Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~ 216S837
BOIL13D SW13ET AND PROCESS FOR ITS MANUFACTUR~3
The present invention relates to a new boiled sweet
having a water content greater than the usual contents for
this type of confectionery and having, in spite of this high
water content, a very high stability.
The invention also relates to a process for the
manufacture of this boiled sweet and the use, during its
production, of a special carbohydrate composition.
Boiled sweets, also commonly called hard sweets or
hard boiled candies, are solid and essentially amorphous
confectionery products. They are obtained by extensive
dehydration of carbohydrate syrups. Generally, mixtures of
powdered sucrose and of concentrated syrups of starch hydro-
lysates, in proportions ranging from 40/60 to 65/35 by
commercial weight (i.e. from 45/55 to 70/30 by dry weight),
are boiled. These mixtures normally contain water in
sufficient quantity to dissolve the sucrose crystals
entirely. These mixtures are then boiled at temperatures of
up to 130-150C at ambient pressure so as to evaporate most
of the water, then the boiling is completed under vacuum so
as to further reduce the water content and to bring it to a
value which is normally less than 3%. The plastic mass thus
obtained is then cooled until a temperature of between 125
2165837
and 140C is obtained in the case of a process for casting
into moulds, or a temperature of between 90 and 115C in the
case of a process for forming on rolls or an extrusion
process. At this stage, various substances such as
flavourings, colourings, intense sweeteners, acids, plant
extracts, vitamins and pharmaceutical active ingredients are
then added. Boiled sweets having a texture and an appearance
similar to those of glass are obtained after forming or
casting of the massecuite and after returning to room
temperature.
Boiled sweets are required to be stable over time,
that is to say to vary as little as possible from the time
when they are manufactured up to the time when they are
consumed, so as to remain products which are attractive and
pleasant in the mouth.
Now, boiled sweets are unfortunately not stable
products from a thermodynamic point of view. The extent of
their variation depends essentially on their composition
after manufacture, but also on the conditions under which
they are preserved.
Firstly, boiled sweets may become sticky products
during storage. When they are wrapped, it then becomes
difficult or even impossible to remove their wrapping
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materials before they are consumed. They may also cake
without r~m~;n;ng individualized, which is even more
troublesome.
This problematic variation towards a sticky and
syrupy state can be explained by surface phenomena and/or by
depth phenomena.
The origin of the surface phenomena is in the
hygroscopic nature of boiled sweets. It is indeed known that
boiled sweets, which are in essence practically anhydrous
products, always have very low equilibrium relative
humidities, substantially lower than the usual ambient
relative humidities for storage. This explains why an uptake
of water necessarily occurs at the surface of the sweets as
soon as they are and remain exposed to air, as is the case
for lollipops for example. When this water uptake is
sufficiently high, it tends to liquefy the surface of the
sweets and to impart on them the characteristics of a syrup,
that is to say in particular to impart on them a sticky
character. The lower the water content of the boiled sweets,
the quicker this variation appears.
The depth phenomena, which therefore do not only
relate to the surface but to the entire mass of the sweets,
have a thermal origin. More precisely, it is advisable, in
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order for these phenomena to occur, that the storage
temperature slightly exceed the glass transition temperature
of the boiled sweet. This notion to which reference is made
here is extensively described in the excellent article "La
transition vitreuse : incidences en technologie alimentaire~'
[Glass transition : incidents in food technology] by
M. Le Meste and D. Simatos, published in I.A.A. of
January/February, 1990. The glass transition temperature is
the temperature at which, upon heating, a glassy and solid
boiled sweet becomes an amorphous syrupy liquid. This
temperature is normally measured by differential Sc~nning
calorimetry. It can be very easily understood that a boiled
sweet may be subject to a deformation, or even to a complete
flow, when its storage temperature is high and supercedes
its glass transition temperature. The product which
initially has a dry feel becomes sticky. It should be noted
that the higher the water content of the boiled sweet in
question, the greater the risk of variation of this nature
during its storage.
In conclusion, in order to avoid the boiled sweets
becoming sticky products upon storage, it has always
appeared necessary that their water content be neither too
low nor too high.
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Secondly, boiled sweets can have the tendency during
storage to crystallize in an uncontrolled manner and thereby
lose their very attractive glassy appearance, resembling
more in this case barley sugars which, as is known, are very
different from the confectionery products of interest within
the framework of the present invention. This crystallization
can occur only at the surface of the sweet or alternatively
also at the centre of the sweet.
The surface crystallization unavoidably requires a
significant water uptake and corresponds to a stage of
additional variation relative to that described above. It
also requires a sufficient concentration of crystallizable
molecules, in general sucrose molecules, in the liquefied
peripheral layer. When these two conditions are met, a
lS crystallization is then observed which occurs from the
surface of the sweet towards its centre. This phenomenon,
when it is uncontrolled, is known by the name of turning. It
makes the sweets completely opaque and white.
The crystallization can also occur very directly at
the centre of the boiled sweet if the latter is very high in
water or if the storage temperature is very high. Under
these conditions, the boiled sweet is then excessively soft
and can no longer be considered as a real solid. It is then
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more a liquid supersaturated with crystallizable molecules
whose variation toward a crystalline state is unavoidable
and practically spontaneous. Specialists designate this type
of crystallization by the term graining.
In the final analysis, in order to avoid the boiled
sweets being unstable and becoming, over time, sticky
products or alternatively turned or grained products, it has
always seemed essential to adjust, on the one hand, their
content of water and, on the other hand, their content of
crystallizable molecules, that is to say generally their
content of sucrose.
These basic recommendations are in most confec-
tionery books but also in a good number of scientific
articles. It is for example possible to mention the article
by J. ~FT.rF~F~ et al., "The physico-chemical characteristics
of boiled sweets n Scientific and Technology Survey, No. 41,
August 1963, BFMIRA, where it was calculated that the water
content of a sucrose-based boiled sweet must be necessarily
less than 3.2% for it to retain a glassy appearance during
storage.
In practice, it happens that the great majority of
confectionery manufacturers follow this recommendation on
water content which has become established in the mind over
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time.
Furthermore, the experience of confectionery
manufacturers has proved to them, as regards the quantity of
sucrose to be introduced in combination with traditional
syrups of starch hydrolysates, that the ratio conferring the
maximum of stability to the boiled sweets should be close to
50/50 by commercial weight.
It should be noted that the hydrolysates, which are
obtained by acid or acid and enzymatic hydrolysis of starch,
are still today practically the only syrups used to prepare
sugar-based boiled sweets. These syrups have a dextrose
equivalent (DE) of between 30 and 42 and a maltose content
on a dry basis of between 10 and 35%. It has nevertheless
been recommended in the past to use glucose syrups of higher
DE and higher in maltose in order to produce boiled sweets
containing less than 3 or 4% of water. Reference can for
example be made to patents GB 1,349,492 and FR 1,420,929.
For economic reasons, some confectionery manufac-
turers have been led not to comply with the recommendations
established for a long time, which are given above and which
relate to the contents of water and of sucrose and have
placed on the market boiled sweets with a higher water
content, that is to say exceeding the value of 4%, which is
21-65837
considered as abnormally high for this type of confectionery
item.
Accordingly, boiled sweets contA;n;ng 4.0% to 5.3%
of water and from 45 to 50% of sucrose are sold especially
in France. Such boiled sweets are obtained by boiling
mixtures containing powdered sucrose and acid hydrolysates
of starch with a DE close to 30 which are present
approximately in equal parts on a dry basis. The use of
these hydrolysates results in a maltose content of these
sweets which is always very low, generally less than 10%.
These boiled sweets are unstable by nature and tend very
rapidly to grain, consequently becoming opaque and white.
Moreover, these sweets which are high in water have
relatively low glass transition temperatures, of the order
of 36C, and as a result tend to deform and to become
sticky, especially during the summer period.
Other boiled sweets having a water content above 4%
are also known. They are sold in particular in the United
States and are almost exclusively prepared using starch
hydrolysates with a DE of between 38 and 42. Their sucrose
and maltose contents represent less than 10% of their
commercial compositions. Such boiled sweets are also very
unstable. They become, in less than a few days, very sticky
216`5837
when they are exposed to air. Furthermore, their glass
transition temperatures, which are very low and close to
only 30C, make them particularly sensitive to variations in
temperature.
It has also been proposed in patent US 3,826,857 to
prepare weakly hygroscopic boiled sweets containing from 4
to 8% of water, from 40 to 70 % of sucrose, and from 15 to
31.5% of maltose, using a maltodextrin with a DE of between
5 and 25. Nothing is however said about the thermal
stability of these boiled sweets. It appears that such
sweets are very difficult to cast or to form due to the
presence of maltodextrins.
Up until now, it seems that no viable solutions
exist which make it possible to prepare essentially
amorphous boiled sweets which are high in water and are
stable. Such products would nevertheless be advantageous in
many respects, especially because of the fact that they
would be of a lower cost for a quality identical to or even
better than that of commercially available products.
The aim of the invention is to overcome the
disadvantages of the prior art and to provide a new boiled
sweet which satisfies, much better than existing products,
the expectations of confectionery manufacturers and the
'
2165837
various requirements of practical use, that is to say having
a substantially improved storage stability.
At the end of detailed research studies, the merit
of the applicant company is to have found that this aim
could be achieved and that it was possible, against all
expectations, to prepare a boiled sweet which is stable
although containing a high water content, that is to say
greater than 4%.
This boiled sweet can be described as "stable" since
over time it does not tend:
-either to become sticky,
-or to ~grain'~, or to ~turn", becoming opaque and
white at the surface or at the centre,
-or to deform at the usual summer temperatures in
temperate climates.
The applicant company has discovered, surprisingly
and unexpectedly, that in order to obtain a stable boiled
sweet having an abnormally high water content, it is
advisable both to considerably reduce the quantity of
sucrose in the confectionery compared with the usual
quantities, and to ensure that the glass transition
temperature of the sweet, which is necessarily reduced
because of the higher water content, is corrected by the
2165837
11
appropriate choice of a carbohydrate composition.
In other words, it is essential, for such a boiled
sweet to be stable, that it have both a sucrose content of
less than 35% and a glass transition temperature at least
equal to 38C, this glass transition temperature being
measured at a water content close to 4.5% (it should be
remembered, in fact, that the glass transition temperature
varies as a function of the water content, this temperature
being lowered as the water content increases).
The subject of the invention is therefore a boiled
sweet characterized in that it has:
-a water content higher than 4~,
-less than 35% sucrose and more than 65% of a
composition of carbohydrates other than sucrose, these
contents being expressed on a dry matter basis,
-and a glass transition temperature at least equal
to 38C, this glass transition temperature being measured at
a water content of about 4.5%.
The invention relates to a boiled sweet
characterized in that it contains more than 4% of water, in
that it contains, relative to its dry matter content, less
than 35% of sucrose and more than 65% of a composition of
carbohydrates other than sucrose, and in that it has a glass
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12
transition temperature at least equal to 38C, this
temperature being measured for a water content of about
4.5~.
Advantageously, this sugar-based boiled sweet
contains more than 4.2%, preferably more than 4.5~, and
still more preferably more than 4.8% of water. Thus, it may
be advantageously manufactured by boiling at a temperature
which is not very high.
The applicant company has discovered that such
stable boiled sweet could be substantially free of
maltodextin and that the depressive effect caused by an
increase in the water content on the glass transition
temperature could be overcome by a judicious choice of a
composition of carbohydrates other than sucrose. This
composition is present in an amount of at least 65% of the
dry matter content of the boiled sweet in accordance with
the invention, should be suitable for conferring on the
boiled sweet a glass transition temperature greater than
38C for a residual water content of about 4.5% and even
better, greater than 38C for the effective water content of
the boiled sweet. The effective water content corresponds to
the final water content of the boiled sweet at the end of
manufacture.
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Compositions of carbohydrate suitable for conferring
the appropriate glass transition temperature may be
compositions having molecular weights, respectively in
number and in weight, between about 350 and about 600 and
between about 600 and about 1700. These values appear also
to give the best results in terms of viscosity, gloss and
hygroscopycity of the boiled sweets.
In concrete terms, this carbohydrate composition can
be chosen from glucose syrups with a DE (dextrose
equivalent) greater than or equal to 44 cont~;n;ng less than
10%, preferably less than 5%, and more preferably less than
3 % of monosaccharides such as D-glucose or fructose. These
syrups are preferably syrups with an average maltose
content. Indeed, it has been observed that when these syrups
have very high maltose contents, between 75 and 90%, the
boiled sweets obtained are rather hygroscopic and are
subject to breaking during wrapping. Furthermore, it is more
difficult with these syrups to produce boiled sweets having
a glass transition temperature exceeding 38C when they
have, in accordance with the invention, a particularly high
water content. Accordingly, syrups cont~in;ng from 45 to 75~
of maltose, more preferably from 45 to 56% of maltose, and
still more preferably from 48 to 52% of maltose are
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14
preferably used according to the invention. Concerning the
maltotriose content of such glucose syrups with a DE greater
than or equal to 44, values between about 0 % and about 30 %
are prefered, but values between about 5 % and about 25 %
are much more prefered.
In a surprising and unexpected manner, it has been
found that these average maltose contents allowed the
microcrystallisation of maltose to be obtained more easily,
for the water content of sweets designated according to the
invention, than for higher maltose contents.
Such maltose syrups can be produced either directly
by hydrolysis of starch, especially under the action of a
beta-amylase, or indirectly by mixing liquid or solid
products, at least one of which is high in maltose.
In this case, the sugar-based boiled sweet in
accordance with the invention contains preferably from 35 to
75~ of maltose, more preferably from 38 to 65% of maltose
and still more preferably from 42 to 50% of maltose relative
to its dry matter content.
The carbohydrate composition which can be used
according to the invention, may also be constituted, in
total or in part, by the said syrups of average maltose
content, but hydrogenated. In this case, the sweets obtained
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are still less intensely colored.
The carbohydrate composition capable of being used
according to the invention may also be oligosaccharides and
polysaccharides which are reputed to be scarcely digestible,
that is to say less digestible than are sugars. They may be
in particular oligosaccharides and polysaccharides,
dextrins, or polyglucoses such as polydextroses, such as
those obtained, after hydrogenation or otherwise, according
to the process described in patent application EP 561,090 of
which the applicant company is proprietor, or alternatively
according to the process described in patent application
EP 368,451 or EP 593 368. This is advantageous especially
when it is desired to prepare boiled sweets with fewer
calories. It is, of course, possible to combine these
products and the maltose syrups described above.
On the other hand, the use of maltodextrins and of
glucose syrups with a DE less than 44 is in general to be
avoided. Indeed, the massecuites thus obtained, with a water
content greater than 4%, are difficult to cast or to form
because of their very high viscosity but also because of
their characteristic of becoming too elastic. Without
wishing to be bound to any particular theory, it seems that
the problems encountered on the production lines are due to
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16
the fact that the products with a DE of less than 44 contain
excessively high quantities of very high molecular weight
polysaccharides.
The use of carbohydrate compositions cont~;n;ng more
than 10% of monosaccharides, which always impart a high
hygroscopicity on the boiled sweet, is also avoided.
As regards sucrose, for reasons linked to stability,
it is preferred that its content in the boiled sweet, on a
dry matter basis, be less than 30%, more preferably less
than 25% and still more preferably less than 15%.
Surprisingly and unexpectedly, the applicant has
discovered that the reduction of the sucrose content does
not significantly lower the sweetness of the boiled sweet in
accordance with the invention, especially when syrups with
an average maltose or maltitol content are used. It must be
noticed that high intense sweeteners, flavors or/and flavor
and sweetness enhancers like maltol or ethyl maltol may be
used without any problem, to adjust the organoleptic
properties of the boiled sweet according to the invention.
It must also be noticed that in some cases, a reduction in
flavor and in acids contents can be achieved in the boiled
sweets according to the invention.
Another characteristic of the boiled sweet in
~_ 2165837
accordance with the invention is that it has a water
activity greater than that of a customary boiled sweet.
Normally, the boiled sweet in accordance with the invention
has a water activity greater than 0.30. In the case
preferred, that is to say that of sweets having even higher
water contents, the water activity is greater than 0.32, or
even greater than 0.35.
The applicant company has observed that an even
greater stability is obtained by making sure that the glass
transition temperature, measured for a water content of
about 4.5% and preferably for the effective water content of
the boiled sweet, is at least equal to 40C, the ideal
situation being to exceed 43C and even better to exceed
45C.
The boiled sweet in accordance with the invention,
which may be any type of boiled sweet such as clear hard
candy, pulled hard candy, filled hard candy, frosted hard
candy or the like, has several advantages.
It can be manufactured at a lower temperature than
normal, which makes it possible to substantially reduce the
manufacturing costs but also to limit the time for blocking
equipment. In general, the boiling temperatures can be
decreased by several degrees and be chosen between 130 and
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150C. Very often, this reduction is as much as S to 20C
compared with the usual temperatures.
It has been observed, moreover, that in the great
majority of cases, the massecuites are less viscous at a
high temperature than the conventional massecuites for
sugar-based sweets. Consequently, the manufacture by casting
proves to be at least as easy as for the customary
formulations.
The boiled sweet in accordance with the invention is
moreover not very hygroscopic. It has been observed that the
rates of water uptake from the ambient atmosphere are lower
than those of traditional boiled sweets from the first few
days following manufacture and that crystallization is
subsequently possible. This is the case in particular during
the use of maltose or maltitol syrups, and especially,
unexpectedly, during the use of syrups having an average
maltose or maltitol content, that is to say a content of 45%
to 75% relative to the dry composition. The crystallization
remains in all cases invisible to the naked eye, such that
the boiled sweet has the advantage of remaining completely
transparent with a high gloss.
The boiled sweet in accordance with the invention
also tends to be very light in colour. This appears to be
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explained in particular by the presence of a quantity of
inversion products of sucrose which is substantially less
than those usually found for this type of confectionery.
Finally, the boiled sweet in accordance with the
invention is very stable to temperature and does not tend to
run or to deform at summer temperatures in our temperature
climate.
The invention also relates to a process for the
preparation of a new stable boiled sweet, although
containing more water than normal. This process is
characterized in that it comprises the preparation of a
syrup cont~;n;ng on a dry basis less than 35% of sucrose and
more than 65~ of a composition of carbohydrates other than
sucrose which is suitable for conferring on the boiled sweet
a glass transition temperature, measured for a water content
of about 4.5%, or for its effective water content, at least
equal to 38C. It is also characterized in that it comprises
the boiling of the syrup thus prepared at a temperature
sufficient to allow the vitrification of a massecuite
cont~;n;ng more than 4%, preferably more than 4.2% and more
preferably more than 4.5% of water.
The other unit operations for the manufacture of the
new boiled sweet may be identical to those normally carried
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216~5i837
out. Accordingly, the boiled sweet can be equally well
shaped by known casting, forming or extrusion techniques,
after the addition of intense sweeteners, coloring agents,
flavoring agents or other substances.
It should be stated that the quantity of water to be
added in order to prepare the carbohydrate syrup intended
for the manufacture of the sugar-based boiled sweet of the
invention can be advantageously substantially reduced
compared to the usual quantities, taking into account the
use of a smaller quantity of sucrose compared to normal.
Finally the invention relates to the use of a
carbohydrate composition having a molecular weight in number
of between about 350 and about 600 and a molecular weight in
weight of between about 600 and about 1700, in the
production of a stable boiled sweet with less than 35 %
sucrose and more than 4 ~ water, according to the invention.
Preferably, the boiled sweet has all the hereabove specified
characteristics.
The invention will be understood more clearly in the
light of the following examples which are intended to be
illustrative of the invention and not limitative.
ExamPle
Comparison of the stability of various sugar-based
~ 2165837
boiled sweets.
Several sugar-based boiled sweets are prepared by
boiling the following mixtures all having an initial dry
matter content close to 75%:
5- a first mixture composed on a dry basis of 50% of
sucrose and of 50% of a glucose syrup with a DE close to 30,
which is marketed by the applicant under the name ROCLYS~
C30 (mixture M1, according to the prior art),
- a second mixture composed, on a dry basis, of 50%
10of sucrose and of 50% of a glucose syrup with a DE close to
42, which is marketed by the applicant under the name
ROCLYS~ A42 (mixture M2, according to the prior art),
- a third mixture composed, on a dry basis, of 50%
of sucrose and of 50% of a syrup with a DE close to 47,
15which is marketed by the applicant under the name FLOLYS~
C47 (mixture M3, according to the prior art). This syrup
contains, on a dry basis, between 48 and 52% of maltose,
- and finally a fourth mixture composed, on a dry
basis, of 20% of sucrose and of 80% of the glucose syrup
20FLOLYS C47 above (mixture M4, according to the invention).
These four mixtures are boiled on a naked flame, at
a chosen temperature, between 135 and 145C, so as to obtain
sugar-based boiled sweets cont~;n'ng about 4.5% of water.
-- 2165837
For simplicity, the products obtained from mixtures Ml, M2,
M3 and M4 are called Bl, B2, B3 and B4 respectively.
Boiled sweets are also prepared from mixture M2 but
by carrying out the boiling at 155C on a naked flame so as
to obtain a residual water content close to 3%. The products
thus obtained are called B5 (according to the prior art).
The characteristics of the various products are the
following:
-Boiled sweets Bl :
* Colour : very pale yellow,
* Composition on a dry basis : D-glucose:1.5%
Maltose :6.0%
Sucrose :50.0%
* Glass transition temperature: 37C
- Boiled sweets B2 :
* Colour : very pale yellow
* Composition on a dry basis : D-glucose:9.0%
Maltose :7.5%
Sucrose :50.0%
* Glass transition temperature: 34C
- Boiled sweets B3 :
* Colour : very pale yellow
* Composition on a dry basis : D-glucose: 1.5%
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Maltose :25.0%
Sucrose :50.0%
* Glass transition temperature: 36C
- Boiled sweets B4 :
* Colour : not coloured
* Composition on a dry basis : D-glucose:2.0%
Maltose :40.0
Sucrose :20.0%
* Glass transition temperature: 44C
- Boiled sweets B5 :
* Colour : dark yellow
* Composition on a dry basis : D-glucose:9.0%
Maltose : 7.5
Sucrose :50.0%
* Glass transition temperature: 48C
The various boiled sweets are stored for 6 months
comprising a summer period.
It is observed that after this period, only the
boiled sweets B4 and B5 remained unchanged, that is to say
did not tend either to become sticky, or to grain or to
turn, or to deform.
The boiled sweets B4 in accordance with the
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24
invention are as stable as are the control products B5,
although they have a higher water content.
Exam~le 2
Comparison of the behaviour of various maltose
syrups.
Several other sugar-based boiled sweets containing
about 4.2% of water and on a dry basis 20% of sucrose only,
are prepared. For that, the following mixtures are used:
- the mixture M4 of Example 1,
- a mixture comprising on a dry basis 20% of sucrose
and 80% of maltose syrup sold by the applicant under the
name FLOLYS D57 (mixture M6). The dry matter content of
this syrup constitutes about 70% of maltose and about 3% of
D-glucose,
- and a mixture comprising on a dry basis 20% of
sucrose and 80% of a maltose syrup cont~;n;ng about 92% of
maltose and about 4% of D-glucose relative to its dry matter
content (mixture M7).
It is observed that these products obtained
according to the invention, are all very stable and very
clear.
The sweets obtained using the mixture M7 are judged
~- ~ 2165837
to be more brittle than the sweets cont~;n;ng the mixture M4
or the mixture M6. The latter are preferred because they
have a glass transition temperature of between 48 and 50C
whereas for the first ones this glass transition temperature
is only about 41C.
Exam~le 3
Comparison of the viscosities at high temperature of
various massecuites.
Boiled sweets are prepared by casting into moulds,
using a pilot boiler.
For that, the following are used:
- a mixture composed, on a dry basis, of 10% of
sucrose and of 90% of FLOLYS C47 syrup described in Example
1 (mixture M8),
- only the syrup FLOLYS~ C47,
- and the mixture Ml given in Example 1 (according
to the prior art)
In the three cases, boiling is carried out at about
140C with the application of a vacuum, so as to obtain
water contents close to 5.0%.
It is observed that the viscosities of the
massecuites, measured with the aid of a ROTOVISKO PK100
2165837
26
apparatus using a PK5 1 cone, are, in the case where the
mixtures M8 and Ml are used, very similar for a temperature
range between 140 and 120C, and correspond to the usual
casting temperatures. The massecuite prepared by the sole
use of the FLOLYS~ syrup is on the other hand slightly more
viscous.
In all cases, it is possible for a casting to be
carried out without major difficultles.
Upon storage, the sweets prepared essentially or
exclusively with the FLOLYS syrup prove to be more stable
than those composed of the mixture Ml. Indeed, the latter,
contrary to the first, tend to grain and to become opaque
over time.
