CA1330270C - Pulverulent, water-dispersable carotenoid formulations and their preparation - Google Patents
Pulverulent, water-dispersable carotenoid formulations and their preparationInfo
- Publication number
- CA1330270C CA1330270C CA000556833A CA556833A CA1330270C CA 1330270 C CA1330270 C CA 1330270C CA 000556833 A CA000556833 A CA 000556833A CA 556833 A CA556833 A CA 556833A CA 1330270 C CA1330270 C CA 1330270C
- Authority
- CA
- Canada
- Prior art keywords
- carotenoid
- solution
- phase
- water
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/24—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by six-membered non-aromatic rings, e.g. beta-carotene
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
- A23L5/40—Colouring or decolouring of foods
- A23L5/42—Addition of dyes or pigments, e.g. in combination with optical brighteners
- A23L5/43—Addition of dyes or pigments, e.g. in combination with optical brighteners using naturally occurring organic dyes or pigments, their artificial duplicates or their derivatives
- A23L5/44—Addition of dyes or pigments, e.g. in combination with optical brighteners using naturally occurring organic dyes or pigments, their artificial duplicates or their derivatives using carotenoids or xanthophylls
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B61/00—Dyes of natural origin prepared from natural sources, e.g. vegetable sources
Abstract
ABSTRACT OF THE DISCLOSURE:
Pulverulent water-dispersable carotenoid formulations in which the carotenoid is dissolved in an edible oil and the oil solution is in the form of small droplets are prepared by a process in which a carotenoid is rapidly dissolved in a volatile, water-miscible, organic solvent at from 50 to 240°C, together with from 1.5 to 20 times the weight, based on the carotenoid, of an edible oil, and an emulsifier, under atmospheric or superatmospheric pressure, the hydrophilic solvent component is transferred to the aqueous phase from the resulting molecular disperse solution by immediate mixing with an aqueous solution of a protective colloid at from 0 to 50°C, the hydrophobic oil phase which contains the carotenoid in solution being formed as the microdisperse phase, and the resulting two-phase mixture is freed from the solvent and the water in a conventional manner. These formulations are in particular useful for coloring food and animal feeds.
Pulverulent water-dispersable carotenoid formulations in which the carotenoid is dissolved in an edible oil and the oil solution is in the form of small droplets are prepared by a process in which a carotenoid is rapidly dissolved in a volatile, water-miscible, organic solvent at from 50 to 240°C, together with from 1.5 to 20 times the weight, based on the carotenoid, of an edible oil, and an emulsifier, under atmospheric or superatmospheric pressure, the hydrophilic solvent component is transferred to the aqueous phase from the resulting molecular disperse solution by immediate mixing with an aqueous solution of a protective colloid at from 0 to 50°C, the hydrophobic oil phase which contains the carotenoid in solution being formed as the microdisperse phase, and the resulting two-phase mixture is freed from the solvent and the water in a conventional manner. These formulations are in particular useful for coloring food and animal feeds.
Description
" ` 133~70 O.Z. 0~50/38936 Pulverulent, water-d;spersable carotenoid formulat;ons ~ ~ . . .
and the;r preparation The present invention relates to the convers;on of carotenoids to a finely divided, pulverulent form, S the carotenoid being dissolved in an edible o;l and the oil solut;on being in the form of very small oil drops.
This formulation is used in particular for coloring food and animal feeds.
The carotenoids constit~te a group of colored pigments which have a yellow to red hue, occur ~idely in nature and impart a typical color to many foods. The most important members of this class of substances are B-carotene, ~-apo-8'-carotenal, canthaxanthine and cit-ranaxathine. These substances ~hich can be synthesized are important colorants for both the food and animal feeds industry and pharmaceutical technology, for exam-ple as substitutes for synthetic colorants, and are of `;
interest, for example, because of their provitamin A
~; activity. -Virtual~y all carotenoids are insoluble ir, water and also have only sl;ght solubility in fats and oils.
This limited solubility and the high sensitivity to oxidation prevent the relatively coarse-particled pro~
ducts obtained in the synthesis from being used directly for coloring food or animal feeds, since only a low color yield can be achieved and the substances in coarsely crystalline form are poorly absorbed. These effects w-hich are disadvantageous when the carotenoids are used in practice are particularly evident in an aqueous medium, ::
since ~ost of them are completely insoluble therein.
Various methods have been described for improving the color yields and increasing the absorbability, all ~ ~;
of which aim at reducing the crystallite size of the active ingredients and bringing it to a particle size range smaller than 10 ~m. For example, according to Chimia 21 (1967), 329, ~-carotene together with edible oil can be milled to a particle size of from 2 to S ~m "
".
.
.,~ .,"
` 133~7~
- Z - o.Z~ 0050/38936 ' under a nitrogen atmosphere in a colloid mill. Accord-ing to Food Technol. 12 (1958), 527, the coating oil simultaneously protects the active ingredient from ox;-dation. A suspension obtained in this manner and con-taining up to 20 or 30~ of active ingredient can success-; fully be used for coloring fats and oils since the low 'solubility is nevertheless sufficient to dissolve the crystals at the low concentration usually employed.
~hile oily or fatty systems can thus readily be colored ~ith the pure crystalline substances, aqueous systems'are virtually impossibLe to color with the sa;d substances. Fur'thermore, because most of the carotenoids are completely ;nsoluble in ~ater, the pure carotenoids ix~d'~ith the food or ~ith the animal feed are very poorly ut;lized by the human or animal organism. The carotenoids have very limited solubility even in organic solvents, such as alcohols and alkanes.
The desired coloring ind absorptibn properties ;~
can only be achieved via the very finely divided state.
20 A desirable partic~le size is smaller than 1 ~m, ~hich ~;
can be achieved by milling only with damage to the active ingredient, if at all. ``~
Processes which represent a certain amount of progress in comparison are known processes in which the Z5 active ingredient is dissolved in a water-immisc;ble sol-vent, preferably a`chlorohydrocarbon, such as chloroform '~
o~ methyle'ne chloride,'the solution is emulsified by homogenization in a gelatine/sugar solution, and finally .:. . ..
the solvent is'str;pped off from the emulsion, the active 30 ingredient being liberated in finely crystalline form. '''~
This process is described in Chimia 21 (1967), 329, German ~`
Published Application DAS 1,211,911 and German Laid-Open Application DOS 2,534,091. A finely divided powder is ~ then obtained from the resulting suspension by removal of ;~ 35 ~ater.
Ho~ever, the abovementioned process has the dis-advantage that chlorohydrocarbons have to be used in "` ~ 133~27~
- 3 - O.Z. 0050/38936 order to achieve a suffic;ently high concentrat;on of active ingred;ent ;n the emulsion phase. Complete re-moval of the chlorohydrocarbons, wh;ch ;s necessary for ~ ;
toxicological reasons, is technically d;ff;cuLt to achieve.
These disadvantages were overcome by the process of European Patent 65,193, in which a carotenoid is dissolved in a volatile, water-miscible organic solvent at from 50 to Z00C, if necessary under superatmospheric pressure, in less than 1tl seconds, the carotenoid is immediately precipi-tated in colloidal form from the resulting molecular disperse solution by rapid mixing with an aqueous solution of a swel-lable colloid at from 0 to 50C, and the resulting dispers;on is freed from the solvent and the dispersing med;um in a ~ conventional manner. The mean size of the sol;d carotenoid ; 15 particles produced by this method is l3ss than 0.3 ~m.
In another process (cf. U.S. Patent 2,861,891 and Austrian Patent 202,273), a water-dispersable carotenoid formulation is obtained by preparing, at fro~ 100 to 160C, a supersaturated solution of the carotenoid in an edible oil which is li~uid at about 20-40C, emulsifying this super-saturated solution in an aqueous, gelatinous material, and converting the emulsion in a conventional manner to small dry particles. ~ -~; If the dry po~der is redispersed in warm water, ;~
a cloudy, orange yellow e0ulsion is formed again. This can be used, for example, for coloiring food. Important . . .
performance characteristics of these colorant preparations are solubility, hue, color strength, opacity and stab;lity -in the mediun used (R.H. 3unnell, ~. Driscoll and I.C.
aauernfeind~ Food Technol. XII t1958), 1-81). ~`
However, a spectrophotometric investigation of the finely divided carotenoid formulations produced by the stated prior art shows that, particularly at fairly .k~J''.i'~' high concentrations, for example 3 2% of dry powder, the extinction values at the band maximum of the tinctorially effective absorption bands in the visible spectral range are only SOX of the maximum values achievable in a true 133~70 - 4 - o.Z. 0050/38936 solution. From the economic point of view, this is a considerable d;sadvantage since only 50% of the poten-tial color strength of a carotenoid can be utilized, for example for coloring a food, and the dose of the color-S ant therefore has to be doubled in order to obtain thedesired coLor strength. It is also known that the hue of a food colored with carotenoids is determined to a great extent by the particle s;ze and the physical state ~-(solid, solution). With the prior art products, the range of potential differences in the hue of a selected carotenoid is far from being exhausted. It is further- ;
more known that the biological absorption of water-insoluble act;ve ingredients, for example after oral administration, is greatly influenced by the particle size and the physi-cal state. The carotenoid preparations produced accord-ing to the prior art therefore do not satisfy the pre- ~; ;
condition for optimum biological absorption. -~
It is an object of the present invention to pro-vide a process which makes it possible to prepare caroten-~
20 oid formulations which do not have the stated disadvan- - ~`
tages.
~; ~e have found that this object is achieved, ac-cording to the invention, if the carotenoid is rapidly dissolved in a volatile, water-miscible, organic so-lven~
at from 50 to 240C, preferably from 150 to 200C, to-gether with from 1.5 to 20 times the weight, based on the carotenoid, of an edible oil~ and an emulsifier, under atmospheric or superatmospheric pressure, the hydrophilic solvent component is transferred to the aqueous phase~ ~ ~
30 froM the resulting molecular disperse solution by rapid --mixing with an aqueous solution of a protective colloid at from û to 50C, the hydrophobic oil phase which con-tains the carotenoid in solution being formed as the ~icrodisperse phase, and the resulting two-phase mixture is freed from the solvent and the water in a conventional manner.
The novel procedure utililes ehe fact that the ;~
~ ;;; .,' '', :~ .
.
'~' , ~ 5 - O.Z. 0050~38936 solubility of the carotenoids in a solution of an edible oil ;n water-miscible solvents, which is very low at low temperatures increases substantia~ly with increasing tem-perature, but, despite the high temPeratures~ a short S residence time at elevated temperatures substantially prevents isomerization which affects the hue, the color strength and the biological activity. However, this was in contradiction to the fact that the isomer;zation which usually occurs on heating in hot oil is itself used to 1û inhibit recrystallizat;on in the drops of the emulsified o;l phase when the temperature is reduced, the said re-crystallization having an adverse effect on the hue and the color strength of the desired end product. lt was therefore surprising that, in spite of suppress;ng the tendency to isomerizatio~ at elevated temperatures, and after cool;ng, the product obtained by the novel pro-cedure contains the caroteno;d, spectrophotometrlcally detectable, as a molecular disperse, suPersaturated oil solution stabilized to recrystallization, in the form of submicroscoPic oil particles, and, compared w;th prior art products, has up to 100% greater color strength coupled with a shift in the hue to previously unaccessible ranges. -The photochemical stability of the hydrosols prepared by - ~-. .
the novel process is super;or to that of the products pre-pared according to the prior art by a factor of more than 5.
The carotenoids which can be used for carrying out the invention are the known, obtainable, natural or synthetic members of this class of compounds, which can 3û be used as color-imparting materials, for example carot-ene, lycopene, bixine, zeaxanthine, cryptoxanthine, cit-ranaxanehine~ luteine, canthaxanthine, astaxanthine,~
apo-4'-carotenal, 3-apo-8'-carotenal, 3-apo-12'-carotenal, 3-apo-8'-carotenic acid and esters of hydroxyl-contain-ing and carboxyl-containing members of this group, for example the lower alkyl esters and preferably the methyl and ethyl esters. The compounds which have been readily 6 ~ 7 ~ z ooSo/38936 available industrially to date, such as B-carotene, can- -thaxanthine, B-apo-8'-carotenal and ~~apo-8'-carotenates, are part;cularly preferred.
Water-miscible, heat-stable, volatile solvents contain;ng only carbon, hydrogen and oxygen, eg. alcohols, ethers, esters, ketones and acetals, are particularly suit-able for carry;ng out the novel process. Ethanal, n-propanol, isopropanol, butane-1,2-diol 1-methyl ether, propane-1,2- ~-diol 1-n-propyl ether and acetone are preferably used.
In general, it is advantageous to use solvents which are not less than 10% water-miscible, have a boil-ing point of less than 200C and/or contain less than 10 carbon atoms.
Suitable edible oils are oils which are liquid 15 at from Z0 to 40C. Examples are vegetable oils, such ~
as corn oil, coconut oil, sesame oil, peanut oil, soybean ~ ~ ;
oil or co~tonseed oil. Peanut oil is particularly pre~
ferred. Other suitable oils or fats are shortening, beef dripping and butter fat. The edible oils are gener~
aLly used ;n an amount of from 1.5 to 20, preferably from 3 to 8, times the we;ght of the carotenoid, and the total oil content of the carotenoid formulation should not ex~
ceed 60% by weight if it is intended to prepare a dry powder.
Su;table protective colloids are any conventional -~
protective colloids perm;tted ;n food and an;mal feeds, examples are gelat;ne, starch, dextr;n, dextran, pect;n, gum arabic, case;n, caseinate, whole milk, skimmed milk, milk powder or mixtures of these. Ho~ever, it ;s also possible to use polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose, carboxymethylcellulose, hydroxypropyl-cellulose and alginates. For further details, reference may be made to R.A. Morton, Fast Soluble Vitamins, Intern.
Encyclopedia of Food and Nutr;tion, Vol. 9, Pergamon 35 Press, 1970, pages 128-131~ To increase the mechanical stability of the end product, it is advantageous to add to the colloid a plasticizer, such as sugar or sugar .: .
~ ~.
" 133~0 ~ 7 O.Z. 0050/38936 alcohols, eg. sucrose, glucos~, lactose, invert sugar, sorbitol, mannitol or glycerol. M;nor amounts of methyl esters or propyl esters of p-hydroxybenzoic acid, sorbic acid and Na benzoate may also be added as preservatives.
The ratio of protective colloid, pLasticizer and oil to carotenoid is in general chosen so that the result-ing end product conta;ns from 0.5 to 10, preferabLy from 2 to 5, % by we;ght of carotenoid, from 5 to 50% by we;ght of an edible oil, from 10 to 50% by we;ght of a pro-tective collo;d and from 20 to 70% by weight of a plas-ticizer, all percentages being based on the dry we;ght of the powder, as well as m;nor amounts of a stabilizer~
The mean particle size of the oil phase present ;n the ~
powder and supersaturated molecular disperse carotenoid ~-15 is less than 0.3 ~m, and the half width of the size ~ ~;
distribution is less than 50%. The product contains virtually no oil particles having a particle size greater than 1 ~m.
To increase the stability of the active ingredient to oxidative degradation, ;t is advantageous to add stabil~
izers, such as ~-tocopherol, lecithin, tert-butylhydroxy-toluene, tert-butylhydroxyanisole, ethoxyquine or ascorbyl palmitate.
They can be added to either the aqueous phase or the solvent phase but are preferably dissolved together with the colorants and the oil, in the solvent phase.
~ The novel process gives a viscous liquid which ; has a deep coloration and from which the solvent can be removed in a conventional manner depending on the boil-ing point, for example by d;stillation, under atmospheric or reduced pressure, or by extraction with a water-.
immiscible solvent. Preferably, however, the solvent is removed together with the water by spray drying or spray granulation.
The dry powder obtained can be redissolved in water with uniform fine distribution of the active in-gredient in the particle size range < 0.5 ~m. The ~
, ','.'' ~.' ' ., .. ~...
:, . . .::
.. :
. .-: : :::
.:
- ".'- ' ''.
"' ' ~
8 I 3 3 0 ~ ~ ~ Z . 0050,38936 photochemical stability test shows that the resulting hydrosol of the act;ve ingredient is extremely stable despite being finely d;vided.
If necessary, the microdisperse oil phase super-saturated with carotenoid can also be brought to a suitable pH and then flocculated together with the protective colloid -~
and thus converted to a form from which the solvent and a major part of the dispersing medium can be removed in a simple manner by filtration or centr;fuging~ The co-acervate thus obtained is then further dried in a conven~
tional manner and converted to granules.
Specif;cally, the novel process ;s carr;ed out as follo~s, for example using an apparatus as shown schematically in F;g. 1.
15The apparatus is divided into parts I, II and ~-~
III. Part II is the high temperature sect;on, while in parts I and III the temperatures are less than 50C.
In vessel (1), a suspension of the carotenoid to-gether with the oil in the selected solvent in a concen-20 tration of from 2 to 20% by ~eight, based on the mixture, `
with or ~ithout the addition of from û.1 to 1û% by weight of stabilizers, is initially taken. Vessel (2) conta;ns the solvent without admixed carotenoid. The suspensions of active ingredient and the solvent are fed to the mix~
25 ing chamber t7) via the pumps (3) and (4) respectively; ;~
the mixing ratio can be predetermined by choosing the particular deLivery of the pumps, and is selected so that, ~9 depending on the solvent and the residence time, the resulting carotenoid concentration in the mixing chamber 30 is from 0.5 to 10~ by weight, based on the solutlon. The -volume of the mixing chamber (7) is such that the resi-dence time in (7) is preferably less than 1 second at the selected delivery of the pumps (3) and (4).
3efore entering the mixing chamber, the solvent is brought to the desired temperature by means o~ the heat exchanger (6), while the oil-containing suspension of active ingredient is kept at belo~ 50C by feed;ng it ,.. 133~70 - 9 - O~Z. 0050/38936 via the thermally insulated l;ne t5). As a result of turbulent mi~ing in (7) at from 50 to 24~C, preferably fro~ 150 to 200C, the active ingredient goes into solu- ~ ~
tion, and, after a short res;dence time, preferably less ~ -than 1 second, the result;ng solution passes via (8) into the second mixing chamber (11), in which, by admixing an aqueous protective colloid/plasticizer solution via pump (9) and feed line (10), the molecular disperse carotenoid solution is divided into a two-phase mixture with forma-10 tion of a microdisperse oil phase containing the active ~
ingredient in supersaturated solution and a homogeneous, ~ `
aqueous phase containing the water-miscible solvent. The microdisperse two-phase mixture is then discharged via line (12) and the pressure rel;ef valve and fed to the stock vessel (14). To obta;n a very high concentration of active ingredient, the dispersion can be circulated via the suction line (15).
If the pressure relief valve (13) is set at above .
one bar, it is even possible to use solvents at tempera- ~-tures above their boiling point (under atmospheric pres-sure) in the novel process. ~ -A pulverulent preparation can be obtained from the dispersion in a conventional manner, for example as; -described in German Laid-Open Application DOS 2,534,091, by spray drying or by spray cooling or by coating the particles, separation and drying in a fluidized bed. ;~
For spray drying, the dispersion is either first `~ freed from the solvent by distillation, preferably under reduced pressure, or by extraction with a water-immiscible solvent, or the entire mixture is spray-dried and water ` and solvent are stripped off together in the spray tower in this manner.
The carotenoid powder is obtained in either dry or free-flowing form at the bottom of the spray tower. `~ -35 In some cases, it may be advantageous additionally to :
carry out complete drying in a fluidized bed. Instead ~ `~
of preparing the powder formulation by spray drying, it ~: .'. ` .'~
- . . , -. ~ : ~::
, :,, , ..',, ,' ,'": `:',' ,' I ~ 3 V 2 70~ z . ooso/38936 is also possible to use any other methods to convert the caroteno;ds already f;nely d;str;buted ;n the water/o;l/
solvent dispers;on into powder form.
A known and equally su;table method comprises, S for example, emulsify;ng the dispersion freed from the solvent with liquid paraffin, cooling the mixture, separat- -~
ing the liquid paraffin from the coated carotenoid par~
~icles, washing the result;ng carotenoid prepara~ion with naphtha and drying the preparation in a fluidized ;
bed.
In the novel procedure, it was particularly sur~
prising that the use of the stated ~ater-misc;ble sol-vents mixed ~ith an edible oil which may additionally contain emulsifiers, such as ascorbyl palmitate, mono-and diglycerides, esters of monoglycerides with aceticacid, citric acid, lactic acid or diacetyltartaric acid, polyglycerol fatty acid esters, sorbitan fatty acid es- -ters, propylene glycol fatty ac;d esters, stearoyl 2-lactylates or lecithin, permits the preparation of highly supersaturated solutions in uhich, in spite of suppres-sion of the trans-cis isomerization, no recrystallization of the carotenoid takes place ~ithin the submicroscopic oil drops supersaturated with active ingredient in the microdisperse oil phase, after the phase separation in-duced by turbulent mixing with the aqueous protectivecolloid solut;on, even during removal of the volatile solvent, for example by distillation or spray dry;ng, and after cool;ng.
It is furthermore surpr;sing that admixing of the solvent-containing o;l solut;on of the caroteno;ds with the aqueous protective collo;d solution induces phase ;~
separat;on dur;ng wh;ch the disperse oil phase ;s ob-ta;ned in the form of extremely small part;cles, as can-; not be obtained by mechan;cal homogenizat;on. This f;nely dispersed state of the oil phase supersaturated w;th ac~
tive ingredient is also ma;nta;ned dur;ng removal of the volat;le solvent, for example by spray drying. It is : .: :
. ~.: :::-:
:::: . .
:' ~' , 13~27~
0.Z. 0050/38936 easily Possible to obta`in preparations in which the major fraction in the o;l phase has a particle size of 0.2 ~m, without part;cles of active ingred;ent larger than 1 ~m -~`
simultaneously being present. The absorption spectrum 5 of such carotenoid preparations shows the band form and ~--extinction typical of the molecular disperse solut;on of a carotenoid in an edibLe oil, even after spray drying and redissolution in an aqueous medium.
The Examples which follow illus~rate the novel process.
S g of 3-trans-carotene are suspended in Z40 9 of a solution of 4 g of ascorbyl palmitate, 5 9 of a-tocopherol and 20 9 of peanut oil in ;sopropanol, the ` 15 pressure relief valve (13) is set at 25 bar and the said suspension is mixed in mixing chamber (7) with 360 9 of isopropanol which has been heated to 225C in heat ex-changer (6). The suspension is metered at 2 l/h and the~ .
solvent at 3 l/h, and the residence time in mixing cham-ber (7) is 0.35 second. The molecular disperse solution formed at 190C is then fed to mixing chamber (11), in ~;~ which turbulent mixing with 4,000 9 of an aqueous solu-tion of 60 9 of gelatine and 90 9 of sucrose, brought to pH 9 with lN NaOH, at a metering rate of 27 l/h results ~ 25 in phase separation ~ith formation of a microdisperse oil~ ;
;~ phase which contains the 3-carotene in the form of a `
supersaturated solution. A microdisperse two-phase mix- -ture having a yellow hue and a temperature of 50C is ob~
tained in collecting vessel (14). ParticLe size analy- `~-sis by proton correlation spectroscoPy gives a mean par~
t;cle size of the oil phase of 210 nm and a distribution width of ~40Z.
.. .....
Removal of the solvent under reduced pressure at 50C in a distiLLation apparatus gives a viscous l;quid ~; 35 which can be converted to a stable, water-soLubLe dry po~der by spray drying. The ~-carotene content of this dry powder is 2.4% by weight.
,, .
;': ' ~
and the;r preparation The present invention relates to the convers;on of carotenoids to a finely divided, pulverulent form, S the carotenoid being dissolved in an edible o;l and the oil solut;on being in the form of very small oil drops.
This formulation is used in particular for coloring food and animal feeds.
The carotenoids constit~te a group of colored pigments which have a yellow to red hue, occur ~idely in nature and impart a typical color to many foods. The most important members of this class of substances are B-carotene, ~-apo-8'-carotenal, canthaxanthine and cit-ranaxathine. These substances ~hich can be synthesized are important colorants for both the food and animal feeds industry and pharmaceutical technology, for exam-ple as substitutes for synthetic colorants, and are of `;
interest, for example, because of their provitamin A
~; activity. -Virtual~y all carotenoids are insoluble ir, water and also have only sl;ght solubility in fats and oils.
This limited solubility and the high sensitivity to oxidation prevent the relatively coarse-particled pro~
ducts obtained in the synthesis from being used directly for coloring food or animal feeds, since only a low color yield can be achieved and the substances in coarsely crystalline form are poorly absorbed. These effects w-hich are disadvantageous when the carotenoids are used in practice are particularly evident in an aqueous medium, ::
since ~ost of them are completely insoluble therein.
Various methods have been described for improving the color yields and increasing the absorbability, all ~ ~;
of which aim at reducing the crystallite size of the active ingredients and bringing it to a particle size range smaller than 10 ~m. For example, according to Chimia 21 (1967), 329, ~-carotene together with edible oil can be milled to a particle size of from 2 to S ~m "
".
.
.,~ .,"
` 133~7~
- Z - o.Z~ 0050/38936 ' under a nitrogen atmosphere in a colloid mill. Accord-ing to Food Technol. 12 (1958), 527, the coating oil simultaneously protects the active ingredient from ox;-dation. A suspension obtained in this manner and con-taining up to 20 or 30~ of active ingredient can success-; fully be used for coloring fats and oils since the low 'solubility is nevertheless sufficient to dissolve the crystals at the low concentration usually employed.
~hile oily or fatty systems can thus readily be colored ~ith the pure crystalline substances, aqueous systems'are virtually impossibLe to color with the sa;d substances. Fur'thermore, because most of the carotenoids are completely ;nsoluble in ~ater, the pure carotenoids ix~d'~ith the food or ~ith the animal feed are very poorly ut;lized by the human or animal organism. The carotenoids have very limited solubility even in organic solvents, such as alcohols and alkanes.
The desired coloring ind absorptibn properties ;~
can only be achieved via the very finely divided state.
20 A desirable partic~le size is smaller than 1 ~m, ~hich ~;
can be achieved by milling only with damage to the active ingredient, if at all. ``~
Processes which represent a certain amount of progress in comparison are known processes in which the Z5 active ingredient is dissolved in a water-immisc;ble sol-vent, preferably a`chlorohydrocarbon, such as chloroform '~
o~ methyle'ne chloride,'the solution is emulsified by homogenization in a gelatine/sugar solution, and finally .:. . ..
the solvent is'str;pped off from the emulsion, the active 30 ingredient being liberated in finely crystalline form. '''~
This process is described in Chimia 21 (1967), 329, German ~`
Published Application DAS 1,211,911 and German Laid-Open Application DOS 2,534,091. A finely divided powder is ~ then obtained from the resulting suspension by removal of ;~ 35 ~ater.
Ho~ever, the abovementioned process has the dis-advantage that chlorohydrocarbons have to be used in "` ~ 133~27~
- 3 - O.Z. 0050/38936 order to achieve a suffic;ently high concentrat;on of active ingred;ent ;n the emulsion phase. Complete re-moval of the chlorohydrocarbons, wh;ch ;s necessary for ~ ;
toxicological reasons, is technically d;ff;cuLt to achieve.
These disadvantages were overcome by the process of European Patent 65,193, in which a carotenoid is dissolved in a volatile, water-miscible organic solvent at from 50 to Z00C, if necessary under superatmospheric pressure, in less than 1tl seconds, the carotenoid is immediately precipi-tated in colloidal form from the resulting molecular disperse solution by rapid mixing with an aqueous solution of a swel-lable colloid at from 0 to 50C, and the resulting dispers;on is freed from the solvent and the dispersing med;um in a ~ conventional manner. The mean size of the sol;d carotenoid ; 15 particles produced by this method is l3ss than 0.3 ~m.
In another process (cf. U.S. Patent 2,861,891 and Austrian Patent 202,273), a water-dispersable carotenoid formulation is obtained by preparing, at fro~ 100 to 160C, a supersaturated solution of the carotenoid in an edible oil which is li~uid at about 20-40C, emulsifying this super-saturated solution in an aqueous, gelatinous material, and converting the emulsion in a conventional manner to small dry particles. ~ -~; If the dry po~der is redispersed in warm water, ;~
a cloudy, orange yellow e0ulsion is formed again. This can be used, for example, for coloiring food. Important . . .
performance characteristics of these colorant preparations are solubility, hue, color strength, opacity and stab;lity -in the mediun used (R.H. 3unnell, ~. Driscoll and I.C.
aauernfeind~ Food Technol. XII t1958), 1-81). ~`
However, a spectrophotometric investigation of the finely divided carotenoid formulations produced by the stated prior art shows that, particularly at fairly .k~J''.i'~' high concentrations, for example 3 2% of dry powder, the extinction values at the band maximum of the tinctorially effective absorption bands in the visible spectral range are only SOX of the maximum values achievable in a true 133~70 - 4 - o.Z. 0050/38936 solution. From the economic point of view, this is a considerable d;sadvantage since only 50% of the poten-tial color strength of a carotenoid can be utilized, for example for coloring a food, and the dose of the color-S ant therefore has to be doubled in order to obtain thedesired coLor strength. It is also known that the hue of a food colored with carotenoids is determined to a great extent by the particle s;ze and the physical state ~-(solid, solution). With the prior art products, the range of potential differences in the hue of a selected carotenoid is far from being exhausted. It is further- ;
more known that the biological absorption of water-insoluble act;ve ingredients, for example after oral administration, is greatly influenced by the particle size and the physi-cal state. The carotenoid preparations produced accord-ing to the prior art therefore do not satisfy the pre- ~; ;
condition for optimum biological absorption. -~
It is an object of the present invention to pro-vide a process which makes it possible to prepare caroten-~
20 oid formulations which do not have the stated disadvan- - ~`
tages.
~; ~e have found that this object is achieved, ac-cording to the invention, if the carotenoid is rapidly dissolved in a volatile, water-miscible, organic so-lven~
at from 50 to 240C, preferably from 150 to 200C, to-gether with from 1.5 to 20 times the weight, based on the carotenoid, of an edible oil~ and an emulsifier, under atmospheric or superatmospheric pressure, the hydrophilic solvent component is transferred to the aqueous phase~ ~ ~
30 froM the resulting molecular disperse solution by rapid --mixing with an aqueous solution of a protective colloid at from û to 50C, the hydrophobic oil phase which con-tains the carotenoid in solution being formed as the ~icrodisperse phase, and the resulting two-phase mixture is freed from the solvent and the water in a conventional manner.
The novel procedure utililes ehe fact that the ;~
~ ;;; .,' '', :~ .
.
'~' , ~ 5 - O.Z. 0050~38936 solubility of the carotenoids in a solution of an edible oil ;n water-miscible solvents, which is very low at low temperatures increases substantia~ly with increasing tem-perature, but, despite the high temPeratures~ a short S residence time at elevated temperatures substantially prevents isomerization which affects the hue, the color strength and the biological activity. However, this was in contradiction to the fact that the isomer;zation which usually occurs on heating in hot oil is itself used to 1û inhibit recrystallizat;on in the drops of the emulsified o;l phase when the temperature is reduced, the said re-crystallization having an adverse effect on the hue and the color strength of the desired end product. lt was therefore surprising that, in spite of suppress;ng the tendency to isomerizatio~ at elevated temperatures, and after cool;ng, the product obtained by the novel pro-cedure contains the caroteno;d, spectrophotometrlcally detectable, as a molecular disperse, suPersaturated oil solution stabilized to recrystallization, in the form of submicroscoPic oil particles, and, compared w;th prior art products, has up to 100% greater color strength coupled with a shift in the hue to previously unaccessible ranges. -The photochemical stability of the hydrosols prepared by - ~-. .
the novel process is super;or to that of the products pre-pared according to the prior art by a factor of more than 5.
The carotenoids which can be used for carrying out the invention are the known, obtainable, natural or synthetic members of this class of compounds, which can 3û be used as color-imparting materials, for example carot-ene, lycopene, bixine, zeaxanthine, cryptoxanthine, cit-ranaxanehine~ luteine, canthaxanthine, astaxanthine,~
apo-4'-carotenal, 3-apo-8'-carotenal, 3-apo-12'-carotenal, 3-apo-8'-carotenic acid and esters of hydroxyl-contain-ing and carboxyl-containing members of this group, for example the lower alkyl esters and preferably the methyl and ethyl esters. The compounds which have been readily 6 ~ 7 ~ z ooSo/38936 available industrially to date, such as B-carotene, can- -thaxanthine, B-apo-8'-carotenal and ~~apo-8'-carotenates, are part;cularly preferred.
Water-miscible, heat-stable, volatile solvents contain;ng only carbon, hydrogen and oxygen, eg. alcohols, ethers, esters, ketones and acetals, are particularly suit-able for carry;ng out the novel process. Ethanal, n-propanol, isopropanol, butane-1,2-diol 1-methyl ether, propane-1,2- ~-diol 1-n-propyl ether and acetone are preferably used.
In general, it is advantageous to use solvents which are not less than 10% water-miscible, have a boil-ing point of less than 200C and/or contain less than 10 carbon atoms.
Suitable edible oils are oils which are liquid 15 at from Z0 to 40C. Examples are vegetable oils, such ~
as corn oil, coconut oil, sesame oil, peanut oil, soybean ~ ~ ;
oil or co~tonseed oil. Peanut oil is particularly pre~
ferred. Other suitable oils or fats are shortening, beef dripping and butter fat. The edible oils are gener~
aLly used ;n an amount of from 1.5 to 20, preferably from 3 to 8, times the we;ght of the carotenoid, and the total oil content of the carotenoid formulation should not ex~
ceed 60% by weight if it is intended to prepare a dry powder.
Su;table protective colloids are any conventional -~
protective colloids perm;tted ;n food and an;mal feeds, examples are gelat;ne, starch, dextr;n, dextran, pect;n, gum arabic, case;n, caseinate, whole milk, skimmed milk, milk powder or mixtures of these. Ho~ever, it ;s also possible to use polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose, carboxymethylcellulose, hydroxypropyl-cellulose and alginates. For further details, reference may be made to R.A. Morton, Fast Soluble Vitamins, Intern.
Encyclopedia of Food and Nutr;tion, Vol. 9, Pergamon 35 Press, 1970, pages 128-131~ To increase the mechanical stability of the end product, it is advantageous to add to the colloid a plasticizer, such as sugar or sugar .: .
~ ~.
" 133~0 ~ 7 O.Z. 0050/38936 alcohols, eg. sucrose, glucos~, lactose, invert sugar, sorbitol, mannitol or glycerol. M;nor amounts of methyl esters or propyl esters of p-hydroxybenzoic acid, sorbic acid and Na benzoate may also be added as preservatives.
The ratio of protective colloid, pLasticizer and oil to carotenoid is in general chosen so that the result-ing end product conta;ns from 0.5 to 10, preferabLy from 2 to 5, % by we;ght of carotenoid, from 5 to 50% by we;ght of an edible oil, from 10 to 50% by we;ght of a pro-tective collo;d and from 20 to 70% by weight of a plas-ticizer, all percentages being based on the dry we;ght of the powder, as well as m;nor amounts of a stabilizer~
The mean particle size of the oil phase present ;n the ~
powder and supersaturated molecular disperse carotenoid ~-15 is less than 0.3 ~m, and the half width of the size ~ ~;
distribution is less than 50%. The product contains virtually no oil particles having a particle size greater than 1 ~m.
To increase the stability of the active ingredient to oxidative degradation, ;t is advantageous to add stabil~
izers, such as ~-tocopherol, lecithin, tert-butylhydroxy-toluene, tert-butylhydroxyanisole, ethoxyquine or ascorbyl palmitate.
They can be added to either the aqueous phase or the solvent phase but are preferably dissolved together with the colorants and the oil, in the solvent phase.
~ The novel process gives a viscous liquid which ; has a deep coloration and from which the solvent can be removed in a conventional manner depending on the boil-ing point, for example by d;stillation, under atmospheric or reduced pressure, or by extraction with a water-.
immiscible solvent. Preferably, however, the solvent is removed together with the water by spray drying or spray granulation.
The dry powder obtained can be redissolved in water with uniform fine distribution of the active in-gredient in the particle size range < 0.5 ~m. The ~
, ','.'' ~.' ' ., .. ~...
:, . . .::
.. :
. .-: : :::
.:
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8 I 3 3 0 ~ ~ ~ Z . 0050,38936 photochemical stability test shows that the resulting hydrosol of the act;ve ingredient is extremely stable despite being finely d;vided.
If necessary, the microdisperse oil phase super-saturated with carotenoid can also be brought to a suitable pH and then flocculated together with the protective colloid -~
and thus converted to a form from which the solvent and a major part of the dispersing medium can be removed in a simple manner by filtration or centr;fuging~ The co-acervate thus obtained is then further dried in a conven~
tional manner and converted to granules.
Specif;cally, the novel process ;s carr;ed out as follo~s, for example using an apparatus as shown schematically in F;g. 1.
15The apparatus is divided into parts I, II and ~-~
III. Part II is the high temperature sect;on, while in parts I and III the temperatures are less than 50C.
In vessel (1), a suspension of the carotenoid to-gether with the oil in the selected solvent in a concen-20 tration of from 2 to 20% by ~eight, based on the mixture, `
with or ~ithout the addition of from û.1 to 1û% by weight of stabilizers, is initially taken. Vessel (2) conta;ns the solvent without admixed carotenoid. The suspensions of active ingredient and the solvent are fed to the mix~
25 ing chamber t7) via the pumps (3) and (4) respectively; ;~
the mixing ratio can be predetermined by choosing the particular deLivery of the pumps, and is selected so that, ~9 depending on the solvent and the residence time, the resulting carotenoid concentration in the mixing chamber 30 is from 0.5 to 10~ by weight, based on the solutlon. The -volume of the mixing chamber (7) is such that the resi-dence time in (7) is preferably less than 1 second at the selected delivery of the pumps (3) and (4).
3efore entering the mixing chamber, the solvent is brought to the desired temperature by means o~ the heat exchanger (6), while the oil-containing suspension of active ingredient is kept at belo~ 50C by feed;ng it ,.. 133~70 - 9 - O~Z. 0050/38936 via the thermally insulated l;ne t5). As a result of turbulent mi~ing in (7) at from 50 to 24~C, preferably fro~ 150 to 200C, the active ingredient goes into solu- ~ ~
tion, and, after a short res;dence time, preferably less ~ -than 1 second, the result;ng solution passes via (8) into the second mixing chamber (11), in which, by admixing an aqueous protective colloid/plasticizer solution via pump (9) and feed line (10), the molecular disperse carotenoid solution is divided into a two-phase mixture with forma-10 tion of a microdisperse oil phase containing the active ~
ingredient in supersaturated solution and a homogeneous, ~ `
aqueous phase containing the water-miscible solvent. The microdisperse two-phase mixture is then discharged via line (12) and the pressure rel;ef valve and fed to the stock vessel (14). To obta;n a very high concentration of active ingredient, the dispersion can be circulated via the suction line (15).
If the pressure relief valve (13) is set at above .
one bar, it is even possible to use solvents at tempera- ~-tures above their boiling point (under atmospheric pres-sure) in the novel process. ~ -A pulverulent preparation can be obtained from the dispersion in a conventional manner, for example as; -described in German Laid-Open Application DOS 2,534,091, by spray drying or by spray cooling or by coating the particles, separation and drying in a fluidized bed. ;~
For spray drying, the dispersion is either first `~ freed from the solvent by distillation, preferably under reduced pressure, or by extraction with a water-immiscible solvent, or the entire mixture is spray-dried and water ` and solvent are stripped off together in the spray tower in this manner.
The carotenoid powder is obtained in either dry or free-flowing form at the bottom of the spray tower. `~ -35 In some cases, it may be advantageous additionally to :
carry out complete drying in a fluidized bed. Instead ~ `~
of preparing the powder formulation by spray drying, it ~: .'. ` .'~
- . . , -. ~ : ~::
, :,, , ..',, ,' ,'": `:',' ,' I ~ 3 V 2 70~ z . ooso/38936 is also possible to use any other methods to convert the caroteno;ds already f;nely d;str;buted ;n the water/o;l/
solvent dispers;on into powder form.
A known and equally su;table method comprises, S for example, emulsify;ng the dispersion freed from the solvent with liquid paraffin, cooling the mixture, separat- -~
ing the liquid paraffin from the coated carotenoid par~
~icles, washing the result;ng carotenoid prepara~ion with naphtha and drying the preparation in a fluidized ;
bed.
In the novel procedure, it was particularly sur~
prising that the use of the stated ~ater-misc;ble sol-vents mixed ~ith an edible oil which may additionally contain emulsifiers, such as ascorbyl palmitate, mono-and diglycerides, esters of monoglycerides with aceticacid, citric acid, lactic acid or diacetyltartaric acid, polyglycerol fatty acid esters, sorbitan fatty acid es- -ters, propylene glycol fatty ac;d esters, stearoyl 2-lactylates or lecithin, permits the preparation of highly supersaturated solutions in uhich, in spite of suppres-sion of the trans-cis isomerization, no recrystallization of the carotenoid takes place ~ithin the submicroscopic oil drops supersaturated with active ingredient in the microdisperse oil phase, after the phase separation in-duced by turbulent mixing with the aqueous protectivecolloid solut;on, even during removal of the volatile solvent, for example by distillation or spray dry;ng, and after cool;ng.
It is furthermore surpr;sing that admixing of the solvent-containing o;l solut;on of the caroteno;ds with the aqueous protective collo;d solution induces phase ;~
separat;on dur;ng wh;ch the disperse oil phase ;s ob-ta;ned in the form of extremely small part;cles, as can-; not be obtained by mechan;cal homogenizat;on. This f;nely dispersed state of the oil phase supersaturated w;th ac~
tive ingredient is also ma;nta;ned dur;ng removal of the volat;le solvent, for example by spray drying. It is : .: :
. ~.: :::-:
:::: . .
:' ~' , 13~27~
0.Z. 0050/38936 easily Possible to obta`in preparations in which the major fraction in the o;l phase has a particle size of 0.2 ~m, without part;cles of active ingred;ent larger than 1 ~m -~`
simultaneously being present. The absorption spectrum 5 of such carotenoid preparations shows the band form and ~--extinction typical of the molecular disperse solut;on of a carotenoid in an edibLe oil, even after spray drying and redissolution in an aqueous medium.
The Examples which follow illus~rate the novel process.
S g of 3-trans-carotene are suspended in Z40 9 of a solution of 4 g of ascorbyl palmitate, 5 9 of a-tocopherol and 20 9 of peanut oil in ;sopropanol, the ` 15 pressure relief valve (13) is set at 25 bar and the said suspension is mixed in mixing chamber (7) with 360 9 of isopropanol which has been heated to 225C in heat ex-changer (6). The suspension is metered at 2 l/h and the~ .
solvent at 3 l/h, and the residence time in mixing cham-ber (7) is 0.35 second. The molecular disperse solution formed at 190C is then fed to mixing chamber (11), in ~;~ which turbulent mixing with 4,000 9 of an aqueous solu-tion of 60 9 of gelatine and 90 9 of sucrose, brought to pH 9 with lN NaOH, at a metering rate of 27 l/h results ~ 25 in phase separation ~ith formation of a microdisperse oil~ ;
;~ phase which contains the 3-carotene in the form of a `
supersaturated solution. A microdisperse two-phase mix- -ture having a yellow hue and a temperature of 50C is ob~
tained in collecting vessel (14). ParticLe size analy- `~-sis by proton correlation spectroscoPy gives a mean par~
t;cle size of the oil phase of 210 nm and a distribution width of ~40Z.
.. .....
Removal of the solvent under reduced pressure at 50C in a distiLLation apparatus gives a viscous l;quid ~; 35 which can be converted to a stable, water-soLubLe dry po~der by spray drying. The ~-carotene content of this dry powder is 2.4% by weight.
,, .
;': ' ~
3~27~ ~
- 12 - O.Z. 0050/38936 Redissolving the dry powder in cold water gives a yello~ solution in which the oil phase is again present -~
as a microdisperse phase having a particle size of Z20 nm +30%.
Spectrophotometric investigation of this solution shows the ~-carotene band form typical of a molecular disperse solution (Fig. 2a). In contrast, the prior art gives a product which, for the same concentrat;on of ac-tive ingredient in aqueous solution, gives an absorption spectrum sho~ing the typical curve of a ~-carotene solid-state spectrum (Fig. 2b). The ratio of the extinction values at the band maxima is 2.1. Hence, the novel pro-cess g;ves a preparation which has more than twice the ; color strength of a prior art preparation.
In Spiee of the extremely finely divided nature and the high color strength, the hydrosol exhibits ex-cellent stability in the photostability test. Under standardized irradiation conditions, a loss of active ingredient of 10X is recorded during an irradiation time ; 20 of 270 minutes. In the case of products having a 3-carotene content of Z.4~ and prepared according to the prior art, a loss of active ingredient of 10% is ob-served under the same irradiation conditions after only 50 minutes.
EXAMPLE Z
A two-phase mixture is obtained as described in ExampLe 1, but with the use of 10 9 ~-trans-carotene,- `
8 9 of ascorbyl palmitate and 40 9 of peanut oil; in the -said mixture, the oil phase supersaturated ~ith ~-carotene -is in the form of submicroscopic droplets having a mean ; particle size of 249 nm +52%.
The dry powder obtained by spray drying contains ~-SX of active ingredient and, after redissolution in water, -;~
gives a hydrosol having a mean particle size of 289 nm 35 +54X. Compared with the prior art product, the extinction `~
ratio at the band ~~xinun is 1.8.
,:,:
, :
133~
.
;` - 13 - O.Z. 0050/38936 A dry powder is obta;ned as descr;bed ;n Example 1, but w;th the use of 5 9 of canthaxanthine; after re- .
d;ssolution ;n water, the said powder gives a hydrosol having a mean particle size of 191 nm +42%. The ext;nc-tion at the band maximum at ~ ~ 478 nm is 90% of the theoretical maximum value, whereas prior art products give extinct;on values which are no more than 5û~ of the :-theoretical values.
EXAMPLE 4 . :
A dry powder is obtained as described in Example ;~ 1, but with the use of 60 9 of gum arabic as a protective ~: colloid; after dissolution in water, the said powder gives a hydrosol having a mean particle size of 359 nm +42%. : :
' ~ :
' ~ . . ,;
.: ,- :.
~ , . . ~:
. ...:
.~":',';, :`
.' ,,.'~' ' ` .:',.`-;' ~`
''' ~.':
' -, :', !
- 12 - O.Z. 0050/38936 Redissolving the dry powder in cold water gives a yello~ solution in which the oil phase is again present -~
as a microdisperse phase having a particle size of Z20 nm +30%.
Spectrophotometric investigation of this solution shows the ~-carotene band form typical of a molecular disperse solution (Fig. 2a). In contrast, the prior art gives a product which, for the same concentrat;on of ac-tive ingredient in aqueous solution, gives an absorption spectrum sho~ing the typical curve of a ~-carotene solid-state spectrum (Fig. 2b). The ratio of the extinction values at the band maxima is 2.1. Hence, the novel pro-cess g;ves a preparation which has more than twice the ; color strength of a prior art preparation.
In Spiee of the extremely finely divided nature and the high color strength, the hydrosol exhibits ex-cellent stability in the photostability test. Under standardized irradiation conditions, a loss of active ingredient of 10X is recorded during an irradiation time ; 20 of 270 minutes. In the case of products having a 3-carotene content of Z.4~ and prepared according to the prior art, a loss of active ingredient of 10% is ob-served under the same irradiation conditions after only 50 minutes.
EXAMPLE Z
A two-phase mixture is obtained as described in ExampLe 1, but with the use of 10 9 ~-trans-carotene,- `
8 9 of ascorbyl palmitate and 40 9 of peanut oil; in the -said mixture, the oil phase supersaturated ~ith ~-carotene -is in the form of submicroscopic droplets having a mean ; particle size of 249 nm +52%.
The dry powder obtained by spray drying contains ~-SX of active ingredient and, after redissolution in water, -;~
gives a hydrosol having a mean particle size of 289 nm 35 +54X. Compared with the prior art product, the extinction `~
ratio at the band ~~xinun is 1.8.
,:,:
, :
133~
.
;` - 13 - O.Z. 0050/38936 A dry powder is obta;ned as descr;bed ;n Example 1, but w;th the use of 5 9 of canthaxanthine; after re- .
d;ssolution ;n water, the said powder gives a hydrosol having a mean particle size of 191 nm +42%. The ext;nc-tion at the band maximum at ~ ~ 478 nm is 90% of the theoretical maximum value, whereas prior art products give extinct;on values which are no more than 5û~ of the :-theoretical values.
EXAMPLE 4 . :
A dry powder is obtained as described in Example ;~ 1, but with the use of 60 9 of gum arabic as a protective ~: colloid; after dissolution in water, the said powder gives a hydrosol having a mean particle size of 359 nm +42%. : :
' ~ :
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Claims (4)
1. A pulverulent, water-dispersable carotenoid formulation in which the carotenoid is dissolved in an edible oil and the oil solution is in the form of small droplets which are dispersed as a pulverulent matrix, obtainable by rapidly dissolving a carotenoid in a volatile, water-miscible, organic solvent at from 50 to 140°C, together with from 1.5 to 20 times the weight, based on the carotenoid, of an edible oil, and an emulsifier, under atmospheric or superatmospheric pressure, then immediately mixing with an aqueous solution of a protective colloid at from 0 to 50°C
and thus transferring the hydrophilic solvent component to the aqueous phase, the hydrophobic oil phase which contains the carotenoid in solution being formed as the microdisperse phase, and freeing the resulting two-phase mixture from the solvent and the water.
and thus transferring the hydrophilic solvent component to the aqueous phase, the hydrophobic oil phase which contains the carotenoid in solution being formed as the microdisperse phase, and freeing the resulting two-phase mixture from the solvent and the water.
2. A process for the preparation of a pulverulent water-dispersable carotenoid formulation in which the carotenoid is dissolved in an edible oil and the oil solution is in the form of small droplets, wherein:
a carotenoid is rapidly dissolved in a volatile, water-miscible, organic solvent at from 50 to 240°C, together with from 1.5 to 20 times the weight, based on the carotenoid, of an edible oil and an emulsifier, under atmospheric or superatmospheric pressure, so as to form a molecular disperse solution;
the so formed molecular disperse solution is mixed with an aqueous solution of a protective colloid at from 0 to 50°C, the hydrophilic solvent component contained in said molecular disperse solution being then transferred to the aqueous phase of said aqueous solution, the hydrophobic oil phase which contains the carotenoid in solution being then formed as the micro-disperse phase; and the two-phase mixture that is so obtained is freed from the solvent and the water.
a carotenoid is rapidly dissolved in a volatile, water-miscible, organic solvent at from 50 to 240°C, together with from 1.5 to 20 times the weight, based on the carotenoid, of an edible oil and an emulsifier, under atmospheric or superatmospheric pressure, so as to form a molecular disperse solution;
the so formed molecular disperse solution is mixed with an aqueous solution of a protective colloid at from 0 to 50°C, the hydrophilic solvent component contained in said molecular disperse solution being then transferred to the aqueous phase of said aqueous solution, the hydrophobic oil phase which contains the carotenoid in solution being then formed as the micro-disperse phase; and the two-phase mixture that is so obtained is freed from the solvent and the water.
3. A process as claimed in claim 2, wherein the carotenoid is dissolved at from 150 to 200°C.
4. A process as claimed in claim 2, wherein the carotenoid is dissolved in less than 1 second, and the resulting solution is immediately cooled by mixing with the aqueous solution of the protective colloid and converted to the microdisperse two-phase mixture.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3702030.7 | 1987-01-24 | ||
| DE19873702030 DE3702030A1 (en) | 1987-01-24 | 1987-01-24 | POWDERED, WATER-DISPERSIBLE CAROTINOID PREPARATIONS AND METHOD FOR THE PRODUCTION THEREOF |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1330270C true CA1330270C (en) | 1994-06-21 |
Family
ID=6319440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000556833A Expired - Fee Related CA1330270C (en) | 1987-01-24 | 1988-01-19 | Pulverulent, water-dispersable carotenoid formulations and their preparation |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0278284B1 (en) |
| JP (1) | JP2620277B2 (en) |
| AT (1) | ATE63752T1 (en) |
| AU (1) | AU599196B2 (en) |
| CA (1) | CA1330270C (en) |
| DE (2) | DE3702030A1 (en) |
| ES (1) | ES2022470B3 (en) |
| GR (1) | GR3002493T3 (en) |
| IL (1) | IL85084A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101999577A (en) * | 2010-10-19 | 2011-04-06 | 上海应用技术学院 | Beta-carotene micro-capsule powder and preparation method thereof |
| EP0986963B1 (en) | 1998-09-14 | 2016-12-07 | Basf Se | Stable, powdery lycopene formulations containing lycopene with a degree of crystallisation of more than 20% |
Families Citing this family (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3610191A1 (en) * | 1986-03-26 | 1987-10-01 | Basf Ag | METHOD FOR PRODUCING FINE-PART, WATER-DISPERSIBLE CAROTINOID PREPARATIONS |
| EP0410236B1 (en) * | 1989-07-25 | 1993-10-27 | F. Hoffmann-La Roche Ag | Process for the production of carotinoid preparations |
| US5079016A (en) * | 1990-05-16 | 1992-01-07 | Kalamazoo Holdings, Inc. | Color-stabilized carotenoid pigment compositions and foods colored therewith having increased resistance to oxidative color fading |
| ZA917708B (en) * | 1990-09-28 | 1992-05-27 | Hoffmann La Roche | Beta-carotene emulsion composition |
| EP0602137B1 (en) * | 1991-09-06 | 2002-01-23 | Cognis Australia Pty Ltd | Carotenoid composition |
| DE4329446A1 (en) * | 1993-09-01 | 1995-03-02 | Basf Ag | Process for the production of finely divided color or active substance preparations |
| DE4424085A1 (en) * | 1994-07-11 | 1996-01-18 | Basf Ag | Preparations of fat-soluble active ingredients dispersible in cold water |
| DE19531254A1 (en) * | 1995-08-25 | 1997-02-27 | Sueddeutsche Kalkstickstoff | Process for the extraction of carotene dyes from solid natural substances |
| DE19609476A1 (en) * | 1996-03-11 | 1997-09-18 | Basf Ag | Stable parenteral administration suitable carotenoid emulsions |
| JP3555640B2 (en) * | 1996-05-10 | 2004-08-18 | ライオン株式会社 | Multicapsulated microcapsules containing natural carotenoids, tablets, food and pharmaceutical compounds |
| DE19649062A1 (en) * | 1996-11-27 | 1998-05-28 | Basf Ag | Liquid, oil-miscible carotenoid preparations |
| DE19651681A1 (en) | 1996-12-12 | 1998-06-18 | Basf Ag | Stable, aqueous dispersions and stable, water-dispersible dry powders of xanthophylls, their production and use |
| WO1998028404A1 (en) * | 1996-12-20 | 1998-07-02 | Eastman Chemical Company | Method for deep bed filtration of microalgae |
| DE19856728B4 (en) * | 1998-12-09 | 2004-04-22 | Henkel Kgaa | Process for the production of nanoparticle dispersions |
| WO2000035577A1 (en) * | 1998-12-11 | 2000-06-22 | Henkel Kommanditgesellschaft Auf Aktien | Method for producing nanoparticle dispersions |
| DE19919751A1 (en) | 1999-04-29 | 2000-11-09 | Basf Ag | Stable, aqueous dispersions and stable, water-dispersible dry powder of xanthophylls, their preparation and use |
| DE19951615A1 (en) * | 1999-10-26 | 2001-05-03 | Basf Ag | Process for the stabilization of liquid, aqueous preparations of fat-soluble substances |
| BR0106674A (en) | 2000-05-30 | 2002-04-30 | Nestle Sa | Primary composition containing a lipophilic bioactive compound |
| EP1213013B1 (en) * | 2000-11-29 | 2007-04-04 | Basf Aktiengesellschaft | Process for preparing solid compositions of water-soluble, hardly water-soluble or water-insoluble active agents |
| EP1227082B1 (en) | 2001-01-24 | 2004-06-16 | Kuraray Co., Ltd. | Process for producing carotenoid emulsion |
| DE20109224U1 (en) * | 2001-06-01 | 2002-10-17 | Marcus Gmbh & Co Kg Dr | Dye mixture for food, pharmaceuticals and cosmetics |
| CA2466158C (en) | 2001-10-19 | 2012-10-16 | Vita Power Limited | A foodstuff supplement and method of producing same |
| NZ536655A (en) * | 2002-05-30 | 2006-09-29 | Phares Pharmaceutical Res N | Oil soluble pigment compositions comprising at least one xanthophyll and at least one suitable solvent |
| CN1993060A (en) † | 2004-08-19 | 2007-07-04 | 帝斯曼知识产权资产管理有限公司 | Novel compositions of fat-soluble substances |
| CN101005768B (en) * | 2004-08-31 | 2012-07-11 | 阿克佐诺贝尔股份有限公司 | Method for pigment solubilisation, a pigment composition and its use |
| JP5459939B2 (en) * | 2006-06-09 | 2014-04-02 | 富士フイルム株式会社 | Carotenoid-containing emulsion composition, method for producing the same, food containing the same, and cosmetics |
| EP2192160B1 (en) * | 2008-12-01 | 2016-08-17 | Aquanova Ag | Micellar integrated oxidation protection for natural dyes |
| CN102341005A (en) | 2009-03-05 | 2012-02-01 | 巴斯夫欧洲公司 | Formulation of Astaxanthin Derivatives and Use Thereof III |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2861891A (en) * | 1956-12-13 | 1958-11-25 | Hoffmann La Roche | Water dispersible carotenoid compositions and process of making the same |
| DE1211911B (en) * | 1959-09-08 | 1966-03-03 | Hoffmann La Roche | Process for the production of a carotenoid preparation particularly suitable for coloring food and feed |
| US3998753A (en) * | 1974-08-13 | 1976-12-21 | Hoffmann-La Roche Inc. | Water dispersible carotenoid preparations and processes thereof |
| US4316917A (en) * | 1980-04-21 | 1982-02-23 | Hoffman-La Roche Inc. | Stable carotenoid solutions |
| DE3119383A1 (en) * | 1981-05-15 | 1982-12-02 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING FINE DISTRIBUTED, POWDERED CAROTINO PREPARATIONS |
| JPS5813367A (en) * | 1981-07-16 | 1983-01-25 | Toyo Ink Mfg Co Ltd | Aqueous dispersion of carotenoid dyestuff |
| FR2578719B1 (en) * | 1985-03-12 | 1990-02-09 | Christian Best | COLORED FOOD COMPOSITION FOR PARTICULARLY DECORATION |
| DE3610191A1 (en) * | 1986-03-26 | 1987-10-01 | Basf Ag | METHOD FOR PRODUCING FINE-PART, WATER-DISPERSIBLE CAROTINOID PREPARATIONS |
-
1987
- 1987-01-24 DE DE19873702030 patent/DE3702030A1/en not_active Withdrawn
-
1988
- 1988-01-12 IL IL85084A patent/IL85084A/en not_active IP Right Cessation
- 1988-01-19 CA CA000556833A patent/CA1330270C/en not_active Expired - Fee Related
- 1988-01-22 ES ES88100886T patent/ES2022470B3/en not_active Expired - Lifetime
- 1988-01-22 EP EP88100886A patent/EP0278284B1/en not_active Expired - Lifetime
- 1988-01-22 AT AT88100886T patent/ATE63752T1/en not_active IP Right Cessation
- 1988-01-22 AU AU10708/88A patent/AU599196B2/en not_active Ceased
- 1988-01-22 DE DE8888100886T patent/DE3862872D1/en not_active Expired - Lifetime
- 1988-01-22 JP JP63011047A patent/JP2620277B2/en not_active Expired - Lifetime
-
1991
- 1991-06-03 GR GR91400708T patent/GR3002493T3/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0986963B1 (en) | 1998-09-14 | 2016-12-07 | Basf Se | Stable, powdery lycopene formulations containing lycopene with a degree of crystallisation of more than 20% |
| CN101999577A (en) * | 2010-10-19 | 2011-04-06 | 上海应用技术学院 | Beta-carotene micro-capsule powder and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3702030A1 (en) | 1988-08-04 |
| DE3862872D1 (en) | 1991-06-27 |
| ATE63752T1 (en) | 1991-06-15 |
| IL85084A0 (en) | 1988-06-30 |
| AU599196B2 (en) | 1990-07-12 |
| JPS63196242A (en) | 1988-08-15 |
| GR3002493T3 (en) | 1992-12-30 |
| ES2022470B3 (en) | 1991-12-01 |
| EP0278284B1 (en) | 1991-05-22 |
| IL85084A (en) | 1992-06-21 |
| JP2620277B2 (en) | 1997-06-11 |
| AU1070888A (en) | 1988-07-28 |
| EP0278284A1 (en) | 1988-08-17 |
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