Note: Descriptions are shown in the official language in which they were submitted.
3S~Ei7;
Background oE t:he Invention
A cons~derable amoullt of effort h~ been devoted Eor
many year~ to provide solid particulate flavorin~ materials
in which a flavoring oil is contained in the particulate
matrix. Various attempts have been made to fix essential
flavoring oils in many different types of organic matrices
to provide stable free flowing powders which contain the
flavoring oils for Elavor release when incorporated into ~ ;
many types of foods. Typical examples of flavor fixation
are illustrated in rather recent patents, namely, U.S.
Patents 3,314,803; 3,554,76B and 3,736,149. These patents
illustrate attempts to incorporate a flavoring oil or volatile
ingredient into a carbohydrate matrix, particularly volatile
acetaldehyde. With respect to U.S. Patent 3,314,803,
the fixation of acetaldehyde in mannitol is disclosed wherein
relatively Iow amounts of acetaldehyde on the order of about
10% or less are initially fixed in a matrix with deterioration
or loss of the fixed acetaldehyde over a period of time. In
connection with UcS. Patent 3,554,768, a composition is
20 ` disclosed which contains acetaldehyde fixed in a carbohydrate
such as either a hydrophilic colloid, partially hydrolysed
starch or sugar, and mixtures of such car~ohydrates are
sugyested. More particularly, the 3,55~,768 patent in its
operating examples suggests that either lactose, lactose-
maltose, larch gum, tapioca dextrin and gum arabic may be
employed as matrices for a method of spray-drying aqueous
acetaldehyde compositions to provide spray-dried producks,
but only low levels of acetaldehyde fixation are achieved
and such levels are reduced upon storage~ In connection with
U.S. Patent 3,736~149, flavoring compositions are disclosed
which comprise a flavoring agent including acetaldehyde
fixed in a matrix material containing lactose~ a hydxocolloid
,
--2--
bm:
. .
i67Z
gum and a starch hydrolysate, wherein ~he patent: sugg~sts
that p~efercl~ly about. 5 to 50% of lactose is pre~ent in the
~tabilized acetaldehyde compositions. Furthermore, in the
3,736,149 patent the operating examples disclose that the
lactose is present in an amount of about 15-20% by weight
with the balance being a mixture of starch hydrolysate and
hydrocolloid gum of about 80-85~ by weight based upon the
three components. In both the 3,554,768 and 3,736,149 ~;~
patents, initial flavor fixation levels of about 10% or less
are obtained with a reduction in the flavor level with the
passage of storage time. The above mentioned patents are
merely illustrative of the considerable volume of patent
literature related to the fixation of flavoring agents in ~;
various matrices and it is not the purpose in this rather
brief background of the invention to fully detail all of the ~;
prior art in this area. Merely illustrative of other patents
included in such patent literature are United States Patent
Nos. 2,088,622; 2,258,567; 2,369,847; 2,555,465; 2,673,157i `~
2,702,262; 2,80g,895; 2,824,807; 2,856,291; 2,857,281; -
2,929,723; 2,935,409; 3,041,180; 3,264,11~; 3,336,139;
3,764,346 and 3,787,592.
In view of the vast body of art in the area of
fixed flavor compositions, to applicant's knowledge, it has ,
not heretofore been previously reported or known that
volatile flavoring agents could be fixed in certain
carbohydrate matrices in significantly large amounts without ;
detrimental amounts of flavoring agents on the particle
surfaces, and it has not heretofore been known to provide a
method for producing such particulate flavor compositions in
an effective manner without loss of flavoring components.
-3-
bm: -
~ ~)8S~7Z
:~ Summary o the ~nvention
,~,
Thls inv~ntion is directed to novel particulate
flavoring m~terials and methods of producing same. The
~' parkiculate flavoring materials, according to the principles
of this inven~ion, comprise a flavoring agent fixed in a
particulate matrix of a disaccharide and certain
~; carbohydrate materials. It has been found that particulate ;-~
flavoring materials can be produced which contain substantial
amounts of flavoring agent entrapped in the particle matrix
~; 10 on the order of at least about 30% to about 60% or more of
the flavoring agent per total particle weight and wherein
less than about 4~ of flavoring agent is unentrapped on the
surface of the particles.
Furthermore, it has been found that a particulate
flavoring composition can be prepared by formin~ an aqueous
mixture of ~he flavoring agent, a disaccharide and a
carbohydrate ma~eria~ and spray-drying the aqueous mixture
und~r the in~luence of heak to form a particulate flavoring
composition having substantial amounts of fixed flavoring
, 20 agent in the matrix with only an insignificant amount of
unentrapped agent on the surface of the particles. Another
! advantage o~ the method is that all ox neaxly all o~ th~
flavoring agenk starting material can ba Eixed in the
particulat~ matrix.
~his invention is predicated in part upon the
discovery that certain combinations of disaccharides and
carbohydrates can be employed in aqueous admixture with a
flavoring agent and, where the ratio of the disaccharide to
the carbohydrate; in the aqueous admixture is controlled, the
aqueous mixtures may be spray-dried ant at least 30~ flavoring
agent is fixed per total particle weight with less than about
4% of the flavoring agent unentrapped on the surface of the
.
-4-
bm: ` i
~108S67Z
~. ' .
pa~ticles. The ratio o~ a particular disaccharide to a
~ particular carbohydrate has been found to uary somewhat,
,,, :
but neverthelecls w.ithin the scope of this invention it will
b~ appreci~ted that ~here may be variances to achieve the
substantial entrapment of the flavoring agent in the matrix
with minimal residual agent on the particle surface.
More particularly, in one of the preferred
embodiments, sucrose is employed with a carbohydrate material
such as a hydrophilic colloid gum or a starch hydrolysate as
the matrix composition for flavoring oil fixation. According
to this embodiment, sucrose within the range of about 50 to
about 95% by weight and a starch hydrolysate within the range `-
of about 50 to about 5% by weight, based upon the total
weight of these ingredients may be dispersed in aqueous
admixture with an amount o~ flavoring oil. The 1avoring
oils are contained in amounts at least about 30 to about ~0
by volume based on the total matrix and oil ingredients.
This aqueous admixture may be spray-dried under the influence
of heat! e.g., warm air, using typical nozzle spray-drying
appara`tus where the drying temperatures are generally of about
180F to about ~50F. ~or example, flavoring oil ~ixa-tion
in sucros~,h~drolysed starch o~ at least abou-t 30~ to about
60~ by volume/woi~ht has been achievecl. Fuxthermore, &ven
with such signi~icant amounts of flavoring oil fixation,
surface oil on the spray-dried particles is less than about
~%~ Even more surprising, where about 50~ to about 95~
by weight of qucrose is combined with a hydrolysed starch
of about 5 to about 50% by weight, at least 30~ by volume
~; flavoring oil fixation with les~ than about 2~ particle
sur~ace oil is achieved. The exact mechanism for such
superior entrapment with lack of residual surface oil is
not known but empirical results have been obtained, As
. .
_5_
;; ;
i bm:
~V~S67Z
mentioned ahove~ it has been found essential tha-t the ratio
o~ the sucro.se to the particular car~ohydrate be maintained
within a range to achieve the advantageous results For
exAmple, wher~ ~ucro~e is employed with a starch hydrolysate~
as the amount of hydrolysed starch increases about 50%, the
initial amount of total oil in the particles ma~ be greater
than 30~, however, the surface oil increases above 4% and
this is found to be unsatisfactory. When the amount of
surface oil increases above about 4%, the flavoring
composition becomes susceptible to alteration by chemical
change thereby deviating from t~e taste sought in the
` flavoring composition and in the food preparations containing
same. Such alteration affects the entire flavoring
composition Oftentimes, compositions become rancid and must
be discardéd; and considerable economic loss may be incurred
depending upon the volume of spoilage, On the other hand~
with the compositions o~ this invention substantial amounts
of flavoring agents may be enkrapped, and stored for
significant periods of time without loss or deterioration
of essentail flavoring components. Also, by reason of the
substantial amount of flavoring agent fixation in a
particulate matrix, subs~antial savings in the manu;~acture,
~torage and shipment o~ such flavoring materials is achieved~
The advantages and objectives oP thi~ lnven-tlon
can be achleved with a number of Elavoring agents.
Accordingly, the term "flavoring agent", as used herein~
encompasses any one o~ a number oE mixtures or Elavoring
oils, solid~, or other liquids or essences well known as
flavor enhancers. Exemplary are grape, orange, cranberry,
lemon and lime oils or extracts; flavoring solids or liquids
including imitation strawberry, imitation raspberry, ~-
imitation cherry, imitation peach etc. Other natural or `
~ '
-6-
bm:
- ~ V ~ S 6 7 Z
syn~hetic flavoring agents can be employed~ Accordingly,
it is t~ b~ un~ers~ood that these mentioned ~lavoring agents
are exemplary o ~he type which may be used and are not
l;rnitations on the saope o~ this invention. When the ~lavor
agent is an oil or liquid, the percentages of entrapment or
sùrface residue are expressed as ~ per total particle weight.
When flavoring solids are employed, these percentages are by
weight, and where mixtures are employed percentage ratios of
each may be determined. More broadly, therefore, the
percentages expressed may be either by volume or by weight
depending upon whether liquid or solid flavoring agents are
employed.
Only certain matrix materials have been found to ;
provide the advantageous results and objectives o~ this
invention. It is essential to employ a combination of a
disaccharide, such as sucrose and lactose, and a
carbohydrate material selected from a group which may be
broadly classed hydrophilic colloids and starch hydrolysates~
t: Typical of hydrophilic colloids which may be used in the
present invention is gum arab}c. Of the hydrolysed starches
or the starch hydrolysates useful in accordance with this
invention are those o~ the typ~ mention~d in tha for~going
patents, namely, U.S. Patent 3,554,768 and 3,736,1~9.
Elowov~r, in contrast ~o th~ disalo~uro oE ~h~se and oth@r
patents, a particular disaccharide such as sucrose has been
found to provide the desired fixation with a hydrocolloid
gum such as gum arabic or hydrolysed starch, or mixtures
thereof, at certain rakios. When other ratios are employed,
~ either the aqueous mixture may not be particulated such as by
¦ 30 spray-drying, or substantial fixation of at least about 30%
j flavoring agent with less than about 4% surface residue
cannot be achieved, or more than 25% o~ the agent is lost in
-7
~; bm:
~' , , ;:
, :, . .. . .
~ V~S672
processing. When lactose is employed as the disacchar;.de,
mixtures with hydrocolloid gum arabic where the ratios of
60~ sugar to 90% gum are employed, using similar procedures
based upon experience with sucrose, the flavor fixation
drops drastical].y to below 20~ and surface residue increas~s,
or flavor volatiles are lost. It has also been established
that a disaccharide sucrose or lactose alone, or the
carbohydrate gum or hydrolysed starch alone, as the matrix
material will either not permit aqueous mixtures with
flavoring oils to be spray-dried under normal conditions,
or if they are spray-dryable, the products will not fix
significant amounts of oil at levels achieved by this
invention without significant surface oil levels, and even
flavor oils will be lost in processing Even further,
monosaccharides have not been ~ound suitable to achieve the
advantages and objectives o this invention when a-~empts
are made to use these compounds alone or in combination with
other carboh~drates at levels similar to those used with the
disaccharides of ~his invention.
Accordingly, in this invention, the combination and
ratio of the particular disaccharide to the particular
carbohydrate is essential to achieve the substantial flavor
entrapment with lack o~ residual surEace Elavor agen-t in the
particulatc Elavoring composition. These particulate
oompo~itlons and tho mcthods oE ~his inven~ion will bo fur-thcr
understood, and the advantages and objectives obtained, in
accordance with the following examples.
EXAMPLE 1
~n aqueous solution of sucrose was prepared by
dissolving 3.9 lbs. of sucrose in 1,5 gal. of water. To this
solution was added 2,6 lbs, of Kadex* 123-100, a starch
hydrolysate prepared from tapioca starch by oxidation with
* Trademark .
-8- . :
bm:
~ 8S672
hydrolysation and having a Dex~rose Equivalen~ (D.E.) of
about 1-2, (a product of Stein Hcill Company) and mixed well.
A 25% by weight sodium benzoate solution in an amount o~ 1
flu:id ounce was added to the ~ucrose-nlodified starch
solution. rrhe sodium benzoate was added merel~ as a
perservative. An orange oil in an amount of 64 fluid ounces
~density about 0.85 g/cc) was added to the resultant
mixture to provide a 40% by volume per weight of ingredients -
and the entire mass was mixed well to form an emulsion. The
emulsion was then fed into a nozzle type spray dryer at
2500 psi. The sprayed particles were introduced into a
vertical dryin~ chamber fed with heated air whose inlet
temperature was about 300F and the oulet temperature was
about 180F. Particles were collected at the bottom of the
drylng chamber. A particulate flavoring composition was
prepared upon spray-drying which was analy~ed to contain
about 35% by volume orange oil Elavor/weigh~ basis (cc per
100 grams of particulate composition). This determination
may be made in the case of orange oil by distillation of the
oil from the resultant particles. In addition, a surface oil
analysis was run by the addition of an amount of the spray-
dried particles to a perchloroe-thylene solven-~ and, aftex
shaking of the particLes ~or abou~ 1/2 ~o 1 minute, then
~epar~ting the solvent ;rom tho ex-tracted ~urEac~ o;Ll, ;it
w~s dctermined that the surface oil was about 1~ volume/weight.
EXAMPLES 2-6
A ~aries o~ examples were performed varying the
xatio o~ the ~uarose to the carbohydrate component as
reported in Example 1, employing the same procedures. In
this series of examples, only the amount of starch
hydrolysate and sucrose was varied, respectively, from about
50%-10% by weight of starch hydrolysate to 50%-90% weight of
bm:
1~151S67Z
sucrose on a t~tal parts by weight basis for the two matrix
components. In each ~xampl~ the amount of orange oil
remained the same and was about 40~ by volume/weight as
above ~or addi.tion to the aqueous admixture prior to
spr~y-drying. Following the same spray-drying procedures,
particulate flavoring compositions were obtained in the
manner accordiny to Example 1 and the results are reported
in the following Table I.
TABLE I
EXAMPLES -
2 3 D~ 5 6
% Starch Hydrolysate 50 ~0 30 20 10
~ Sucrose 50 60 70 80 90 ,
TOT~L OIL 37 35 36 36 36
SURFACE OIL 1.8 1.5 0.65 0.70.6
As demonstrated by Examples 2-6, where the amount
of sucrose was present in the aqueous admixture within the
range of about 50 to about 90~ by weight and the amount of
hydrolysed starch was pres~nt from about 10 -to abou-t 504 by
weight, the total volatilc Elavoxin~ oil conten~ o;E the
partiaulate composit:Lon was in ~xaes~ o~ 30%, namely, 35-373
volume/total particle woigh~; and ~hc cn~rapped oil was about
35~ volume/weight. The surface oil content of the particulate
flavoring composition was less than 2~ by volume, namely,
0.6-1.8~ volume/weight. Remarkably~ therefore, within the
range of sugar from about 50-95~ to hydrolysed starch of ;
about 50-5% by weight, the unentrapped surface oil in the
particulate composition was less than about 2% by volume/
weight. Accordingly, in the most preferred practice of the
--10--
bm:
1~)8S672
inventlon where a signi~icantly high percent of ~lavor oil
entrapment i5 desired, i.e,, within the range o~ 30-60~
with a matrix of sucrose-hydrolysed starch, the ratio of
such matrix materials is on the order of about 50-95~ and
50-5~, rcspectively, On the other hand, when 60/40 or
70/30 percent~ges of hydrolysed starch to sucrose are
spray-dried, higher surface oil content and less entrapped ~- :
oils are obtained. ~
These examples also demonstrate that nearly all . !
of the flavoring oil of the aqueous mixtures was fixed in
the particulate matrix, e.g., 35% of the 40% charged, or in
excess of 85% by volume. ~ .
When lemon flavor liquid is employed as the
flavoring oil and particulate compositions were prepared in
accordance with Example 1 to obtain an entrapped oil content
of about 36~ with a surface oil of about 1.5~, storage of
the product at 113F for 36 weeks exhibited organoleptic
stability,
EXAMPLE 7
.20 The procedure of Example 1 was followed wherein
the same ingredients were employed with the same spray-
drying process except 89 fluid ounces of gum solution (3.5
lbs. of gum arab:Lc per gallon o~ sol~l~ion) were subski~uted
for the starch hydrolysa~e and tha additional wa~er wa~
reduc~d Erom .L.5 cJallons to 0.8 ~allon~. Upon spray-drying
at the same conditions a particulate flavoring composition
was obtained containing total entrapped oil and unentrapped
sur~ae oll comparable to Example 1, namely, about 35~
: volume/weight total oil and 1.5~ volume/weight of surface oil.
EXAMPLE 8
The ingredients and procedures of Example 1 were
repeated, except that a mixture of Kadex* 123-100 and gum
* Trademark
--11--
~n: ' '
,, . "
~S672
solution were substituted for the Kadex* 123-100 of Example
1. ln this example, ~5 fluid ounces of the gum arabic
solution (35 lbs. of gum arabic per gallon of solution) and
1.3 lhs. of Kadex* 123-100 wcre employed. Upon spray-drying
under the same conditions of Example 1, a particulate . .
.flavoring composition was obtained containing about 35
volume/weight of total flavoring oil and about 2 2% volume/
weight surface oil. .
EXAMPLE 9
The ingredients and procedures of Example 1 were
repeated, except in this example Morrex* 1918 (a 10-12 D E
starch hydrolysate prepared from a high amylopectin-
containing starch, a product of Corn Products Company) was
substituted for the Kadex* 123-100 starch hydrolysate on a
sim1lar parts by we.ight basis. The ratio of sucrose to
modified starch in this example was about 60 to 90% by weight, .
respectively. Upon spray-drying according to the procedure
of Example 1, a particulate flavoring composition was obtained
with about 34~ volume/weight of total flavoring oil in the
particulate matrix and about 1.25~ volume/weight of
: unentrapped surace oil. Accordingly, about 33~ by volume/
weight was entrapped in the particulate matrix.
I:XAMP~ 0
Examplo 1 was repeatccl employing ~imilar procedures
and ingredients, except substituting lactose for the sucrose
wherein the ratio of the disacchari;de to the hydrolysed
~tarch was 60~ to 90~ by weight. Upon spray-drying, a
particulate flavoring composition was obtained with about
34% volume/weight of total flavoring oil in the particulate
matrix and about 3.2% volume/weight of the unentrapped
surface oil.
* Trademark .;
-12-
bm:
~L~85~7Z
In c~mparison to the results obtained according to
the above examples, attempts were made to employ mono-
saccharid~s such as fructose or dextrose with Kadex 123-100
under ~im:ilar spra~-dryiny conditions, but aqueous mixtures
o~ such monosaccharides at a similar ratio wi~h the
carbohydrate (i.e. 60%/40%~ were not capable of being spray-dried `~
as in Example 1. When percentages of the monosaccharides
to the carbohydrates were decreased to 30~/70% to enable
spray-drying, initial flxed oil content dropped below 30%
hy volume/weight and the residual or surface oil was higher
than 4% by volume, e.g., 5-6% by volume. When lactose was
employed with gum arabic in a ratio of 60%/40%,
respectively, the surface oil of the particulate composition
was about 5% and the initial fixed oil was about 24% b~
volume/weight, also indicating a loss of about 40~ ~lavorin~
oil durin~ spray-drying. Similar resul~s were ob~ained when
lactose was employed with a combination oE 20~ Kadex 123-100,
20% gum arabic and 60% lactose. Furthermore, when hydrolysed
starch (Morrex 1918 or Kadex 123-100) or gum arabic is
employed alone as a matrix material, flavoring oil loss or
high surface oil has been observed in processing.
I~ will be appreciated tha-~ ~hc temperatures and
condi~ions used in spray-drying are related to the type o~
drier and atomizer available, par~icl~ size desired and ~ha
like. Typically, the inlet temperature of the drier may be
about 250-450~F and the outlet temperature about 180-300F.
While ~he atomiz~r as described above was a single fluid
high pressure nozzle, it may be a centrifugal dish or a
two-fluid nozzle using air, steam, or inert gas as the
atomizing agent. Driers themselves may be vertical or
hor;.zontal.
-13-
; bm:
.. .
8S67Z
In view of the above detailed description and
operating example.s, other modiicat.ions and embodimellts
will become apparent to a person of ordinary skill in the
art and such ar~ wi~hin ~he scope of this invention.
--14--
bm:
. I
