This invention relates to a starch hydrolysate which can be optionally hydrogenated as well as the process for preparing said hydrolysate and uses thereof. Its glucidic spectrum corresponds to: PA0 a content of monosaccharides (DP=1) less than 14%, PA0 a content of disaccharides (DP=2) less than 35%, preferably less than 20%, PA0 a content of oligosaccharides of DP 4 to DP 10 ranging from 42% to 70%, preferably from 42 to 60%, the oligosaccharides of DP 5 to DP 7 representing by themselves a proportion preferably higher than 25% and more preferably higher than 30%, PA0 a content of polysaccharides of DP higher than 10, less than 32%, and preferably less than 25%. The hydrolysate is useful in the preparation notably of human foodstuff.

The invention relates to a starch hydrolysate, possibly hydrogenated. 
It also relates to the process for preparing this hydrolysate as well as 
the uses thereon. 
It is a particular object of the invention to providing a hydrolysate which 
is not too viscous, which is stable in solution, which has good nutrient 
and physiological qualities, good physical properties, good 
anticrystallizing power, and which, if necessary, is not cariogenic. 
Now, applicant has found that hydrolysates responding to this group of 
properties had to be neither too rich in polysaccharides of high molecular 
weight, nor too rich in saccharides of low molecular weight, the glucid 
spectrum having, on the contrary, to show a relatively high content of 
oligosaccharides, it being understood that the saccharides, 
oligosaccharides and polysaccharides concerned are present possibly in the 
form of the corresponding hydrogenated products. 
Consequently, the starch hydrolysates, possibly hydrogenated, which are the 
subject matter of the invention, have from a very general point of view, a 
relatively high content of oligosaccharides simultaneously with a 
comparatively low content of saccharides and of polysaccharides, and they 
comprise linear or branched chains. 
Thus, the above-said optionally hydrogenated hydrolysates have a relatively 
high content of oligosaccharides of DP 4 to DP 10, preferably from DP 5 to 
DP 7 (DP=degree of polymerisation) and a comparatively low amount of mono- 
and di-saccharides as well as of polysaccharides with a DP higher than 10, 
those of these hydrolysates which are non-cariogenic being in hydrogenated 
form and having a very low content of polyols of DP higher than 20, this 
content being advantageously less than 3% and, preferably, less than 1.5%. 
The optionally hydrogenated hydrolysates according to the invention are 
characterized by a glucid spectrum corresponding to: 
a content of monosaccharrides (DP=1) less than 14%. 
a content of disaccharides (DP=2) less than 35%, preferably less than 20%, 
a content of oligosaccharides of DP 4 to DP 10 ranging from 42% to 70%, the 
oligosaccharides of DP 5 to DP 7 representing by themselves a proportion 
preferably higher than 25%, and more preferably higher than 30%. 
a content of polysaccharides of DP higher than 10 less than 32%, preferably 
less than 25%. 
The hydrogenated hydrolysates corresponding to the above-said glucid 
spectrum and which, in addition, are devoid of cariogenic character, have, 
besides, a content below 3%, preferably below 1.5%, of polyols of DP 
higher than 20. 
The percentages which have just been discussed are percentages by weight, 
expressed on the dry matter of hydrolysates. 
The hydrolysates according to the invention with a particularly 
advantageous glucid spectrum will be described below.

Applicant has found that, for numerous applications, both in the industrial 
field and in the food field, dietetics or pharmaceutical field, there was 
obvious interest in having available a starch hydrolysate with a well 
defined composition, and in particular with a relatively high content of 
oligosaccharides of DP 4 to DP 10. Too large an amount of saccharides with 
low molecular weight or of polysaccharides can in fact show, for very 
precise applications, a good many drawbacks. 
Applicant has observed that an increase in the proportion of high molecular 
weight polysaccharides (DP higher than 10) accounts for an increase in the 
viscosity of the hydrolysates and especially in a lack of stability in 
solution (retrogradation) of the latter. 
Thus, it has observed more particularly that syneresis phenomena, appearing 
on storage for long periods (several weeks) of the mixtures used for the 
preparation of foundry moulds and cores (silicates+borax+hydrogenated 
glucose syrups) and which are manifested by heterogeneities within the 
mixture, were due especially to the presence of polyols of high DP. 
These same phenomena occur on storage of the syrups alone, whether or not 
hydrogenated, which presents drawbacks for certain applications such as 
the use of the hydrolysates concerned in foodstuff for patients. In this 
application, besides the absence of retrogradation on storage, a quick 
absorption of carbon hydrates is sought, and thus the content of high 
molecular products, considered as being slowly assimilated, is to be 
limited. 
Applicant has also shown that the very high molecular weight products (DP 
higher than 20) which are present in hydrogenated syrups are essentially 
responsible for the acidification which is produced by the bacteria of the 
mouth, which acidification causes attack on the dental enamel. Such 
hydrogenated hydrolysate used in confectionery, and, in particular, in 
hard candies must not contain polyols with a DP higher than 20, or at the 
most, an amount less than 3% to preserve the non-cariogenic character. 
The low molecular weight saccharides constitute products which are more 
easily assimilable, from the nutritional point of view, but they possess a 
high sweetening power, a strong osmolality and can account for certain 
intestinal disorders. Their presence in too large an amount is 
consequently not wanted, in some products intended for patient foodstuff, 
where a light sweet taste, a weaker osmolality and a good physiological 
tolerance of products is sought. In some applications, such as the 
manufacture of foundry moulds or cores, the presence of mono- and 
di-saccharides in too large an amount reduces the physiological qualities 
aimed at (compressive strength). Thus, a hydrogenated glucose syrup used 
in foundry, as a breakdown agent, must contain a quantity of sorbitol (DP 
1), sufficient to ensure the control of the water content of the medium in 
which the syrup is used, without this amount reaching the values liable to 
cause a reduction in the physical properties; for example, too much 
sorbitol and/or also too much maltitol (DP 2) would cause too sudden a 
change in the mixture silicate-syrup on casting (breakage of the mould or 
core). 
In confectionery, in the preparation of hard candies, the starch 
hydrolysates with a high content of products of DP 1 and DP 2 are 
difficult to handle. The hard candies are not stable on storage, because 
of too high a hygroscopy. 
Taking the foregoing into account, the uses according to the invention, of 
the above-said hydrolysates are situated in various fields according to 
the glucid spectrum. 
These uses comprise: 
preparation of binders for foundry moulds and cores; 
human feeding notably manufacture of jams, chocolates, sausages, 
ice-creams, chewing-gums and hard candies, the food concerned being not 
cariogenic when these hydrolysates are hydrogenated and when their content 
of product of DP higher than 20 is less than 3%; 
infant dietetics and feeding of patients; 
preparation of polyurethanes and 
constitution of blood plasma substitutes. 
The process according to the invention for preparing hydrolysates, 
according to the invention, whose content of products of DP 4 to DP 10 is 
from 42% to about 55% and whose content of products of DP 1 is less than 
about 5% comprises the action on a previously gelatinized or liquefied 
starch, preferably by enzymatic action (DE less than 20) of 
.alpha.-amylase, this enzyme being applied in the proportion of 3000 to 
20000 I.U./kg d.m. for 8 to 48 hours. 
The process according to the invention for preparing hydrolysates, 
according to the invention, with a content of products of DP 4 to DP 10 
ranging from 42% to about 50% and with a relatively high content of about 
5 to 14% of products of DP 1, in which process .alpha.-amylase and 
1,4-amyloglucosidase are made to act simultaneously, is characterized by 
the fact that said .alpha.-amylase and 1,4-amyloglucosidase are applied to 
a starch previously liquefied by the acid or enzymatic route to a D.E. of 
25 at the most, in the proportion of 500 to 4000 I.U./kg d.m. as regards 
the first and in the proportion of 30 to 500 I.U./kg d.m. as regards the 
second, the action being continued for 10 to 48 hours until the production 
of a D.E. of 30 to 40. 
The process according to the invention for preparing hydrolysates with a 
content of oligosaccharides of DP 4 to 10 higher than about 55% and with a 
content less than 1.5% of products of DP higher than 20 and/or with a 
content as low as desired, of products of DP less than 4, is characterized 
by the fact that a hydrolysate of D.E. close to 30 obtained by acid or 
enzymatic liquefaction of a starch is fractionated by molecular sieving, 
for instance by elution on a cationic resin, the first fractions which 
contain the products of high DP and/or the last fractions containing the 
products of DP less than 4, being eliminated. 
To obtain the corresponding hydrogenated products, the hydrolysates 
obtained at the end of the above-defined process are subjected to 
conventional hydrogenation, notably by the Raney nickel method. 
It is possible to transform these hydrolysates into powder form by 
resorting to conventional methods such as spraying. 
It is possible to use as a raw material for the manufacture of the 
above-said hydrolysates, modified or unmodified starches from any source 
such as root starches, corn starches, waxy-maize, starches from wheat, 
from manioc and the like. 
The foregoing considerations are illustrated by the examples which relate 
to preferred embodiments. 
EXAMPLE I 
A suspension of starch with 35% of dry matter and with pH 6 is liquefied 
conventionally by means of a thermoresistant .alpha.-amylase of the type 
Bacillus Licheniformis, by passage at 106.degree. C. for 3 minutes, then 
is maintained at 95.degree. C. until a D.E. of 16 is obtained. The enzyme 
is then inhibited by a quick passage at a temperature of 160.degree. C. It 
is cooled to 60.degree. C. and 100 liters of this hydrolysate is incubated 
for 30 hours with 8000 I.U. of .alpha.-amylase of the Bacillus Subtilis 
type. The D.E. which is obtained is then 28.0. 
The glucidic distribution of the thus obtained hydrolysate is summarized in 
Table I. 
TABLE I 
______________________________________ 
Products of % by weight 
______________________________________ 
DP 1 2.0 
DP 2 8.0 
DP 3 12.0 
DP 4 6.8 
DP 5 11.6 
DP 6 20.2 
DP 7 5.2 
DP 8 1.8 
DP 9 2.1 
DP 10 2.3 
between DP 10 and DP 20 
9.0 
DP higher than 20 19.0 
______________________________________ 
The hydrolysate is purified by successive passages over activated charcoal, 
anionic and cationic resin. After a concentration of 62,5% 
(weight/volume), the solution is stabilized by addition of 0,1% of sorbic 
acid. The osmolality of this product is 450 millios mole/kg. 
Different samples of the solution were done and placed respectively at 
4.degree. C. and 50.degree. C. for a period of four weeks. 
No turbidity is observed on any of the samples. This hydrolysate was 
administered orally to several patients. Their impression was judged as 
being very in favour of the product, both as regards its taste and 
tolerance, secondary effects such as nausea and diarrhoea being absent. 
Other tests were carried out, by perfusion of the hydrosylate into the 
jejunum. 
It was proved that the hydrolysate releases glucose in the blood at speed 
as high as the glucose itself. 
At the same time, these experiments have proven that the luminal 
concentration of glucose released by the hydrolysate remained low, thus 
limiting the risk of diarrhoea. 
EXAMPLE 2 
A suspension of starch is liquefied by means of hydrochloric acid 
conventionally to a D.E. of 19.0. After adjustment of the dry matter 
content to 35% and of the pH to 5.2, to 100 l of the syrup is added at the 
same time 1900 I.U. of .alpha.-amylase and 75 I.U. of amylo 1-4 
glucosidase per kg of dry starch. It is incubated at 60.degree. C. The 
enzymatic reaction is stopped by bringing the substrate rapidly to a high 
temperature as soon as the D.E. reaches 34, that is to say after 20 hours. 
The glucid distribution of this syrup is summarized in Table II. 
TABLE II 
______________________________________ 
Products of % by weight 
______________________________________ 
DP 1 12.2 
DP 2 9.8 
DP 3 15.4 
DP 4 9.0 
DP 5 11.0 
DP 6 11.7 
DP 7 7.0 
DP 8 3.4 
DP 9 3.0 
DP 10 2.0 
between DP 10 and DP 20 
5.3 
DP higher than 20 10.2 
______________________________________ 
This glucid distribution is shown in FIG. 1. 
The preponderance according to the invention of products of DP 4 to DP 10 
is clearly apparent therein. 
After filtration and purification, the syrup is hydrogenated. 
The preparation of three mixtures called products A, B and C and 
constituted in the following manner was then undertaken: 
a pre-mixture containing 1000 grams of a syrup of hydrogenated glucose 
(identified below and different for each of the products A, B and C) 
brought previously to 71% of dry matter, 67 grams of anhydrous borax and 
90 grams of water, was made up. This pre-mix was then added in the 
proportion of 20% by weight to a sodium silicate used currently in the 
foundry industry, of SiO.sub.2 modulus equal to 2.4 and having a dry 
matter content Na.sub.2 O of about 55%. 
As regards product A, the hydrogenated glucose syrup is constituted by the 
above-said product of the invention and has a D.E. before hydrogenation of 
34. 
As regards product B, the glucose syrup is constituted by a hydrogenated 
glucose syrup of the prior art having a D.E. before hydrogenation of 33 
and containing 25% of maltitol. 
As regards product C, the glucose syrup is constituted from a hydrogenated 
glucose syrup of the prior art having a basic D.E. of 55 and containing 
50% of maltitol. 
The hydrogenated hydrolysates which enter into the composition of the three 
products A, B and C which will be used in the foundry tests have the 
glucid distributions which are reported in Table III. 
TABLE III 
______________________________________ 
Product Product Product 
Products of A B C 
______________________________________ 
DP 1 12.2 5.2 7.5 
DP 2 9.8 24.0 52.0 
DP 3 15.4 17.1 17.5 
DP 4 to DP 10 47.1 30.0 15.5 
DP 5 to DP 7 29.7 11.5 7.4 
between DP 10 and DP 20 
5.3 4.5 6.5 
DP higher than 20 
10.2 19.2 1.0 
______________________________________ 
The preparations A, B and C obtained are kept on a water-bath at 40.degree. 
C. for 24 hours; this constitutes an accelerated ageing test. 
The viscosity was then measured and it was verified whether syneresis 
existed. The results were: 
______________________________________ 
Product A Product B Product C 
______________________________________ 
Viscosity 1780 2300 1200 cp 
Syneresis no yes no 
______________________________________ 
It appears that the hydrolysate of the invention, whilst having a low basic 
D.E., does not give rise to prejudicial syneresis, whilst having a lower 
viscosity more suitable for use in the field of preparing foundry moulds 
and cores. 
The products A, B and C were then used for the fabrication of specimens 
i.e. test-pieces using a sand for foundry works. The sand and the various 
products were mixed on a planetary Hobart type apparatus, in the 
proportion of 3.5% of product with respect to the sand. 
On a GF raming apparatus (type SPRA of the STOKVIS Company) samples of 163 
g, of 50.8 mm height and a 50 mm diameter, were formed. 
Six sets of three specimens were prepared respectively from products A, B 
and C. A controlled flow of carbon dioxide gas was passed through the mass 
of these specimens (25.degree. C.-5.5 l/mn at a pressure of 350 g/cm2). 
The blowing times tested were 5, 10, 20, 30, 60 and 120 seconds. 
When the blowing was finished, a shearing force was applied on an INSTRON 
apparatus (an apparatus marketed by INSTRON limited Co., of England) 
machine 1122. 
The results of the measurements are assembled in Table IV. 
TABLE IV 
______________________________________ 
Shearing force 
Specimens based 
in g-cm.sup.2 after various blowing times 
on 5 s 10 s 20 s 30 s 60 s 120 s 
______________________________________ 
Product A 2400 3900 5800 6400 7500 8800 
Product B 1500 3750 5200 6100 7600 8500 
Product C 1300 2750 4500 5500 7000 7600 
______________________________________ 
On examining these results, it is observed that due to the use of the 
hydrolysate according to the invention (Product A) the physical 
characteristics of the corresponding test-piece are higher than the 
physical characteristics of the test-pieces comprising the hydrolysates of 
the prior art (Products B and C). 
Another series of test specimens was subjected to a carbon dioxide blow for 
5 seconds under the previously defined conditions. They were then stored 
(temperature of 20.+-.1.degree. C. and relative humidity of 65%) for 
varying times and subjected to shearing forces on the GF apparatus. 
The results of the measurements are collected in Table V. 
TABLE V 
______________________________________ 
Shearing force 
Test specimens 
in g-cm.sup.2 after various storage times 
based on 1 h 2 h 6 h 24 h 
______________________________________ 
Product A 6100 6800 8800 15000 
Product B 6100 6600 8300 15600 
Product C 2600 5050 7000 12800 
______________________________________ 
These measurements confirmed the preceding series. Without syneresis, the 
product A preserves a performance level equal to that of the product B. 
EXAMPLE III 
A suspension of potato starch with 35% of dry matter is liquefied 
conventionally by .alpha.-amylase to a DE of 27.0. 
This hydrolysate is passed over a column containing 400 cubic centimeters 
of LEVATIT Ca 9220 brand resin (cationic type resin) placed in the calcium 
form and this in the proportion of 150 cm3/hour and at 80.degree. C. 
The first eluted fractions contain the polysaccharides of very high 
molecular weight. They are separated from the syrup and represent about 
30% by weight of the starting syrup. The hydrolysate no longer containing 
higher polysaccharides has the composition indicated in Table VI. 
TABLE VI 
______________________________________ 
Products of % by weight 
______________________________________ 
DP 1 5.0 
DP 2 12.0 
DP 3 14.0 
DP 4 10.0 
DP 5 14.7 
DP 6 28.0 
DP 7 7.5 
DP 8 3.5 
DP 9 2.6 
DP 10 2.7 
DP higher than 10 
nil 
______________________________________ 
This glucidic distribution is represented by the graph of FIG. 2. The 
preponderance according to the invention of the product of DP 4 to DP 10 
is clearly apparent. 
After concentration to 50% of dry matter, this hydrolysate is hydrogenated. 
The syrup obtained can be perfectly suitable for the manufacture of 
sweets. In order to do this, 1% of citric acid and 0.25% (on dry matter) 
of saccharin are added to the syrup and the mixture is preheated to 95% 
before it is passed in a continuous vacuum cooker of the Hamac Hansella 
type. The product is allowed to cool on a refrigerated surface at 
80.degree. C. 
The plastic mass thus obtained is placed in a rolling mill shaped into a 
ribbon, moulded and cut up. The sweets thus obtained are wrapped 
immediately after cooling They are hard brittle and have an excellent 
taste. In addition, they have the advantage of being non-cariogenic due to 
the absence of polyols of DP higher than 20 and the syrup. 
The above said hydrogenated syrup has been used for the manufacture of 
chewing-gum as a constituant of a liquid phase. 
In order to do so, 20 parts by weight of basic gum (such as the marketed 
under the name "Firm Paloja" by L. A. Dreyfus Company) softened to 
75.degree. C., are kneaded with 15 parts by weight of hydrogenated syrup 
to 75% of dry matter, the sweetening power of which was increased by 
addition of 0.15% on dry matter of saccharin. The solid phase constituted 
by 52% of powder of sorbitol and 8% of powder maltitol is progressively 
added and the kneading is carried on for 30 minutes. The chewing-gum thus 
obtained is non-cariogenic, did not have recrystallization at the surface, 
they are not sensitive to variations in hygrometry and in temperature of 
the atmosphere in which they were stored and have an excellent taste. 
As result of which and whatever the embodiments adopted, there is thus 
provided by the invention a starch hydrolysate whose characteristics 
emerge clearly from the foregoing. 
As is self evident and as emerges from the foregoing, the invention is in 
no way limited to those of its types of application and embodiments which 
have been more particularly described; it encompasses, on the contrary, 
all modifications.