Note: Descriptions are shown in the official language in which they were submitted.
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POURABLE FATTY DISPERSIONS
The present invention relates to pourable fatty dispersions
consisting of a triglyceride oil in which a non-fat phase
is dispersed and which dispersion further contains a
stabilising amount of triglyceride fat. A preferred fatty
dispersion is liquid margarine.
STATE OF THE ART
Margarine consists of a continuous fat phase and an aqueous
phase which is dispersed as fine droplets in the fat phase.
In contrast to common margarine which has a semi-solid,
plastic, spreadable consistency, liquid margarine is
pourable at ambient temperature.
All margarine fat consists of a mixture of a fat which at
ambient temperature is fully liquid (an oil), and a fat
which is solid at ambient temperature, the so-called
hardstock fat which has stabilising functionality. The
ratio of liquid and solid fat is chosen such that after
proper processing together with an aqueous phase a product
with a suitable plastic consistency is obtained. In common
margarine the crystals of the solid fat form a network
throughout the liquid oil resulting into a structured fat
phase. The aqueous phase droplets are fixed within the
spaces of the lattice of solid fat crystals. In this way
coalescence of the droplets and separation of the heavier
aqueous phase from the fat phase is prevented. Wrapper
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margarines need more solid fat than tub margarines and tub
margarines need more than liquid margarines. Moreover,
liquid margarines need a different kind of stabilising fat.
The presence of hardstock fat aims to stabilise the
margarine emulsion. Unstable liquid margarines show phase
separation. Phase separation, particularly oil exudation,
becomes visible as a layer of oil on the surface of the
liquid margarine.
It is desired that a stable liquid margarine of good
quality is substantially free from oil exudation, yet
exhibits good pourability. It is difficult to combine good
stability with good pourability. The solid fat crystals are
needed for the stability of the emulsion, but on the other
hand may adversely affect its pourability. Liquid margarine
manufacture therefore requires a hardstock fat with
properties which are delicately balanced.
The problem of preparing a satisfactory liquid margarine
has been addressed since long as appears from the content
of e.g. US 3595674, SU 553964, JP 51133453, US 5756142, US
3338720, US 4446165, US 4341812, GB 1092236.
Although prior art mentions several fully hydrogenated fats
for use as liquid margarine hardstock fat, seldom a
specification of their performance is found. Generally,
vaguely defined mixtures of fully hydrogenated fats are
included in such prior art references, however, without
specification of type of fats, blend ratios or performance.
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TABLE I
LIQUID MARGARINE (80$ FAT) PREPARED WITH SUNFLOWER OIL
AND COMMON MARGARINE HARDSTOCK FATS
Stability and Pourability
Hardstock HS (2) Oil Bostwick
fat (HS)(1) (wt.%) exudation * value (4) # @
(3)[v/v o] [cm/15 sec]
SINGLE
FAT
1 SF69 2 4.5 - 23 + -+
2 B065 2 4.5 - 23 + -+
3 RP68 2 4.5 - 23 + -+
4 P058 2 11 - 2 - --
5 dfPOs (5) 2 7.3 - 20 + -+
6 AR60 2 3 - 20 + -+
7 CS62 2 10 - 24 + -+
8 RPh70 2 0.7 + 22 + ++
FAT
BLEND
9 dfPOs/ 0.8/ 0.7 + 4 - +-
RPh70 1.2
in(P058/ 1.2/ 6 - 18 + -+
PK39) (6) 0.8
(1) Abbreviations explained in Table II
(2) Percentage of hardstock fat on fat phase
10 (3) * . Oil exudation is measure for stability,
+ . oil exudation 2 or less, adequate
- . oil exudation >2, not adequate
(4) # . Bostwick value is measure for pourability
+ . Bostwick value >- 15, adequate
- . Bostwick value <15, not adequate
@ ++ . good quality liquid margarine hardstock
-+, +-, - . stability and/or pourability not adequate
(5) dfPOs is dry fractionated palm oil stearin with a slip
melting point of 52°C.
(6) The fat mixture is used after interesterification.
Table I shows the poor performance of some common margarine
hardstock fats when applied in a liquid margarine.
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Stability is measured by an oil exudation test and
pourability by the Bostwick test. The standard for
stability is an oil exudation rating being 2 or less and
the standard for pourability is a Bostwick value being at
least 15.
A liquid margarine having a pourability rating < 15 is too
thick and lacks acceptable pourability.
An oil exudation rating > 2 points to an unacceptable
inhomogeneous product appearance and bad kitchen
performance.
Both tests and a general liquid margarine preparation are
described later in the specification.
Hence in the context of the present specification an
emulsion, or, generally, a fatty dispersion is pourable and
stable when it complies with the above standards.
TABLE II
FULLY HYDROGENATED FATS
Abbreviation Name starting fat Melting point (C)
SF69 Sunflower seed oil 69
B065 Soybean oil 65
RP68 Low erucic rapeseed 68
oil
P058 Palm oil 58
RPh70 High erucic rapeseed
oil 70
PK39 Palm kernel oil 39
AR60 Arachidic oil 60
CS62 Cottonseed oil 62
Fully hydrogenated high erucic rapeseed oil (shortly
denoted as fully hardened rapeseed oil or RPh70) has
appeared to be the only hardstock fat which complies with
the above standards. It is widely used for the manufacture
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of satisfactory liquid margarines which combine good
stability with good pourability. Presently, from all above
mentioned fats solely fully hardened rapeseed oil is
employed for the preparation of high quality liquid
5 margarine. Its use is described e.g. in US 5,756,142.
RPh70 is unrivalled as hardstock fat also for use in other
pourable fatty dispersions consisting of a triglyceride oil
in which a non-fat phase is dispersed. WO 98/47386, for
example, deals with the stabilisation of a pourable fatty
dispersion containing herbs as the dispersed phase. Besides
RPh70, other fats are mentioned as possible hardstock fat:
hardened sunflower seed oil, hardened soybean oil, hardened
palm oil, hardened cottonseed oil or mixtures thereof.
Besides RPh70 only hardened sunflower seed oil has been
exemplified. The product is said to have "acceptable
properties".
Generally, liquid margarines are prepared with 2 - 5 wt.o
of hardstock fat on total fat phase.
RPh70 may be unsurpassed as liquid margarine hardstock fat,
its use also has less favourable aspects. RPh70 is derived
from a fat with a high erucic acid content. From a
nutritional point of view erucic acid should be avoided in
food compositions. Hydrogenation of the unsaturated erucic
acid does not fully remedy this. Another drawback of RPh70
is its high price.
Besides that, liquid margarine hardstock fats are wanted
which have a stability and pourability performance which is
better than what RPh70 can offer.
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SUMMARY OF THE INVENTION
We have discovered the parameters which define well
performing hardstock fats to be used for the manufacture of
liquid margarines. First it was found that for proper
performance such fats should solidify as small mixed
crystals rather than as an extended fat crystals lattice
such as is needed for the plastic consistency of common
margarines.
Then, the conditions for the formation of such mixed
crystals have been found to be related in a specific way to
the amount and the nature of the triacylglycerides (TAGS)
which constitute the hardstock fat.
The present invention provides a hardstock fat suited for
stabilizing a pourable dispersion of a non-fat phase in a
triglyceride oil, which hardstock fat consists of a mixture
of triglycerides, characterized in that,
~ at least two triglycerides having a melting point >55°C
each have a concentration of at least 5 wt. o,
~ the amount of triglycerides having fatty acid residues
with a difference in chain length of the longest and the
shortest residue being at least four carbon atoms is at
least 15 wt.% and
~ the amount of triglycerides having a melting point of
25-55°C is <_25 wt. o.
Fully hardened high erucic rapeseed oil (RPh70) fulfills
the conditions of this definition. This fat has been found
earlier by chance and is an isolated representative of the
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group of invented fats. Because it is known, RPh70 is
excluded from the invention by a disclaimer.
The invention comprises also liquid margarines and other
pourable fatty dispersions containing hardstock fat and
which fat is comprised in the invention.
DESCRIPTION OF FIGURES
Figure 1 is a reference table containing most
triacylglycerides (TAG's) each with its melting temperature
(TSL) in its most stable modification and with the
difference in carbon chain length of the shortest and the
longest aryl group.
Data sources (e.g.): Wesdorp, L.H. "Liquid-multiple solid
phase equilibria in fats", PhD-thesis, (1990) TU Delft;
Garti, N., Sato, K.: "Crystallization and polymorphism of
fats and fatty acids", ISBN: 0-8247-7875-8).
Abbreviations explained in Table III below.
Figure 2 (single fats) and Figure 3 (fat blends) show for a
number of fats (abbreviations explained in Tables II and
III) the TAG composition as far as the TAG's are present in
an amount of at least 0.1 wt. o.
They also mention the TAG's melting temperature (TSL) and
carbon number difference of longest and shortest acyl
group.
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TABLE III
Abbrev Common name Systematic name
A arachidic acid eicosanoic acid
B behenic acid docosanoic acid
Ci capric acid decanoic acid
Cy caprylic acid octanoic acid
E elaidic acid 9-octadecenoic acid (E)
L linoleic acid 9,12-octadecadienoic acid
(Z, Z)
La lauric acid dodecanoic acid
Le linolenic acid 9,12,15-octadecatrienoic
acid (Z,Z,Z)
My myristic acid tetradecanoic acid
O oleic acid 9-octadecenoic acid (Z)
P palmitic acid hexadecanoic acid
S stearic acid octadecanoic acid
Tc lignoceric acid tetracosanoic acid
DETAILED DESCRIPTION
Hardstock fats which are prepared for use in margarine fat
consist for at least 90 wt.o of saturated triglycerides.
The hardstock fat is mixed with a liquid fat. The liquid
fat may contain some saturated triglycerides but the amount
is too low for stabilisation. The present saturated
triglycerides and the saturated triglycerides added by
admixture of the hardstock fat together are by definition
the hardstock fat part of the margarine fat blend.
The invented hardstock fats crystallize with a crystal
habitus which makes those fats suited for satisfactory
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performance in a liquid margarine. Particularly, those fats
crystallize as small mixed crystals which on the one hand
properly stabilize the margarine emulsion and minimize oil
exudation to an acceptable extent and on the other hand
allow a good pourability.
The absence of relatively high amounts of low melting
triglycerides prevents that the solid phases of hardstock
fats would crystallize on top of each other. This so-called
sintering is the cause of the undesired brittle crystal
structure which adversely affects the emulsion pourability.
It has been found that particularly triglycerides melting
at 25-55°C are inclined to enhance sintering and spoil the
pourability. Therefore the invention requires all such
triglycerides to be present in a concentration <-25 wt. o.
Preferably, those triglycerides melting at 25-55°C are
present in a concentration even <_20 wt. o. More preferably,
all triglycerides melting at the wider range of 20-55°C are
present in a concentration <-20 wt. o.
Triglycerides having fatty acid residues with a difference
in chain length of the-longest and the shortest residue of
at least four carbon atoms must be present in an amount of
at least I5 wt.o and these, preferably, have a melting
point >55°C.
We have found that liquid margarines containing hardstock
fat with the above triacylglycerides (TAG) specification
satisfy the abovementioned stability and pourability
standards. Their properties may be as good as those of
RPh70 stabilized liquid margarines.
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A hardstock fat is said to stabilize properly a liquid
dispersion of a non-fat phase in a triglyceride oil,
denoted as a fatty dispersion, when the oil exudation test
is passed with a rating 2 or less. A stabilizing amount of
5 hardstock fat is the minimum amount which is necessary for
imparting a proper stability to the dispersion. Only 2 wt.o
of an invented hardstock fat is needed for attaining such
stability. A liquid margarines containing this amount of
the invented hardstock fats is stable and nevertheless
10 exhibits a proper pourability which means that the rating
according to the Bostwick test is at least 15.
The present invention deals with the performance of
hardstock fats in preventing oil exudation in fat
continuous dispersions, while an acceptable pourability of
the dispersion is maintained. For proper comparison of data
all measurements are carried out with liquid margarines all
of which contain 80 wt.o of fat and 20 wt.o of a dispersed
aqueous phase. The present invention is applicable,
however, with fat phases containing 1 - 80 wt.o of a
dispersed fat immiscible phase.
The hardstock fats according to the invention are novel.
Starting from one or more known fats, preferably vegetable
fats, they can be obtained by processing usual triglyceride
fats comprising blending, interesterification,
hydrogenation or by a combination of these treatments in
any proper order. Acidolysis with a fatty acid or a mixture
of fatty acids may be a proper process for substituting the
fatty acid residues of a chosen starting fat by desired
fatty acid residues.
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That the hardstock fat preferably is a vegetable fat means
that when choosing for blending or processing the
constituting fats less than 10 wt.o of non-vegetable fat
calculated on total hardstock is used.
Interesterification and acidolysis may be applied either as
a chemical process or as an enzymatic rearrangement
process. Methods for carrying out those common fat
treatments are well known in the art.
Suitable hardstock fats according to the invention comprise
blends of (weight ratios between brackets) RPh70 and SF69
(1/1), B065 and RPh70 (7/3), SF69 and in(RPh70) (1/1),
in(RPh70) and B065 (3/1), further RPh70 interesterified
with itself (denoted as in(RPh70)), the product of
acidolysis of P058 with arachidic acid (3/1) and the
product of interesterification of SF69 with glyceride
tribehenate (4/1). Abbreviations are explained in Table II.
The ratios of the fats in the blends can not be chosen
arbitrarily. For showing a satisfactory performance the
triglycerides composition of the final blend should comply
with the claim definition. Given the triglyceride
composition of a desired claimed fat the man skilled in the
art of triglyceride fat technology is able to calculate
which fats and which fat treatments he needs to obtain the
desired fat. When an enzymatic rearrangement has been
involved it may be necessary to subject the obtained fat to
a triglycerides analysis for establishing correctly whether
the fat fits in the claim definition.
Since for most generally available fats the triglyceride
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composition is known or can be analyzed and the OC and TSL
are known data, the man skilled in the art of fat
technology is able to choose and process available fats in
such way that a fat is obtained showing the desired
triglyceride composition and which fits in the claim
definition.
For example, given the qualitative and quantitative
triglycerides composition of starting fats in(RPh70) and
B065, the effect of blending a (3/1) mixture of both
components is shown in Table IV.
TABLE IV
STARTING FATS PRODUCT BLEND
Triglyceridesintra-esterified
in starting RPh70 (A)
fats and B065 (B) 75 A + 25 B
product blend
wt.'k wt. ~ wt. ~
With OC >_ 68.9 0.6 51.8
4
TSZ > 55C
For which
TSL=15 -55C 0 0 0
S.B.B 15.4 0 11.6
TSL=73 . 5C
S.S.B 14.1 0 10.6
TSL-7 0 .
7 C
S.S.S 6.5 65.8 16.5
TSL=7 3 .
0C
P.S.S 1.9 28.0 7.0
TSL=65 . 0C
Other TAG's 39.4 0.6 6.1
with OC _>
4
TSL > 55C
Complies withYes No Yes
claim 1
0C >_ 4 means a difference of at least 4 carbon atoms
between the longest and the shortest fatty acid residue
TSL denotes melting point triglyceride.
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Fatty acids abbreviations explained in Table III. Relevant
data for the constituting triglycerides can be found in
textbooks, while many are collected in the Table of Figure
1.
The hardstock fats according to the present invention are
suited not only for stabilizing liquid margarines, but also
for any other pourable fatty dispersion. With a fatty
dispersion is meant a continuous liquid fat in which a fat
immiscible phase has been dispersed. Besides of a dispersed
aqueous phase such fat immiscible phase may also consist of
solid particles, such as powders, speckles or herbs. The
hardstock fat helps to prevent or retard settling of the
dispersed particles.
A product consisting of a stabilized pourable fatty
dispersion which comprises a liquid oil and a hardstock fat
can be obtained by admixing the invented hardstock fat as
such into the liquid oil at any proper point of time when
preparing the product. Alternatively, the hardstock fat may
be incorporated into the liquid oil by admixing the fats
constituting the hardstock blend separately with the oil,
with the final effect that a stabilized pourable fat phase
is obtained which can not be distinguished from a fat phase
obtained by direct addition of the invented hardstock fat
to the fat phase. It is noticed that when choosing fatty
material with hardstock functionality the presence of fully
saturated triglycerides already present in the liquid oil
part of the fat phase of the dispersion also contributes to
the fat phase stabilisation and therefore is considered to
be a part of the hardstock fat contained in the fat phase
of the ready dispersion. In the context of the present
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specification the totality of all saturated triglycerides
present in a triglycerides fat mixture is by definition the
hardstock fat part of that mixture. A saturated
triglyceride contains only saturated acyl moieties.
Hence the invention also comprises a stabilized, yet
pourable fat phase containing 1 - 80 wt.o, preferably 1 -
60 wt.%, more preferably 1 - 40 wt.o of a dispersed fat-
immiscible phase, such pourable fat phase including liquid
margarines, where the fat phase contains hardstock fat
consisting of 1 - 10 wt.o and preferably 1 - 2 wt.o on
total fat phase of saturated triglycerides, which hardstock
fat complies with the above mentioned definition for a
hardstock fat:
at least two saturated triglycerides having a melting point
>55°C both have a concentration of at least 5 wt. o,
at least 15 wt.o of all saturated triglycerides have fatty
acid residues with a difference in chain length of the
longest and the shortest residue of at least four carbon
atoms,
the amount of saturated triglyceride with a melting point
in the range 25-55°C is __<25 wt.o and
with the proviso that pourable fat phases containing a
fully hydrogenated high erucic rapeseed oil as the sole
stabilizing hardstock fat are excluded from the invention.
The at least 15 wt.% of saturated triglycerides which have
fatty acid residues with a difference in chain length of
the longest and the shortest residue of at least four
carbon atoms, preferably have a melting point of >55°C.
The pourable fat phase preferably is constituted by fats
from vegetable origin, which means that it contains
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preferably less than 10 wt.o of fat of non-vegetable
origin.
The invention also comprises the use of the hardstock fat
5 as defined in the claims for the stabilisation of a
triglyceride fat phase in which fat phase 1 - 80 wt.o of a
fat-immiscible phase is dispersed.
All concentrations in this specification are weight
10 concentrations unless indicated otherwise. Weight
concentrations of triglycerides are calculated on total
hardstock fat unless specified otherwise.
15 The invention is illustrated by the following examples:
G E N E R A I
Measuring oil exudation
A stoppered all glass measuring cylinder of 100 ml is
filled up with the sample to the top mark. After two weeks
storage at 15°C the thickness of the separated oil layer is
measured and expressed as vol.o on total sample volume. The
vol.o is the rating for emulsion stability.
Measuring pourability
Pourability is measured according to the standard Bostwick
protocol which is provided with the equipment. The Bostwick
equipment consists of a 125 ml reservoir provided with a
outlet near the bottom of a horizontally placed rectangular
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tub and closed with a vertical barrier. The tub's bottom is
provided with a 25 cm measuring scale, extending from the
outlet of the reservoir. When equipment and sample both
have a temperature of 15°C, the reservoir is filled with
125 ml of the sample after it has been shaken by hand ten
times up and down. When the closure of the reservoir is
removed the sample flows from the reservoir and spreads
over the tub bottom. The path length of the flow is
measured after 15 seconds. The value, expressed as cm per
15 seconds is the Bostwick rating, which is used as yard
stick for pourability. Table V shows Pourability categories
for liquid margarine.
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TABLE V
POURABILITY CATEGORIES MARGARINE
FOR LIQUID
very thick Bostwick 1,
<
thick Bostwick - 5,
1
squeezeable Bostwick - 15,
5
pourable Bostwick 15.
>_
EXAMPLES 1 - 5
GENERAL LIQUID MARGARINE PREPARATION
In a premix tank a mixture is prepared consisting of 20
wt.o of aqueous phase, 78 wt.o of sunflower seed oil and 2
wt.o of hardstock fat. Table VI shows a general
composition.
TABLE VI
COMPOSITION OF LIQUID MARGARINE
Wt . L1CIL11C3 margara.ne
~
80 Fat phase
18.4 Water
1.0 Salt
0.6 Emulsifier
The temperature of the premix is increased to 65°C, at
which temperature all hardstock fat will liquefy. After 10
minutes stirring at this temperature the mixture is cooled
to 35°C. Consecutively, the mixture is conducted at a
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throughput of 4 kg/h through a scraped surface heat
exchanger (800 rpm, exit 18°C), a second scraped surface
heat exchanger (800 rpm, exit 5°C), a 150 ml resting unit
and finally through a 150 ml pin stirrer unit (1500 rpm,
exit 17°C). The pin stirrer delivers a liquid margarine
which is ready for packaging.
Using the above general preparation for liquid margarines
products have been obtained with fat phase compositions
mentioned in Table VII.
TABLE VII
LIQUID MARGARINE (80$ FAT) STABILISED WITH HARDSTOCK FAT
Stability and Pourability
Oil Bostwick
Exam Hardstock HS (2) exudation value (4)
Ple fat (HS)(1) (wt.~) (3)[v/v * [cm/15 sec]# @
%]
1 in(RPh70) 2 0.5 + 15 + ++
2 in(RPh70)/ 1.5/0.5 1.5 + 17 + ++
B065
3 SF69/RPh70 1/1 0.7 + 21 + ++
4 B065/RPh70 1.4/0.6 1.0 + 17 + ++
5 B065/RPh70 1/1 0.8 + 15 + ++
6 RPh70/SF69 1.5/0.5 0.5 + 22 + ++
COMPARISON
7 RPh70 2 0.7 + 22 + ++
(1) Abbreviations explained in Table II
(2) Percentage of hardstock fat on fat phase
(3) * . Oil exudation is measure for stability,
+ . oil exudation 2 or less,
- . oil exudation >2
(4) # . Bostwick value is measure for pourability,
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+ . Bostwick value >_ 15,
- . Bostwick value <15
++ . good quality liquid margarine hardstock
which satisfies the stability as well as the pourability
standards.
The stability and pourability performance of the products
have been measured according to the standard methods above.
For comparison the stability and pourability ratings of a
liquid margarine prepared with RPh70 have been included.
