III III|||||| USOO5436329A United States Patent 19 11 Patent Number: 5,436,329 Caboche 45 Date of Patent: Jul. 25, 1995

(54) HYPOCARIOGENIC HYDROGENATED SACCHARDES FOREIGN PATENT DOCUMENTS 0171964 7/1985 European Pat. Off. . 75 Inventor: Jean-Jacques Caboche, Bethune, 0368451 9/1989 European Pat. Off. . France 1-12761 10/1985 Japan . 2-163101 12/1988 Japan. 73) Assignee: Roquette Freres, Lestrem, France 8502758 11/1984 WIPO . 21 Appl. No.: 998,603 OTHER PUBLICATIONS 22 Filed: Dec. 30, 1992 SIGMA Technical note in TDFAB-1, Jun. 91. "J. Assoc. Off. Anal. Chem' vol. 68, n° 2, 1985, p. 399. 30 Foreign Application Priority Data "Starch Chemistry and Technology”-Second edition Mar. 19, 1992 FR France ...... 9203314 Edited by Roy L. Whistler, 1984, Academic Press Inc. 51 Int. Cl.9 ...... C08B30/18; C08B30/20, Primary Examiner-Marian C. Knode C08B30/12 Assistant Examiner-Francisco Prats 52 U.S. C...... 536/103; 536/123.1; Attorney, Agent, or Firm-Larson and Taylor 536/123.13; 435/95; 435/96; 435/99; 435/100; 57 ABSTRACT 435/101; 127/29; 127/38 The invention relates to a composition containing 58 Field of Search ...... 517/54, 60,536/122.1, hypocariogenic hydrogenated saccharides which can 536/123.13, 103; 127/29, 38; 435/95, 96, 99, be used as sweetening composition or as texturing agent 100, 101 in food products and in some pharmaceutical or veteri (56) References Cited nary products. This composition is characterized in that it has a concentration of 0.1 to 80% of hydrogenated U.S. PATENT DOCUMENTS monosaccharides, a concentration of 0.1 to 96% of 2,436,967 3/1948 Leuck ...... 127/29 hydrogenated disaccharides, a concentration of 11 to 3,766,165 10/1973 Rennhard ...... 127/29 96% of hydrogenated mono- and disaccharides, a con 4,017,363 4/1977 McMullen et al...... 195/31 centration of 1 to 40% of polysaccharides which are not 4,206,285 6/1980 Poulson et al...... 405/96 hydrolyzed by amyloglucosidase, the balance for 100% 4,445,938 5/1984 Verwaerde et al...... 536/1.1 consisting of hydrogenated oligosaccharides or poly 4,497,846 2/1985 Boursier et al. . ... 426/660 saccharides. 4,766,207 8/1988 Deger et al...... 536/18.6 4,965,354 10/1990 Yanaki et al...... 536/124 5,051,500 9/1991 Elmore ...... 536/50 28 Claims, No Drawings 5,436,329 1. 2 syrups then have the big disadvantage of not conferring HYPOCAROGENIC HYDROGENATED sufficient viscosity on the products in which they are SACCHARDES used. Yet, such a viscosity is required in products such as chewy pastes, boiled sweets, nougats, pharmaceutical The subject of the invention is a composition contain syrups or elixirs or toothpastes. ing hypocariogenic hydrogenated saccharides which Some of the abovementioned hydrogenated products can be used as sweetening composition or as texturing are moreover very hygroscopic, which can present agent in products intended to be ingested by humans or problems especially in the manufacture of boiled animals, that is to say especially in food products, and in sweets, the manufactured sweets then having a real some pharmaceutical or veterinary products. 10 tendency to regain water, and the disadvantages of The invention also relates to a process for preparing sticking to the wrapping paper. the said composition, as well as the application of this Moreover, there could be clear advantage in being composition in products intended to be ingested by able to vary the water activity in the sweetening com humans or annals. positions as a function of the intended subsequent uses. The expression "products intended to be ingested by 15 Yet, this possibility does not exist at the present time, humans or animals' is understood to mean products even using mixtures of two or three hydrogenated prod intended for ingestion or for oral administration, such as ucts such as those mentioned above. various foodstuffs like confectionery products, pastries, Finally, for some applications, it might also be desir creams, drinks, jams, sauces, ice creams, prepared ani able to be able to freely vary the boiling point of the mal fodder, as well as pharmaceutical, veterinary, di 20 etary or health products such as for example elixirs, sweetening composition, to modify its hygroscopicity cough syrups, lozenges or tablets, chewy pastes, chew or alternatively to modify, in a given direction, the glass ing guns, pastilles, mouth washes, and toothpastes and transition temperature or the freezing point. gels. A very obvious demand therefore exists for the food The expression "hypocariogenic hydrogenated sac 25 industry and the pharmaceutical or veterinary industry charides' is understood to mean hydrogenated saccha to be able to have a sweetening composition rides which are acidified to a lesser degree by the bac which is hypocariogenic, and is highly stable to en teria present in the mouth than conventional sugars Zymes, such as sucrose, glucose or fructose. which has a high sweetening power, Such hypocariogenic hydrogenated saccharides are 30 which does not necessarily require the addition of already known. There may be mentioned for example artificial sweeteners (it being possible for this to sorbitol, xylitol, maltitol, erythritol, lactitol, hydroge cause unpleasant organoleptic properties or limita nated isomalitulose (known under the trademark tions in the stability to heat), PALATINIT (R) or more generally under the name which has good technological properties in all types ISOMALT), mannitol, arabitol, threitol, isomaltitol. 35 of application, Syrups containing some of these various products are which is compatible with most ingredients used in already marketed, such as for example sorbitol syrups, products intended to be ingested and which can be maltitol syrups containing about 50-55% maltitol, such premixed, where appropriate, with any one of as for example LYCASIN (R) 80/55 marketed by the them, applicant company, or maltitol syrups containing about whose water activity can be easily regulated accord 72-78% maltitol relative to the dry matter, such as for ing to the application envisaged, example MITISORB (R) 75/75 marketed by the appli whose hygroscopicity, glass transition temperature, cant company or maltitol syrups sold under the trade freezing point and boiling point can be varied ac mark MALTIDEX(R) 100, MALTIDEX(R) 200, cording to the application chosen, MALBIT (R) and FINMALT (R). 45 which has sufficient viscosity and texture so as to However, none of the abovementioned products, or confer on the finished products acceptable "me mixtures of these various products, has all of the quali chanical' properties and texture, ties, advantages or technological properties which it which does not require the addition of texturing addi might be desirable to find in a hypocariogenic sweeten tives or auxiliary products, ing composition. 50 which does not present risks of crystallisation in ap Indeed, some of the abovementioned products, such plications where such a risk would be damaging, as for example sorbitol, maltitol, xylitol, erythritol or or which, on the contrary, can induce limited and mannitol, when they are used at high strengths and controlled crystallisations in some applications concentrations, have a damaging tendency to crystal where a superficial microcrystallisation or granula lise, which makes them unsuitable for use in many food, 55 tion are intentionally sought. pharmaceutical or veterinary products. However, the applicant company has had the great Moreover, some products such as mannitol, lactitol, merit of being able to reconcile all these numerous qual threitol, and hydrogenated isomalitulose do not possess ities and properties, reputed incompatible up until now, a high sweetening power. This limits their applications by preparing and developing a new composition con for example in confectionery products or pharmaceuti 60 taining hypocariogenic hydrogenated saccharides. cal syrups where a pronounced sweet taste is sought The composition containing hypocariogenic hydro before everything else. This requires the addition of genated saccharides conforming to the invention is thus artificial sweeteners such as saccharin, aspartame or characterised in that it has, the concentrations being cyclamates and acesulfame K, which are relatively ex expressed by weight relative to the dry matter of the pensive products and may be unstable. 65 said composition: However, some products have a high sweetening a concentration of 0.1 to 80%, preferably 0.1 to 75% power and are difficult to crystallise. This is the case for and still more preferably 0.1 to 70% of hydroge example for some maltitol syrups. Nevertheless, these nated monosaccharides, 5,436,329 3. 4 a concentration of 0.1 to 96%, preferably 0.2 to 94% 7) 5 mg of protease powder (Sigma product No. P and still more preferably 0.3 to 90% by weight of 3910) are added to each of the beakers. hydrogenated disaccharides, 8) The beakers are covered with an aluminium foil a concentration of 11 to 96%, preferably 22% to 94% and they are incubated at 60° C. for 30 min, with and more preferably 35 to 90% by weight of hy 5 continuous stirring. The incubation time of 30 min drogenated mono- and disaccharides, starts from the moment when the internal tempera a concentration of 1 to 40%, preferably 1.5 to 30% ture of the beakers reaches 60 C. and still more preferably 3 to 26.5% by weight of 9) The mixture is cooled to room temperature. polysaccharides which are not hydrolysed by amy 10) 10 ml of 0.205M H3PO4 are added to each of the loglucosidase in an F test (described below), 10 beakers in order to adjust the pH to 4.5-0.2. The the balance for 100% consisting of hydrogenated pH is checked. It is carefully adjusted, where ap oligo- and polysaccharides. propriate, with the sodium hydroxide or phos The hydrogenated monosaccharides may be chosen phoric acid solutions. from the group comprising sorbitol, mannitol, galac 11) 0.3 ml of amyloglucosidase is added (Sigma prod titol, xylitol, threitol, arabitol and erythritol. 15 uct No. A9913) to each beaker. The hydrogenated disaccharides may be chosen from 12) Each of the beakers is covered with an aluminium the group comprising maltitol, hydrogenated malitulose, foil and incubated for 30 minutes at 60 C., with hydrogenated isomalitulose (mixture of glucopyranosi continuous stirring. The incubation time of 30 min do-1,6-mannitol and glucopyranosido-1,6-sorbitol), iso starts from the moment when the internal tempera maltitol, lactitol, and hydrogenated inulobiose. 20 ture of the beakers reaches 60 C. The hydrogenated oligosaccharides and polysaccha 13) 280 ml of 95% ethanol (v/v), preheated to 60° C., rides may consist of maltotritol, maltotetraitol and are added to each of the beakers. (95% ethanol other hydrogenated oligo- and polysaccharides ob v/v: 50 ml of demineralized water, pure alcohol tained by hydrolysis of starch followed by a hydrogena complement to 1000 ml at 20 C.). tion. However, the said hydrogenated oligosaccharides 25 14) A precipitate is allowed to form by allowing the and polysaccharides may also consist of cellobiitol, mixtures to stand at room temperature for at least cellotriitol, xylobiitol, xylotriitol, inulotritol and other 60 minutes, or overnight (the same time for each of hydrogenated oligo- and polysaccharides obtained by the 4 tests). hydrolysis, generally acid hydrolysis, of cellulose, xy 15) The contents of each of the beakers are filtered lans and fructans such as for example inulin followed by 30 under vacuum over a sintered glass crucible and hydrogenation. Celite bed, and they are successively and carefully In order to determine on the compositions the con washed with: centration of polysaccharides which are not hydrolysed three times 20 ml of 78% ethanol (v/v) (78% etha by the enzyme amyloglucosidase, the F test is used nol v/v: 220 ml of demineralized water, pure which corresponds to the test for the determination of 35 ethanol complement to 1000 ml at 200 C.) "total food fibres' developed by the company SIGMA two times 10 ml of 95% ethanol (v/v) Chemical Company P.O. Box 14508, St. Louis, Mo. and two times 10 ml of acetone. 63178 USA and which is described in detail in the 16) The four filters are dried overnight at 70° C. SIGMA technical note No. TFAB-1 of June 1991. under vacuum. This test consists essentially in determining the 17) These filters are cooled in a desiccator before amount of material contained in the hydrolysate, which being weighed to within 0.1 ng, this weight being is not hydrolysed by an amyloglucosidase in the pres regarded as the sum of the weight of the filtration ence of a thermoresistant a-amylase and a protease. residue (polysaccharides not hydrolysed by amylo This amount is expressed in percentage relative to an glucosidase, plus proteins, plus ash) and the weight amount of about 1 g of hydrolysate previously dried 45 of the crucible with Celite. under vacuum at 70 C. overnight. 18). The protein concentrations of two of the four To carry out this test, the procedure is as follows: filtration residues resulting from the four tests are 1) Four samples of about 1 g of hydrolysate previ determined by proceeding according to the Kjel ously dried under vacuum and cooled in a desicca dahl method, using a correction coefficient of 6.25. tor overnight are weighed to within 0.1 mg and are 50 19). The amounts of ash are determined on the other introduced into a 400 ml tall-shaped beaker. two filtration residues by placing the crucibles in 2) 50 ml of phosphate buffer (0.05M) at pH: 6.0 are an oven at 525 C. for 5 hours. added to each of the four beakers. 20) The amounts of polysaccharides not hydrolysed 3) 0.05 ml of a solution of alpha-amylase (Sigma prod by amyloglucosidase are calculated for the four uct no. A 3306) is added to each of the beakers and 55 tests as indicated in the SIGMA technical note and mixed thoroughly. a mean value is calculated for these amounts which 4) Each beaker is covered with an aluminium foil is expressed in terms of the mean of the amounts of before being placed in a boiling water bath to incu hydrolysate material dried overnight at 70 C. bate them for 30 min starting from the moment under vacuum, taking into account in the calcula when the temperature in the beakers reaches 95 C. tion, the results of the four blank tests (without dry The mixture is gently stirred at regular 5 minute hydrolysate) carried out in parallel. intervals. This F test constitutes a variant of the test for the 5) The solutions are cooled to room temperature. determination of total food fibres in foodstuffs de 6) The pH of the solutions is adjusted to 7.5-0.1 by scribed in “J. Assoc. Off. Anal. Chem.” Vol 68, No. 2, adding to each beaker 10 ml of 0.171N NaOH. The 65 1985, p 399. pH is checked and it is adjusted where appropriate It has the advantage of being standardised, of being with sodium hydroxide (0.171N) or phosphoric able to be carried out using a complete analytical kit and acid (0.205M). - of being repeatable and reproducible. 5,436,329 5 6 The concentrations of polysaccharides which can be bility of adjusting the viscosity, the boiling point, the precipitated in ethanol and which are not hydrolysed by glass transition temperature, the freezing point, the amyloglucosidase can also be determined on the con hygroscopicity and the sweetening power. positions conforming to the invention using another test To prepare the sweetening composition conforming which has been termed test A, by carrying out the pro to the invention, the procedure is carried out as follows cedure as follows. or in a similar manner. A sample of 10 g of the sweetening composition con First, a fraction comprising the polysaccharides not forming to the invention, adjusted by the addition of digested by amyloglucosidase is prepared. To do this, at water or by evaporation to a Brix of 75-0.2, equivalent least one dextrin and/or polyglucose is subjected to an to a refractive index of about 1.478, is used for the deter 10 enzymatic treatment comprising at least the action of a mination of the level of hydrogenated polysaccharides Saccharifying enzyme such as amyloglucosidase or beta which can be precipitated in ethanol. It is recalled that amylase, the conditions for this treatment being chosen Brix is a unit of measurement which is commonly used such that the DE of the dextrin and/or polyglucose in the starch industry and that the Brix of a syrup is very hydrolysate obtained at the end of this treatment is easily determined by a refractometer reading. A Brix of 5 between 5 and 80, preferably between 10 and 65, the 75 generally corresponds, for the compositions con hydrolysate obtained then being hydrogenated and then forming to the invention, to a dry matter content ap purified in a manner known per se. proximately equal to 75%. The term "polyglucose' is understood to mean the The sample of 10 g of the sweetening composition products predominantly consisting of 1-6 bonds, ob conforming to the invention at 75 Brix is supplemented tained by condensation or rearrangement from glucose with 30 cm3 of distilled water and 60 cm3 of absolute or from one or more sugars, which may be reduced, ethanol. The mixture is allowed to stand for one hour at under the combined action of heat and acids in a me O'C. It is then centrifuged at 0° C. for 15 min at 10,000 dium practically devoid of water. Such polymers have g. The pellet obtained is dried in a vacuum oven main been described many times and can be obtained by pro tained at 80 C. The weight of the precipitate obtained, 25 cesses such as those described especially in U.S. Pat. P1, represents the weight of polysaccharides which can Nos. 2,436,967, 3,766,165, 4,965,354, 5,051,500, JP be precipitated in ethanol contained in the 10 g of initial 01-12761 and JP 02-163101. Advantageously, these pol sample, that is to say about 7.5 g of dry matter. ymers are obtained from glucose and citric acid, option In order to determine the concentration, in the sweet ally in the presence of sorbitol. ening composition conforming to the invention, of hy 30 Within the scope of the present invention, the term drogenated polysaccharides which can be precipitated "dextrin' is understood to mean the products obtained in ethanol and which are not hydrolysed by amyloglu by heating starch adjusted to a low moisture level, gen cosidase, an A test is used which consists in subjecting erally in the presence of acidic or basic catalysts. This the previously obtained ethanol-precipitated polysac "dry roasting' of starch, most commonly in the pres charides to an enzymatic attack using a thermoresistant 35 ence of an acid, results both in a depolymerisation of the alphaamylase, a protease and an amyloglucosidase, then starch and a condensation of the starch fragments ob in carrying out a precipitation of the polysaccharides tained, and leads to the production of highly branched which are not hydrolysed with 95% ethanol, infiltering molecules. Dextrins are part of the oldest starch deriva the precipitate thus obtained, in washing the latter in tives and their preparation, their applications, the vari alcohol and acetone and finally in determining the ous types of dextrins as well as their properties are weight, P2, of residue obtained. described for example in the book entitled "Starch This test is also described in “J. ASSOC. OF ANAL. Chemistry and Technology'-Second Edition-Edited CHEM.” Vol. 68, No. 2, 1985, p. 399, article to which by Roy L. WHISTLER-1984-Academic Press Inc. reference can be made. Enzymatic treatments of dextrin have already been A composition containing hypocariogenic hydroge 45 proposed in the literature as for example in European nated saccharides conforming to the invention can be Patent Applications No. 0368451 or JP-A-62091501, but characterised in that it has, the concentrations being for other purposes. These prior art documents will be expressed by weight relative to the dry matter of the more fully analysed later. said composition: Preferably, the dextrins obtained by the dry roasting a concentration of 0.1 to 65%, preferably 0.1 to 60% SO of starch in the presence of an acidic catalyst such as and still more preferably 0.1 to 55% of hydroge hydrochloric acid, are used for the preparation of the nated monosaccharides, compositions conforming to the invention. The acid is a concentration of 10 to 96%, preferably 15 to 94% thus sprayed on the starch and the mixture obtained is and still more preferably 15 to 90% by weight of predried, for example from 80 to 130 C. until a water hydrogenated disaccharides, 55 content of less than or equal to about 5% is obtained. a concentration of 1 to 30%, preferably 1.5 to 25% Then the mixture is "roasted' at a temperature of about and still more preferably 2 to 15% by weight of 140 to 250 C. for a period of 30 minutes to about 6 polysaccharides which can be precipitated in etha hours in order to obtain the dextrin, which has at the nol and which are not hydrolysed by amylogluco end of the reaction a DE of about 0.5 to 10. Any type of sidase in an A test described above. starch, and especially maize starch, potato starch, wheat It is essentially by virtue of the presence of the se starch, cassava starch, rice starch or pea starch can be lected concentration of hydrogenated polysaccharides used for the preparation of these dextrins. not hydrolysed by amyloglucosidase that it is possible According to the ISO 1227 standard of 1979, a dex to obtain, by concomitantly selecting on the other hand trin is obtained from starch or starch flour converted by the concentration of hydrogenated mono-, di-, oligo 65 heating in the dry state with or without the addition of and polysaccharides, a sweetening composition possess Small amounts of chemical reagents. Traditionally, dex ing all the qualities required in most applications, such trins are classified into two categories: white dextrins as for example the absence of crystallisation, the possi whose appearance is not very different from that of the 5,436,329 7 8 raw material used, and yellow dextrins, which are pro hydrolysed by amyloglucosidase, the sweetening com duced under more drastic conditions and whose depth position conforming to the invention is then prepared. of colour can be correlated with the degree of modifica For this, starting with a defined percentage of this tion of the native structure. The four types of reaction composition, this percentage quite obviously depending occurring during the dextrinisation are, at low tempera on the concentration of polysaccharides in the said tures, essentially hydrolysis of the alpha 1-4 bonds and fraction, optionally hydrogenated monosaccharides, then, at the higher temperatures, condensation, transg disaccharides, oligosaccharides and polysaccharides are lycosidation and anhydrisation reactions. then added in defined proportions for each of these Dextrins such as those marketed by the applicant groups of constituents. company under the trademarks TACKIDEX DF 165, 10 According to a first variant, there are added to the TACKIDEX DF 155, TACKIDEX JO 55 K can be non-hydrogenated polysaccharide fraction obtained at advantageously used. the end of the enzymatic treatment of dextrin, polyglu The dextrin, polyglucose or mixture of dextrins and cose or a mixture thereof, optionally followed by a /or polyglucoses selected are thus suspended in water at chromatographic enrichment or fractionation step, non a dry matter content of about 20 to 70%, preferably 20 15 hydrogenated monosaccharides, disaccharides or oligo to 45% in order to undergo saccharification using at saccharides and polysaccharides in defined proportions least one saccharifying enzyme consisting of amyloglu for each of these various constituents. And the composi cosidase and/or beta-amylase. tion thus obtained is hydrogenated. Preferably, and although this is not necessary in all According to a second variant, which is preferred, cases, this enzymatic action of beta-amylase and/or the polysaccharide fraction is separately hydrogenated amyloglucosidase may be preceded by the action of an and monosaccharides or disaccharides or oligosaccha alpha-amylase which is preferably thermoresistant. rides and polysaccharides already hydrogenated are Likewise, the saccharification treatment can be fol added thereto in defined proportions for each of these lowed or accompanied by the action of an alpha-amy various constituents. lase. 25 According to a preferred mode, a treatment using an By way of example, a sweetening composition con enzyme which hydrolyses the 1-6 bonds of amylopec forming to the invention canthus be prepared by mixing tin, such as for example isoamylase or pullulanase, can an inulin hydrolysate, birchwood or maize cobs, a also be used. This treatment, using an enzyme which starch hydrolysate and a fraction containing the poly hydrolyses the 1-6 bonds of amylopectin, which may Saccharides obtained by enzymatic hydrolysis of a dex precede, accompany or follow the saccharification trin and/or a polyglucose, these hydrolysates and this treatment, is particularly advantageous insofar as the fraction being mixed in predefined proportions, and the action of this enzyme makes it possible to allow only the mixture thus obtained is then hydrogenated. polysaccharides which are very difficult to digest enzy The sweetening composition prepared under these matically, to remain in the dextrin and/or polyglucose 35 conditions contains at the same time xylitol, arabitol, hydrolysate obtained. sorbitol, mannitol, maltitol as well as hydrogenated The enzymatic action of amyloglucosidase, beta polysaccharides which are not digested by amylogluco amylase and, optionally, alpha-amylase, pullulanase or sidase. isoamylase, on dextrin, polyglucose or on their mixture, As already mentioned above, processes consisting in makes it possible to obtain a fraction comprising, in enzymatically hydrolysing a dextrin have already been addition to glucose, maltose, maltotriose and other oli proposed in the literature. gosaccharides and polysaccharides, polysaccharides Thus, European Patent Application No. 03684.51 which are not digested by amyloglucosidase. describes a process essentially consisting in dissolving a This fraction may be directly hydrogenated or sub pyrodextrin in water and in reacting an alpha-amylase jected to an additional treatment in order to enrich it 45 with the resulting solution. This process is designed to with polysaccharides which are not digested by amylo remove the undesirable odour and taste from pyrodex glucosidase. Such a treatment may consist for example trin and to give dextrins containing dietary fibres. of a membrane procedure such as reverse osmosis or Thus, according to the process described in this pa ultrafiltration, solvent precipitation or chromato tent application, a pyrodextrin is dissolved in water and graphic fractionation. If desired, it is even possible to go SO then hydrolysed using alpha-amylase. However, other as far as practically isolating the said polysaccharides, enzymes may be added after the alpha-amylase treat preferably by chromatographic fractionation on cati ment: this applies to transglucosidase, beta-amylase and onic resins in alkali metal or alkaline-earth metal form glucoamylase. The product obtained at the end of this or on zeolites. enzymatic treatment can then be hydrogenated. Mono This chromatographic fractionation can therefore be 55 saccharides and oligosaccharides may be added to the carried out before hydrogenation and it is then quite initial starch intended to be dextrinised, in order to obviously necessary to subsequently hydrogenate the increase the concentration of indigestible dextrin in the polysaccharides not digested by amyloglucosidase. But final product. in conformity with a preferred embodiment of the in The object of the abovementioned patent application vention, this chromatographic enrichment or separation is therefore essentially to provide a product which is not treatment of the polysaccharides is carried out after very digestible, "low in calorie', which acts as dietary hydrogenation. This thus makes it possible to use only food fibre and which essentially consists of polysaccha one hydrogenation treatment for preparing the compo rides which are not very digestible. The content of the sition containing hydrogenated saccharides conforming product exemplified by "indigestible dextrins' thus to the invention, and, moreover, the separation of the 65 ranges between about 27% and about 95% and the polysaccharides is more effective in this case. concentration, in these products, of polysaccharides Having therefore thus obtained a fraction containing whose degree of polymerisation is equal to or greater optionally hydrogenated polysaccharides which are not than 4, is between about 60% and about 92% by weight. 5,436,329 9 10 Another process for producing dietary food fibres mixture of dextrins and/or polyglucoses, optionally from dextrins has, moreover, been described in Japa comprising additional saccharides, oligosaccharides and nese Patent Application.JP-62091501. This process con polysaccharides, may be carried out in a manner known sists in treating, at a high temperature, a hydrogenated per se, by hydrogenation over RANEY nickel or by starch hydrolysate by carrying out this heating under 5 hydrogenation over noble metals. anhydrous conditions at 150-250 C. in the presence of This hydrogenation is carried out after purification of a catalyst consisting of an inorganic acid or an organic the hydrolysate, for example by a treatment over acti acid. vated carbon, after demineralisation over cationic and Just like the patent application mentioned above, this anionic resins. The hydrogenation may be carried out document therefore relates to the production of prod O for example over a RANEY nickel catalyst, at a temper ucts which are not very digestible in the body, so-called ature of 130 C. and at a hydrogen pressure of 50 bars. “low in calories' and which act in the body as food After hydrogenation, the syrup obtained is filtered fibres. Their object is therefore far removed from the and then demineralised, and then concentrated until the object of the present invention, which is to prepare a concentration at which it is marketed is obtained, which sweetening product consisting of hydrogenated saccha 15 is generally between about 70 and 85 Brix, equivalent to rides with a high sweetening power, which is hypocari about 70% to 85% of dry matter. It may also be dried ogenic and has technological properties which can be for example by spray-drying. used both in sweets, chewing gums and toothpastes, and The hydrogenation is generally carried out until in drinks and pharmaceutical or veterinary elixirs, or there is obtained a percentage ratio of residual reducing other products. 20 sugars to dry matter of less than 0.50, preferably less Moreover, it may be emphasised that the said prior than 0.25 and still more preferably less than 0.20. art documents do not describe or suggest a use of en One of the essential characteristics of the sweetening zymes which hydrolyse the 1-6 bonds of amylopectin, composition according to the invention lies in its enzymes whose expected action within the scope of the hypocariogenicity, that is to say in its capacity to cause present invention makes it possible to produce a fraction 25 a much lower acidification by the bacteria present in the containing hydrogenated polysaccharides with a very mouth, than conventional ordinary sugars such as glu low digestibility, which constitutes quite a significant cose, fructose, sucrose or glucose syrups. advantage. According to a completely advantageous embodi Preferably, the amounts and conditions for the action ment of the invention, the sweetening composition con of the various enzymes used for preparing the fraction 30 forming to the invention has the property of being able obtained by enzymatic hydrolysis of dextrin and/or to be described as non-cariogenic according to a B test. polyglucose, of dextrins or of polyglucoses, and in This B test had been developed by the applicant com tended for the preparation of the hypocariogenic sweet pany in order to monitor the non-cariogenic character ening composition conforming to the invention, are of the hydrogenated hydrolysates marketed from 1978 chosen from the following: 35 under the name LYCASIN (R) 80/55. This simple test is amyloglucosidase: 4,000 to 500,000 international based on the determination in vitro of the acidification units/kg of dry substrate, a temperature of 50° C. to of a given amount of hydrogenated starch hydrolysate 60° C., duration of action from 30 to 100 hours, a after inoculating the medium with saliva. It is based on pH of 5.0 to 6.0, the determination of the drop in pH over time for a beta-amylase: 100 to 10,000 LINTNER units per culture broth containing the test product, after then kilogram of dry substrate, a temperature of 50° C. inoculating with saliva obtained from several donors, in to 60 C., duration of action from 30 to 100 hours, comparison with a control culture broth not containing a pH of 5.0 to 6.0, any carbohydrate. It should be emphasised that this test alpha-amylase: 20 to 2,000 KNU units (Kilo Novo is not adequate for an absolute characterisation of the Units) per kilogram of dry substrate, a pH of 5.0 to 45 non-cariogenicity of a product since its results can vary 6.0, a temperature of 50 C. to 60° C., duration of for example with the quality of the saliva used, but it action from 16 to 100 hours, makes it possible nevertheless to establish valid compar enzyme hydrolysing the 1-6 bonds : 150 to 15,000 isons between the various products. ABM units (ABM, CHESHIRE, ENGLAND) per The detailed procedure for this test is as follows. kilogram of dry substrate, optionally in the pres 50 A series of tubes are prepared containing 10 ml of a ence of 50 to 100 international units of beta-amylase sugar-free nutrient culture medium (trypticase medium per kilogram of dry substrate, a pH of 5.0 to 6.0, a containing 2% dry matter), at p 7, and these tubes are temperature of 50° C. to 60° C., duration of action sterilised by transferring to an autoclave at 120° C. for from 24 to 100 hours. 20 minutes. The enzymes used may be: 55 In a first series of five tubes, 1 ml of sterile water is in the case of amyloglucosidase, fungal amyloglucosi introduced in order to prepare a control series. dases, In a second series of five tubes, 1 ml of an 18% (w/v) in the case of beta-amylase, microbial or plant beta solution of the test product is introduced. amylases, Then the five tubes for each series are inoculated in the case of alpha-amylase, bacterial or fungal al with the same volume of 0.2 ml per tube of a dilution of pha-amylases, human saliva collected from 5 donors. in the case of enzymes hydrolysing the 1-6 bonds, The formation of acids is then monitored by measur those chosen from pullulanase and isoamylase such ing the pH, a first measurement being carried out before as for example: PULLUZYME 750L from ABM incubation and the other measurements being carried or CK20L from AMANO. 65 out after incubations, at 30 C. of 3, 6, 13, 18 and 21 Within the scope of the present invention, the hydro hours respectively. genation of the hydrolysate obtained following the en For a product to be considered as non-cariogenic zymatic hydrolysis of dextrin, of polyglucose or of the based on this B test, the difference in pH observed be 5,436,329 11 12 tween the control after 21 hours and the test product This syrup was then treated with 0.8% (volume/- after 21 hours must not be too pronounced and, in prac volume) of a solution of H2O2 at 35% (v/v) for 24 tice, must not be more than 1 unit of pH. hours, at 70° C. and pH 9.5. Residual hydrogen perox One of the great advantages of the present invention ide was decomposed by adding a small amount of cata is that it provides sweetening compositions which pos 5 lase and then the syrup was deoxygenated under vac sess the property of being non-cariogenic based on this uum before being treated with activated carbon and B test, while nevertheless containing a substantial then demineralised on a bed of mixed resins. amount of hydrogenated oligosaccharides and polysac The syrup was then concentrated to a dry matter charides. content of 40% and was then hydrogenated using 5% Other advantages of the present invention are to 10 RANEY nickel catalyst, at a temperature of 130° C. and provide sweetening compositions which are stable and at a hydrogen pressure of 50 bars. The hydrogenation which can be used as sweetening agent and as texturing was continued until a reducing sugar level of less than agent in products intended to be ingested by humans 0.5% was obtained. and animals, these products possessing a liquid or vis cous, pasty, jelly-like or solid texture, which are com 15 Composition A pletely compatible with the other ingredients used in Part of this syrup conforming to the invention, called these products and which can be optionally premixed, in what follows "base syrup' assaying 15.3% of mal without any drawback, with a preservative, an emulsi titol, 22.4% of polysaccharides with an DP equal to or fier, a flavouring, a sugar, a polyol, an intense sweeten greater than 20, and 16.2% of polysaccharides which ing agent, an acid, a pharmaceutical or veterinary ingre 20 are not hydrolysed by amyloglucosidase according to dient, a fat, an inorganic or organic filler such as poly the F test, was then supplemented with crystallised dextroses, fibres, fructooligosaccharides, gums, an or maltitol in a proportion such that the added maltitol ganic or inorganic gelling agent such as proteins, pec represents 40% of the dry matter content of the total tins, modified celluloses, algae and seed extracts, bacte composition to give the composition. A containing hy rial polysaccharides and silicas. 25 drogenated saccharides according to the invention. These products, which are intended to be ingested by humans or animals, may possess a liquid or viscous Composition B texture, such as drinks, syrups, emulsions, suspensions, Another portion of this base syrup was supplemented elixirs, mouth washes, ampoules with contents to be with crystallised xylitol in a proportion such that the taken orally; a pasty texture, such as non crystallised or 30 added xylitol represents 60% of the dry matter content semi-crystallised confectionery products such as hard of the total composition to give the composition B con sweets, jellies, gums, chewy pastes, caramels, chewing taining hydrogenated saccharides according to the in gums, fodders, and cereal bars; a jelly-like texture, such vention. as food gels, such as custard tarts, jams, jellies, milk The compositions A and B containing hydrogenated desserts or pharmaceutical and veterinary gels, tooth 35 pastes; a solid texture such as pastry, biscuit and bakery saccharides according to the invention were then con products, tablets, side dishes, spray-dried or extruded centrated to a dry matter content of 75%. sweetening or flavouring powders, and pharmaceutical These compositions gave the following carbohydrate or veterinary freeze-dried products. spectra, in addition to which the results obtained in the Another advantage of the composition containing F test and the A test are presented (Table I). hydrogenated saccharides according to the invention is TABLE I being particularly stable to microbial enzymes and to Composition A Composition B oxidising or reducing chemical reagents. Dry matter % 75 75 This advantage can be exploited in the formulation Reducing sugars 0.24 0.20 and preparation of products which are not intended to 45 (% over DM) DP1 sorbitol 2.5 1.7 be ingested by humans and animals, such as for example DP1 xylitol 0 60 cosmetic products, plastics, metal quenching, skin treat DP2 maltitol ment, and casting moulds. and isomaltitol 48.9 6. The examples below, which are given with no limita DP3 4.4 2.6 SO DP 4 2.5 1.8 tion being implied, will illustrate the invention more DP 5 3.0 1.9 clearly. DP 6 2.5 1.9 DP7 2.7 1.8 EXAMPLE 1. DP 8 2.6 1.4 DP9-20 15.5 11.1 Into a 25-liter tank, stirred and thermostatted, were DP & 20 13.8 9.0 introduced 20 liters of a syrup prepared by dissolving in 55 Polysaccharides not 8.7 5.7 water the yellow dextrin TACKIDEX DF 165 to a dry hydrolysed by amylogluco matter content of 35%. sidase in % (F test) Precipitate Pl in ethanol 23 15.3 The pH was adjusted to 5.5 using concentrated so (%). (A test) dium hydroxide and the tank was thermostatted at 55 Precipitate P2 (in 7%) 4.6 3.1 C. before adding thereto: after enzymatic digestion 0.015% of the beta-amylase SPEZYME DBA, from (A test) the company GENENCOR, Viscosity at 20 C. (cps) 7000 3200 0.2% of the pullulanase PULLUZYME 750 L from the company ABM. A cariogenicity test according to the B test was car After 48 hours of saccharification, 0.1% of the alpha 65 ried out on the compositions A and B. The drop in pH amylase MAXAMYL HT 3000, from the company between the control and the compositions A and B GISTBROCADES was added. The saccharification analysed was 0.90 and 0.80 respectively. The composi was stopped after 88 hours. tions A and B are not cariogenic according to the B test. 5,436,329 13 14 nated, purified and concentrated in the same conven EXAMPLE NO. 2 tional manner. Another base syrup was prepared by carrying out the Syrups were thus obtained, whose composition rela procedure as described below: tive to the drymatter content, is presented in Table III. In a 25-liter tank, stirred and thermostatted, were introduced 20 liters of a syrup prepared by dissolving in water the yellow dextrin TACKIDEX DF 165 to a dry TABLE III matter content of 35%. Composition C Composition D The pH was adjusted to 5.5 and the temperature to Dry matter % 75 75 55° C. 0.05% of the amyloglucosidase OPTIDEX C 10 Hydrogenated monosaccharides 50.2 66.1 (xylitol - sorbitol) 300, from the company MILES, was added per kg of Maltitol-isomaltitol 0.4 0.3 dextrin and 0.1% of the alpha-amylase MAXAMYL DP3 1.25 0.8 HT 3000, from the company GIST-BROCADES, and DP 4 2 1.5 then the saccharification was allowed to proceed for 60 DP5 2.7 1.8 hours. 15 DP 6 2.35 1.6 DP7 1.95 1.3 The syrup obtained was treated with hydrogen per DP8 2.1 i.4 oxide as described in Example 1, before being treated DP9-20 5.8 10.5 over activated carbon and then demineralised over a DP 20 21.3 14.2 bed of mixed resins. The mixture was then concentrated Non-hydrolysable 23.2 15.8 to a dry matter content of 50%. This syrup contained 20 polysaccharides in % (F test) 45% of real glucose and 55% of oligo- and polysaccha Precipitate P1 (%) 28. 18.7 rides. (A test) This syrup was fractionated by chromatography on a Precipitate P2 (%) 21.6 14.4 column containing a strong cationic resin, crosslinked (A test) with divinylbenzene and converted to the sodium form, 25 Viscosity (cps) 5900 4800 and having a particle size of between 0.2 and 0.4 mm: the resin C204, marketed by DUOLITE. The fraction ation was carried out for successive loadings of 0.15 EXAMPLE NO. 3 liter of syrup for a column 2 meters high, containing The polysaccharide syrup obtained according to Ex 1.50 liter of resin. The elution of each loading was car 30 ample 2, and whose composition is given in Table II, ried out using water at 60 C., at a flow rate of 0.85 was used, mixed with the crystallised isomalitulose mar liter/hour. keted by the company MITSUI, in order to prepare Each eluate loading was fractionated into two por mixtures containing respectively: tions, one corresponding to the beginning of the elution 35% of isomalitulose (on a dry basis) and containing the polysaccharides, the other corre 35 sponding to the end of the elution and containing essen 50% of isomalitulose (on a dry basis) tially glucose. 66% of isomalitulose (on a dry basis) The eluates corresponding to the polysacchariderich and these syrups were hydrogenated, purified and con fractions were evaporated and then reconcentrated to centrated in order to obtain the compositions E, F and give a polysaccharide syrup whose carbohydrate spec G according to the invention and having the carbohy trum, determined by high performance liquid chroma drate spectra (expressed in % relative to the dry matter tography, is presented in Table II. content) presented in table IV. TABLE II TABLE IV COMPO- COMPO. COMPO DP (glucose) 0.4% SITION E STION F SETION G DP2 (maltose, isomaltose) 0.8% 45 DP3 (maltotriose) 2.5% Dry matter content in % 75 75 75 DP 4 (maltotetraose) 4.0% Hydrogenated mono- 0.3 0.2 0. DP5 5.4% saccharides (sorbitol) DP 6 4.7% Hydrogenated DP7 3.9% disaccharides DP 8 4.2% 50 maititol 0.5 0.4 0.3 DP 9-20 31.6% isomaltitol 16.5 25 33 DP 20 42.6% glucopyranosido-1,6- 16.5 25 33 mannitol DP3 1.7 1.25 0.8 This syrup, called in what follows polysaccharide DP 4 2.7 2 .5 syrup, was used as base to prepare the following com 55 DP 5 3.6 2.7 1.8 positions C and D according to the invention. DP 6 3. 2.35 1.6 DP7 2.6 1.95 1.3 Composition C DP 8 2.8 2. 1.4 DP9-20 21.0 15.8 10.5 Crystallised xylose was dissolved in the polysaccha DP & 20 28.4 21.3 14.2 ride syrup so as to represent 50% of the dry matter Non hydrolysable 30.0 23. 15.9 content of the total composition, and then the resulting polysaccharides (%) (F test) syrup was hydrogenated, purified and concentrated in a Precipitate P1 (%) 37.4 28.1 8.7 conventional manner. (A test) Precipitate P2 (%) 28.8 21.6 14.4 Composition D 65 (A test) Crystallised xylose was dissolved in the same poly Viscosity (in cps) at 44,600 10,000 7,300 saccharide syrup so as to represent 66% of the dry matter content, then the resulting syrup was hydroge 5,436,329 15 16 4 kg of hydrogenated syrup S, EXAMPLE NO. 4 16 kg of the sorbitol syrup NEOSORB (R)70/70 mar In a 25-liter tank, stirred and thermostatted, are intro keted by the applicant company. duced 20 liters of a syrup prepared by dissolving in The composition I was thus obtained after mixing water, to a dry matter content of 35%, the yellow dex- 5 thoroughly. trin TACKIDEX DF 165 marketed by the applicant company. The pH of this syrup is adjusted to 5.5 and the Composition J temperature to 55 C., and then the following are intro- Into a 25-liter tank, stirred and thermostatted at 65 duced: C., are introduced: 0.15% (w/dry w) of the g-amylase Spezyme DBA 10 10 kg of hydrogenated syrup S, from the company GENENCOR, and 0.2% 10 kg of the polyol syrup POLYSORB (R) 70/12/12 (w/dry w) of the pullulanase Pulluzyme 750 L marketed by the applicant. from the company ABM. These compositions gave the following carbohydrate After 86 hours, the mixture is acidified to pH 3.5 and spectra (Table V) the tank is heated to 80 C. for 20 minutes in order to 15 TABLE V inhibit the enzymes. This syrup is filtered and then demineralised over E. SE SE, strong cationic and weak anionic resins and adjusted to a dry matter of 40%. E. latter conte?t 70 70 70 This hydrolysate is then hydrogenated. For that, 5% 20 Moosaccharides in 2, of Raney nickel catalyst is added relative to the syrup. Sorbito 0.8 60.3 8.0 The hydrogenation is carried out at a temperature of Mannitol 25.2 5.8 0.5 130 C., at a hydrogen pressure of 50 bars. It is contin- Disaccharides in 2 16.5 14.3 16.9 ued until a reducing sugar level of less than 0.5% is NEEpolysaccharides in % 16.9 4.6 11.4 obtained. 25 (F test) The hydrogenated hydrolysate is then purified and City, R dry matter content. It contains The compositions H and I are non-cariogenic based 1% of sorbitol, on the B teSt. The composition J may be considered as 22% of maltitol and isomaltitol, 3o hypocariogenic. 25% of polysaccharides which are not hydrolysed The composition H was found to be very useful for according to the F test. preparing sugar-free boiled sugars which are not very This syrup conforming to the invention, called in YEOP. w what follows hydrogenated syrup S, was used as base to The composition I gave good results in the produc prepare the compositions H, I and J according to the 35 tion of toothpastes, conferring on the latter, combined invention. with silicas, an excellent jelly-like texture. Finally, the composition J was used in the prepara Composition H tion of silicated casting moulds. It is a good binding and A portion of the hydrogenated syrup s is diluted to cohesion-promoting agent. 60% dry matter content. 40 EXAMPLE NO. 5 Mannitol F, marketed by the applicant company, is o added to this diluted hydrogenated syrup S, in a propor- Preparation of non-cariogenic chewy pastes compris tion such that the mannitol represents 25% of the dry ing four compositions according to the invention. matter content of the total composition. The mixture is The compositions A, B, C and D obtained according stirred until the mannitol is completely dissolved, and 45 to Examples No. 1 and 2 are used to formulate non-cari then concentrated to 70% dry matter content to give ogenic chewy pastes. r the composition H. A control chewy paste is prepared using a mixture of crystallised xylitol and the syrup LYCASIN (R) 80/55. Composition I The four recipes thus possess similar xylitol concentra In a 25-liter tank, stirred and thermostated at 60° C., 50 " . . the following are introduced: The recipes (in grams) before boiling the chewy pastes are given in Table VI. TABLE VI RECIPE RECIPE 2 RECIPE 3 with compositions with composition with composition RECIPE 4 A and B C D (CONTROL) Polyols: Composition A 732.1 Composition B 204.5 Composition C 245.3 Composition D 186.7 Lycasin 80/55 691.3 749.9 844.6 Crystallised 92.0 xylitol Hydrogenated 39.5 39.5 39.5 39.5 copra Gelatin solution 20.0 20.0 20.0 20.0 Glycerol mono- 3.9 3.9 3.9 3.9 Steatate 5,436,329 17 18 TABLE VI-continued RECIPE RECIPE 2 RECIPE 3 with compositions with composition with composition RECIPE 4 A and B C D (CONTROL) Ratio PolyolsP in 2in ( a (2) X 00 4.3 5.6 2.9 O (1) Pin%: polysaccharides which can be precipitated it possible to obtain sweets having, like in the case of in alcohol and which are not hydrolysed based on traditional sweets obtained with sugar, a water content the A test for the mixture of polyols used. 10 of between 2 and 3%, which is necessary to endow the (2) Polyols in %: amount of polyols present in the sweets with good stability despite the low boiling tem mixture of polyols used. peratures. Furthermore, the sweets obtained are To produce the chewy pastes, the mixture of polyols hypocariogenic. is boiled at a defined temperature (130° C. or 145° C), at I claim: atmospheric pressure; the mixture is allowed to cool to 1. A composition of hydrogenated saccharides com 110 C., the fat, emulsifier and gelatin solution are incor- prising, the concentrations being expressed by weight porated and then the pastes obtained are stretched be- relative to the dry matter of the composition: fore shaping and cutting them. 0.1 to 80% of hydrogenated monosaccharides, The rheological characteristics of the chewy pastes 0.1 to 96% of hydrogenated disaccharides, obtained are given in Table VII below: 20 11 to 96% of hydrogenated mono- and disaccharides, TABLE VII BOILNG TEMPERATURE C. RECIPE RECIPE 2 RECIPE 3 RECIPE 4 130° C. Paste: Paste: Paste: Paste: cotect texture soft correct textile very soft not very sticky slightly sticky very slightly sticky very sticky good machinability difficult to shape good machinability impossible to shape correct strength incorrect strength correct strength no strength 145 C. Paste: Paste: Paste: Paste: firm texture rather brittle texture correct texture soft non sticky non sticky very slightly sticky very sticky good machinability good machinability good machinability difficult to shape correct strength correct strength correct strength correct strength It can be observed that compared with the possibili ties offered in the prior art, the compositions A, B, C 35 and D make it possible to prepare xylitol-containing i to 40% of polysaccharides which are not hydro non-cariogenic chewy pastes, with a texture suitable for lyzed by amyloglucosidase in an F test said poly machine processing and having the correct strength saccharides being obtained by enzymatic hydroly during storage. sis of dextrin or polyglucose, said polyglucose pre EXAMPLE NO. 6 dominantly consisting of 1-6 bonds, obtained by condensation or rearrangement of glucose or one Preparation of hypocariogenic boiled sweets com or more other sugars, wherein said hydrolysis is by prising compositions according to the invention. a saccharifying enzyme selected from the group The compositions F and G obtained according to consisting of amyloglucosidase and beta-amylase to Example 3 are used to prepare boiled sweets. For that, 45 provide a hydrolysate, which is subsequently hy these two compositions with a dry matter content of drogenated, 75%, are dehydrated by boiling using a naked flame, the balance for 100% consisting of hydrogenated and at atmospheric pressure, at the temperatures of 140 oligo- and polysaccharides. C., 145 C., 150 C. and 16O C. 2. The composition according to claim 1 wherein the Control boiled sweets are obtained by boiling ISO 50 concentration of said polysaccharides which are not MALT (R) (equimolar mixture of isomaltitol and hydrolyzed by amyloglucosidase in an F test is 1.5 to glucopyranosido-1,6-mannitol) at the same tempera 30% by weight. tles. 3. The composition according to claim 1 wherein the After boiling, sweets are obtained whose water 20 concentration of said polysaccharides which are not contents were found to be as follows: 55 hydrolyzed by amyloglucosidase in an F test is 3 to TABLE VIII 26.5% by weight. COMPO- COMPO 4. The composition according to claim 1 comprising, TEMPERATURE SITON F STONG ISOMALT the concentrations being expressed by weight relative FOR BOILING WATER. 2 WATER 92 WATER 92. to the dry matter of the composition: 40 C. 3.6 4.0 6.5 60 0.1 to 75% of hydrogenated monosaccharides, 145 C. 2.5 3. 5.0 0.2 to 94% of hydrogenated disaccharides, 150 C. 2. 2.4 4.5 22 to 94% of hydrogenated mono- and disaccharides, 16O C. 1.3 2.0 3.1 1 to 40% of said polysaccharides which are not hy drolyzed by amyloglucosidase in an F test, It is observed that dehydration of the compositions F 65 the balance for 100% consisting of hydrogenated and G according to the invention is easier than that of oligo- and polysaccharides. the ISOMALT syrup. Boiling the compositions accord 5. The composition according to claim 4 wherein the ing to the invention requires less energy, and they make concentration of said polysaccharides which are not 5,436,329 19 20 hydrolyzed by amyloglucosidase in an F test is 1.5 to the balance for 100% consisting of hydrogenated 30% by weight. oligosaccharides or polysaccharides. 6. The composition according to claim 4 wherein the 17. The composition according to claim 16, wherein concentration of said polysaccharides which are not the concentration of said polysaccharides which can be hydrolyzed by amyloglucosidase in an F test is 3 to 5 precipitated in ethanol and which are not hydrolyzed 26.5% by weight. by amyloglucosidase in an A test is 1.5 to 25% by 7. The composition according to claim 1 comprising, weight. the concentrations being expressed by weight relative 18. The composition according to claim 16, wherein to the dry matter of the composition: the concentration of said polysaccharides which can be 0.1 to 70% of hydrogenated monosaccharides, 10 precipitated in ethanol and which are not hydrolyzed 0.3 to 90% of hydrogenated disaccharides, by amyloglucosidase in an A test is 2 to 15% by weight. 35 to 90% of hydrogenated mono- and disaccharides, 19. The composition according to claim 16 compris 1 to 40% of said polysaccharides which are not hy ing, the concentration being expressed by weight rela drolyzed by amyloglucosidase in an F test, tive to the dry matter of the composition: the balance for 100% consisting of hydrogenated 15 0.1 to 60% of hydrogenated monosaccharides, oligo- and polysaccharides. 15 to 94% of hydrogenated disaccharides, 8. The composition according to claim 7 wherein the 1 to 30% of said polysaccharides which can be pre concentration of said polysaccharides which are not cipitated in ethanol and which are not hydrolyzed hydrolyzed by amyloglucosidase in an F test is 1.5 to by amyloglucosidase in an A test, 30% by weight. 20 the balance for 100% consisting of hydrogenated 9. The composition according to claim 7 wherein the oligosaccharides or polysaccharides. concentration of said polysaccharides which are not 20. The composition according to claim 19, wherein hydrolyzed by amyloglucosidase in an F test is 3 to the concentration of said polysaccharides which can be 26.5% by weight. precipitated in ethanol and which are not hydrolyzed 10. The composition according to claim 1, wherein 25 by amyloglucosidase in an A test is 1.5 to 25% by the hydrogenated monosaccharides are selected from weight. the group consisting of sorbitol, mannitol, galactitol, 21. The composition according to claim 19, wherein xylitol, threitol, arabitol and erythritol. the concentration of said polysaccharides which can be 11. The composition according to claim 1, wherein precipitated in ethanol and which are not hydrolyzed the hydrogenated disaccharides are selected from the by amyloglucosidase in an A test is 2 to 15% by weight. group consisting of maltitol, hydrogenated malitulose, 22. The composition according to claim 16 compris hydrogenated isomalitulose, isomaltitol, lactitol, and ing, the concentration being expressed by weight rela hydrogenated inulobiose. tive to the dry matter of the composition: 12. The composition according to claim 1, wherein 0.1 to 55% of hydrogenated monosaccharides, the hydrogenated oligosaccharides and polysaccharides 35 15 to 90% of hydrogenated disaccharides, are selected from the group consisting of maltotriitol, 1 to 30% of said polysaccharides which can be pre maltotetraitol, inulotritol, cellobiitol, cellotriitol, cipitated in ethanol and which are not hydrolyzed xylibiitol, Xylotritol and hydrogenated oligosaccha by amyloglucosidase in an A test, rides and polysaccharides obtained by hydrolysis of the balance for 100% consisting of hydrogenated starch, cellulose, xylans or fructans. 40 oligosaccharides or polysaccharides. 13. The composition according to claim 1 which is 23. The composition according to claim 22, wherein not cariogenic according to a B test. the concentration of said polysaccharides which can be 14. The composition according to claim 1, wherein precipitated in ethanol and which are not hydrolyzed the conditions for the enzymatic treatment of dextrin or by amyloglucosidase in an A test is 1.5 to 25% by polyglucose are selected such that the DE of the hy 45 weight. drolysate obtained at the end of this treatment is be 24. The composition according to claim 22, wherein tween 5 and 80. the concentration of said polysaccharides which can be 15. The composition according to claim 1, wherein precipitated in ethanol and which are not hydrolyzed the conditions for the enzymatic treatment of dextrin or by amyloglucosidase in an A test is 2 to 15% by weight. polyglucose are selected such that the DE of the hy 50 25. A process for preparing a composition according drolysate obtained at the end of this treatment is be to claim 1, comprising the steps of: tween 10 and 65. Subjecting at least one dextrin or one polyglucose, 16. A composition of hydrogenated saccharides com said polyglucose predominantly consisting of 1-6 prising, the concentration being expressed by weight bonds, obtained by condensation or rearrangement relative to the dry matter of the composition: 55 of glucose or one or more other sugars, other to an 0.1 to 65% of hydrogenated monosaccharides, enzymatic treatment by at least one saccharifying 10 to 96% of hydrogenated disaccharides, enzyme selected from the group consisting of amy 1 to 30% of polysaccharides which can be precipi loglucosidase and beta-amylase under conditions tated in ethanol and which are not hydrolyzed by sufficient to obtain an hydrolysate having a DE amyloglucosidase in an A test said polysaccharides between 5 to 80, being obtained by enzymatic hydrolysis of dextrin adding to this hydrolysate, monosaccharides, disac or polyglucose, said polyglucose predominantly charides or oligosaccharides and polysaccharides, consisting of 1-6 bonds, obtained by condensation to obtain a mixture or rearrangement of glucose or one or more other and hydrogenating the mixture to obtain a composi sugars, wherein said hydrolysis is by a saccharify 65 tion consisting essentially of ing enzyme selected from the group consisting of 0.1 to 80% of hydrogenated monosaccharides, amyloglucosidase and beta-amylase to provide a 0.1 to 96% of hydrogenated disaccharides, hydrolysate which is subsequently hydrogenated, 11 to 96% of hydrogenated mono- and disaccharides, 5,436,329 21. 22 1 to 40% of polysaccharides which are not hydro zyme selected from the group consisting of amylo lyzed by amyloglucosidase in an Ftest, the concen glucosidase and beta-amylase under conditions trations being expressed by weight relative to dry sufficient to obtain an hydrolysate having a DE matter of the composition. between 5 to 80, 26. The process according to claim 25 which further hydrogenating the hydrolysate, comprises before hydrogenation a treatment using an alphaamylase. adding to this hydrogenated hydrolysate, hydroge 27. The process according to claim 25 which further nated monosaccharides, disaccharides, oligosac comprises before hydrogenation a treatment using an charides and polysaccharides, to obtain a composi enzyme which hydrolyses the 1-6 bonds of amylopec O tion consisting essentially of tn. 0.1 to 80% of hydrogenated monosaccharides, 28. A process for preparing a composition according 0.1 to 96% of hydrogenated disaccharides, to claim 1, comprising the steps of: 11 to 96% of hydrogenated mono- and disaccharides, subjecting at least one dextrin or one polyglucose, 1 to 40% of polysaccharides which are not hydro said polyglucose predominantly consisting of 1-6 15 lyzed by amyloglucosidase in an F test, the concen bonds, obtained by condensation or rearrangement trations being expressed by weight relative to dry of glucose or one or more other sugars, to an enzy matter of the composition. matic treatment by at least one saccharifying en ck c :

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