more than 90% amylopectin, most preferably with a starch containing more than 95% amylopectin that has practically no amylose.
[0207] A further aspect of the invention relates to the use of the color particles according to the invention for the production of foods, beverages, cosmetics, in particular oral hygiene products, pharmaceuticals, consumer goods, in particular detergents and cleaning agents in liquid, gel or powder form, pet food or pet care products.
[0208] Due to their advantageous properties, the color particles according to the invention are excellently suited for giving the above-mentioned products a visually improved appearance or texture. A significant advantage of the color particles according to the invention is that, due to their stability, the optical appearance or texture can be maintained over the shelf life of the products.
[0209] Most preferably, the color particles according to the invention are used in oral care products such as chewing gums, toothpaste, mouth gels, chewable tablets and chewy sweets, and cosmetic products such as shampoo, shower gel, exfoliating products, creams, lotions, foodstuffs, in particular dairy products such as yogurt, beverages, and detergents and cleaning products such as dishwashing products, liquid soaps, liquid washing emulsions, soaps or toilet cleaners.
[0210] With regard to preferred constituents of the color particles, their preferred or alternative embodiments, their mixing and quantity ratios and their advantageous effects, reference is made to the above detailed description in connection with the color particles according to the invention, which is equally valid for the process according to the invention in accordance with the second aspect of the invention, so that it is unnecessary to repeat it.
[0211] Particularly preferred for use according to the invention are color particles comprising starch with an amylopectin content of more than 90%, in particular potato starch or rice starch.
[0212] The best results are obtained with color particles comprising pure amylopectin potato starch to form the carbohydrate matrix. This starch with over 95% amylopectin content contains virtually no amylose.
[0213] Ultimately, the present invention relates to foodstuffs, beverages, cosmetics, in particular oral hygiene products, pharmaceuticals, consumer articles, in particular detergents and cleaning agents in liquid, gel or powder form, pet food or pet care products, which contain the color particles according to the invention.
[0214] In a preferred embodiment, the food products are selected from the group consisting of instant beverage powders, tea, soup or sauce powders, baked goods, chewy sweets, confectionery and dairy products, preferably yogurt. The color particles are most preferably used to improve the appearance and consistency of the following products: pre-shave products, acidic, alkaline and neutral detergents, e.g. floor cleaners, window glass cleaners, dishwashing detergents, bathroom and sanitary cleaners, scouring agents, solid and liquid WC cleaners, liquid detergents, powder detergents, fabric softeners, laundry soaps, disinfectants, air fresheners in liquid or gel form, personal care products such as solid and liquid soaps, shower gels, shampoos, shaving soaps, shaving foams, bath oils, cosmetic emulsions of the oil-in-water, water-in-oil and water-in-oil-in-water type, e.g., skin creams and lotions, facial creams and lotions, sunscreen creams and lotions, after-sun creams and lotions, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, aftershave creams and lotions, tanning creams and lotions, hair care products such as hair gels, hair lotions, hair conditioners, hair creams and lotions, deodorants and antiperspirants, such as underarm sprays, roll-ons, deodorant sticks, deodorant creams, and decorative cosmetics and oral hygiene products.
[0215] Most preferred are the cosmetics selected from the group that consists of oral care products such as chewing gum, toothpaste, mouth gels, chewing tablets and chewing candies, shampoo, shower gel, exfoliating products, creams and lotions.
[0216] According to a preferred further development of the invention, the color particles according to the present invention are present in these foodstuffs, cosmetics, in particular oral hygiene products, pharmaceuticals, consumer articles, in particular detergents and cleaning agents in liquid, gel or powder form, animal foodstuffs or animal care products in amounts of 0.001 to 10% by weight, even more preferably 0.05 to 4% by weight and most preferably 0.1 to 2% by weight, based on the total weight of the preparation.
[0217] The present invention is described in more detail below by means of examples which, however, do not limit the scope of protection of the objects according to the invention. Unless otherwise indicated, the proportions given below refer to weight.
EXAMPLES
Example 1
[0218] Preparation of the Color Particles According to the Invention
[0219] A suitable raw material compound, as described in the following examples, was metered into a Leistritz ZSE 18-MAXX twin-screw extruder with eight-barrel blocks and several separately temperature-controlled zones and processed with the following operating conditions. The temperature profile in the barrels was controlled as follows: housing 1: unheated; housings 2 to 8: 90° C.; die plate (1 mm hole diameter): 90° C. At a screw speed of 100 rpm, the working pressure was 9 bar; the throughput was 2 kg/h.
[0220] For the production of color particles with a nominal particle size of approx. 1 mm, 1 to 2 knives made of sheet steel and a pelletizing plate with 18 holes with a nominal diameter of 1.0 mm were used. The speed control of the head pelletizer for setting the pellet length was stepless depending on the solids throughput. The granules obtained have a bulk density of approx. 600 to 900 g/liter. Subsequently, dust and oversize particles were removed by a double-deck sieve with sieve sizes of 0.8 mm and 1.25 mm. The sieve losses amounted to less than 5% of the yield.
[0221] The color particles thus obtained were added to the toothpaste bases prepared as described below at a dosage of 1% by weight or to a commercial yogurt, 1.5% fat content, at a dosage of 1% by weight.
Example 2
[0222] Preparation of a Toothpaste Base (Silica Base)
TABLE-US-00002 Block A Weight % Water, demin. 21.81 Sorbitol 70% 45.00 Solbrol M Na-salt 0.15 Trisodium phosphate 0.10 Saccharin 450-fold 0.20 Sodium monofluorophosphate 1.14 PEG 1500 5.00
TABLE-US-00003 Block B Weight % Sident 9 (abrasive silica) 10.00 Sident 22 S (thickening silica) 8.00 Sodium carboxymethyl cellulose 1.10 Titanium (IV) oxide 0.50
TABLE-US-00004 Block C Weight % Water, demin. 4.50 Sodium lauryl sulfate (SLS) 1.50
[0223] The ingredients of block A were mixed and added to a blender. The ingredients of block B were mixed, added to the ingredients of block A in the mixer, mixed under vacuum at 25 to 30° C. for 30 min, then brought to normal pressure and the mixer was stopped. The ingredients of block C were mixed and added to the mixture in the mixer, mixed under vacuum at 25 to 30° C. for 20 to 30 min, then brought to normal pressure and the mixer was stopped.
Example 3
[0224]
TABLE-US-00005 Block A Weight % Water, demin. 21.00 Saccharin 450-fold 0.20 Solbrol M Na-Salt 0.20 Sodium monofluorophosphate 0.80 Sorbitol 70% 29.00
TABLE-US-00006 Block B Weight % Calcium carbonate 35.00 Sident 22 S (thickening silica) 3.50 Sodium carboxymethyl cellulose 1.30 Titanium (IV) oxide 0.50
TABLE-US-00007 Block C Weight % Water, demin 5.50 Sodium Lauryl Sulfate 2.00
[0225] The ingredients of block A were mixed and added to a blender. The ingredients of block B were mixed, added to the ingredients of block A in the mixer, mixed under vacuum at 30-35° C. for 45 min, then brought to normal pressure and the mixer was stopped. The ingredients of block C were mixed and added to the mixture in the mixer, mixed under vacuum at 30-35° C. for 20 min, then brought to normal pressure and the mixer was stopped.
Example 4
[0226] Making a Toothpaste Base (Gel Base)
TABLE-US-00008 Block A Weight % Sorbitol 70% 63.00 Water, demin. 6.81 Saccharin 0.20 Sodium monofluorophosphate 1.14 Solbrol 0.15 Trisodium phosphate 0.10 PEG 1500 (PEG 32) 5.00
TABLE-US-00009 Block B Weight % Sident 9 (abrasive Silica) 8.00 Sident 22 S (thickening silica) 8.00 Sodium carboxymethyl cellulose 0.60
TABLE-US-00010 Block C Weight % Water, demin. 4.50 Sodium Lauryl Sulfate 1.50
[0227] The ingredients of block A were mixed and put into a mixer. The ingredients of block B were mixed, added to the ingredients of block A in the mixer, mixed under vacuum at 40-45° C. for 15 min, then brought to normal pressure and the mixer was stopped. The ingredients of block C were mixed and added to the mixture in the mixer, mixed under vacuum at 40-45° C. for 15 min, then brought to normal pressure and the mixer was stopped.
TABLE-US-00011 TABLE 2 Application test in toothpaste bases with a dosage of 1 wt. %. Application test in toothpaste (3 weeks at 45° C.) Starch component of Gel base Silica base Carbonate base the color particle (according to (according to (according to formulation example 4) example 2) example 3) Potato starch O.K. O.K. O.K. (Eliane ™ Gel 100) Rice starch native O.K. O.K. O.K. Potato starch O.K. O.K. O.K. (Aero-Myl) Wheat starch not O.K. not O.K. not O.K. very soft Potato starch O.K. O.K. O.K. (Paselli ™) Capsul ® Tapioca not O.K.; not O.K.; not O.K.; Particles Particles Particles dissolve when dissolve when dissolve when squeezed out squeezed out squeezed out Note: O.K. = okay; corresponds to stably detectable color particles in the toothpaste base.
TABLE-US-00012 TABLE 3 Application test in commercial yogurt, 1.5% fat, with a dosage of 1 wt. %. Stability in yogurt (1% granules in white yogurt; Starch component of 3 days storage in the refrigerator) the color particle optical mechanical formulation (color bled out?) (easy to rub in?) Rice starch native Particles detectable; Perceptible as not bled out particles Potato starch Particles detectable; Perceptible as (Aero-Myl) not bled out particles Wheat starch Particles bled out; no particles detectable after stirring Potato starch Particles detectable; After rubbing no (Paselli ™) not bled out longer perceptible as particles Capsul ® Tapioca Particles bled out; No particles detectable after stirring Potato starch Particles detectable; Perceptible as (Eliane ™ Gel 100) not bled out particles
[0228] As a comparison of the color particles according to the invention produced from rice or potato starch with color particles produced from corn, wheat or tapioca starch shows, the color particles according to the invention are characterized by good storage stability over a longer period of time and good producibility in the extruder. Even in an application with a (high) water content, the color particles according to the invention do not bleed out or dissolve.
Example 5
[0229] Production of Color Particles with Potato Starch
TABLE-US-00013 Designation Quantity (g) Potato starch (Eliane ™ Gel 100) 721 Sorbitol 200 Water 30 Emulsifier monoglycerides 17 Cosmetic colorant blue CI74160 2 Mint aroma Optacool ® OP 30 Sum: 1,000
[0230] The raw materials were mixed and metered into the extruder. The color particles were produced by means of a laboratory extruder (twin screw extruder, Leistritz ZSE 18 MAXX). The temperature profile in the housings is controlled as follows: housing 1: unheated; housing 2 to 9: 90° C.; die plate (hole diameter 1 mm): 90° C. At a screw speed of 100 rpm, the working pressure was 9 bar; the throughput was 2 kg/h.
[0231] (A) Application in Water
The color particles were added to water (1 g in 20 ml water) and evaluated after one week.
[0232] As such, the color particles were well preserved; they were not bled out and the surrounding water showed no visible turbidity. The color particles were readily spreadable and therefore suitable for the application described above.
[0233] (B) Application in Toothpaste
The color particles were applied in different toothpaste bases at a dosage of 1 wt. %, stored at 45° C. and evaluated after three weeks. Three toothpaste bases (silica base, carbonate base, gel base) prepared as described in examples 2 to 4 served as toothpaste bases.
[0234] As shown by the first row of toothpaste samples illustrated in
Example 6
[0235] Production of Color Particles with Potato Starch
TABLE-US-00014 Designation Quantity (g) Potato starch (Eliane ™ Gel 100) 768 Dextrin from corn (Nutriose ®) 100 Water 100 Emulsifier monoglycerides 17 Food coloring 5 Titanium dioxide E171 Mintaroma Optamint ® 10 Sum: 1,000
[0236] The raw materials were mixed and metered into the extruder. The color particles were produced by means of a laboratory extruder (twin screw extruder, Leistritz ZSE 18 MAXX). The temperature profile in the housings is controlled as follows: housing 1: unheated; housing 2 to 9: 90° C.; die plate (hole diameter 1 mm): 90° C. At a screw speed of 100 rpm, the working pressure was 9 bar; the throughput was 2 kg/h.
[0237] (A) Application in Water
The color particles were added to water (1 g in 20 ml water) and evaluated after one week.
[0238] As such, the color particles were well preserved; they were not bled out and the surrounding water showed no visible turbidity. The color particles were readily spreadable and therefore suitable for the application described above.
[0239] (B) Application in Toothpaste
The color particles were applied in different toothpaste bases at a dosage of 1 wt %, stored at 45° C. and evaluated after three weeks. The toothpaste bases used were the three toothpaste bases described in Examples 2 to 4 (silica base, carbonate base, gel base).
[0240] The color particles were well preserved as such; the surrounding toothpaste base showed no visible bleeding. The color particles were readily spreadable and therefore suitable for the application described above.
Example 7
[0241] Production of Color Particles with Corn Starch
TABLE-US-00015 Designation Quantity (g) Cornstarch 774 Dextrin from corn (Nutriose ®) 100 Water 100 Emulsifier Monoglycerides 11 Food coloring 5 Titanium dioxide E171 Mint flavor Optacool ® MG-E 10 Sum: 1,000
[0242] The color particles were prepared as described in Example 6.
[0243] (A) Application in Water
The color particles were added to water (1 g in 20 ml water) and evaluated after one week. The color particles had become a cloudy mass and were no longer perceptible as particles.
Example 8
[0244] Production of Color Particles with Capsul® Tapioca
TABLE-US-00016 Designation Quantity (g) Capsul ® Tapioca 751 Dextrin from corn (Nutriose ®) 100 Water 100 Emulsifier Monoglycerides 17 Cosmetic Colorant Blue CI74160 2 Mint aroma Optacool ® OP 30 Sum: 1,000
[0245] The color particles were prepared as described in Example 3.
[0246] (A) Application in Water
The color particles were added to water (1 g in 20 ml water) and evaluated after one week. The color particles had become a cloudy mass and were no longer perceptible as particles.
[0247] (B) Application in Toothpaste
The color particles were applied in different toothpaste bases at a dosage of 1 wt %, stored at 45° C. and evaluated after three weeks. Three toothpaste bases (silica base, carbonate base, gel base) were used as toothpaste bases, which were prepared as described in Examples 2 to 4.
[0248] As shown by the second row of toothpaste samples shown in
Example 9
[0249] Analysis of the Viscosity of Different Starches
[0250] The starch powders were each prepared as a 10% suspension in water at room temperature.
[0251] An Anton Paar Rheometer MCR302, cone-plate system, cone type CP-50-1 at a constant shear rate of 5 sec.sup.−1 was used to determine viscosity. Investigations were carried out in a temperature range of 25-90° C.: (i) heating: temperature program 25-90° C. with a heating rate of 13° C. per min, and (ii) cooling: temperature program 90-25° C. with a cooling rate of 13° C. per min. The results of the measurements are given in Table 4 below:
TABLE-US-00017 TABLE 4 Viscosity Viscosity Temperature (heating) (cooling) Raw material (° C.) (mPa .Math. s) (mPa .Math. s) Potato starch 90 19 20 (Eliane ™ Gel 80 53 15 100) 70 193 17 60 21 50 30 40 46 Cornstarch 90 181,200 170,700 80 274,300 179,600 70 91,890 205,900 60 248,200 50 300,200 40 377,000 Wax corn 90 221 352 Capsul ® 80 2 2,425 70 2 1,453 60 626 50 416 40 274 Potato starch 90 491 1,046 (Paselli ™) 80 3 2,107 70 2 1,601 60 389 50 391 40 111 Potato starch 90 110 185 (Aero-Myl) 80 48 721 70 45 783 60 983 50 875 40 908 Rice starch 90 31,340 28,490 80 46,400 26,620 70 186 28,710 60 30,420 50 34,280 40 37,510 Wheat starch 90 87,740 88,270 80 100,800 96,850 70 124,200 108,800 60 129,700 50 158,000 40 207,100 Capsul ® 90 4 4 Tapioca 80 3 3 70 3 2 60 2 50 2 40 2
[0252] The viscosity of the starch has an influence on the stability of the color particles during application. Preferably, the viscosity of the starch used is 10 mPa.Math.s to 50.000 mPa.Math.s, measured as a 10% solution in water at 90° C.