IL28342A - Low calorie sweetener and method of preparation thereof - Google Patents

Description

C O H E N Ζ Ε ΕΤ r S P I S B A C H R E G D . PAT E N T AT TOR N E YS " 24, LEVONTIN STR., P. O. B. 1169 .

I E L · Ά V I v' P A T E N T S & D E S I G N S. O R D I N A N C E 16685/67 SPECIFICATION .

LOW CALORIE SWEETENER AM) METHOD^ OP PREPARATION THEREOF injsn no'sn naiayn nVp nVisn *yya p»naa We , MONSA TO COMPANY, a corporation of the State of Delaware, U.S.A., of 800 North Lindbergh BA$tlsvar The prior art teaches many materials , and combinations of materials, which are described as useful as substitutes for sugar. It will be understood that , as used herein, the term "sugar" refers to granulated table sugar, which is essentially sucrose. By employing such substitute materials or combinations one can attain a desired level of sweetness , accompanied by a reduction of caloric intake. However, it. has generally been found that these substitutes are subject to a variety of disadvantages which reduce their acceptance by consumers.

There are certain substitute sweeteners. in which the sweetness per unit volume is significantly greater than that of sugar.. This enables the user to obtain a desired level of sweet ness with a very small amount of product. Many users object to such products since their habits with sugar dictated the use of certain volumes , and there is a natural human reluctance to change such habits . Another problem encountered with substitute sweeteners, including also those used in greater amounts, lies in the fact the many users find, or think they find, some difference in taste as compared with sugar. Such a difference, whether, real or just imagined, is undesirable in view of the aforesaid reluctance to change an established habit.

In addition, it has been found that some substitute sweeteners are relatively insoluble under all conditions while others are merely difficult to dissolve under certain tempere d to which they are added, and some have a laxative effect on many users. Finally, even with those substitutes which are said to "resemble" sugar, the actual differences in appearance can often be readily recognized by even a casual comparison.

It is therefore a primary object of the present invention to provide a low calorie sweetener composition which overcomes all of the problems previously encountered.

It is a more specific object of this invention to provide a sweetener composition which has the physical appearance, solubility and taste of sugar, which has a substantially reduced caloric content, and which has. a sweetness per unit volume equivalent to that of sugar.

Another object of the invention is to provide processes by which such sweetener compositions can be readily and. reasonably produced.

Still other objects, advantages and features of this invention will become apparent to those skilled in the art upon consideration of the detailed description hereinafter presented.

It has. now been found that a low calorie sweetener composition comprising a corn starch hydrolyzate and an arti-ficial or non-nutritive sweetener displays the desirable features noted above and substantially . avoids the problems of the prior art. Corn starch is the naturally : occuring , highly polymeric carbohydrate which is found in the crown and glutinous regions of the corn kernel. Corn starch hydrolyzates are the products obtained by the partial hydrolysis of corn starch. The methods , by which such hydrolysis is achieved are well known in the art and include both the acid process and the acid-enzyme process. As employed herein, the term "corn starch" refers to starches derived from corn (maize) and which contain both amylose and a c n ati of from about 1:3 to about 1:4 to ether mediate properties.

The hydrolyzates which are employed herein take two forms designated as corn syrups and corn syrup solids. The corn syrups are the clear, colorless,, noncrystallizable , viscous liquids obtained by working up the crude hydrolysis product, and corn syrup solids are the solid substances obtained by dehydrating said corn syrups.

The artificial or non-nutritive sweeteners of this invention include saccharin and the salts thereof, the cyclamate salts and mixtures thereof. Such salts include calcium sacchari sodium - saccharin, calcium cyclamate, sodium cyclamate, potassium cyclamate and ammonium cyclamate.

The corn starch hydrolyzates are classified by their "Dextrose Equivalent" or "D.E . " This is a measure of the re-ducing-sugar content calculated as anhydrous dextrose and expressed as a percentage of the total dry substance. The procedure for determining Dextrose Equivalent is that adopted by th Corn Industries Research Foundation, Inc. Said procedure is described in detail in their publication entitled "Corn Syrups and Sugars" (1965 edition). It is equally applicable to hydrolyzates in the form of corn syrups or in the form of corn syrup solids ; · The corn starch hydrolyzates which are employed in the low calorie sweeteners of this invention are those hydrolyzates having a Dextrose Equivalent or D.E. of from about 15 to about 4 When hydrolyzates having higher D.E. values are used, it has bee found that the sweetener product shows an undesirable degree of hygroscopicity . Such a property presents a problem since the sweetener products tend to cake and Ipse their free . flowability . In addition, the use of hydrolyzates having a lower D.E. value or turbid appearance in the liquid to which they are added.

However, it has now been determined that certain of these lower D.E. hydrolyzates, particularly those having a D.E. value of from about 5 to about 15, can be used in the low calori sweeteners of this invention without giving rise to the aforesaid solubility problem. Specifically, the corn starch hydrolyzates of from about 5 to about 15 D.E. and havinq an Iodine Affinity of less than 1.0 can be successfully employed to produce the low calorie sweeteners of this invention.

As employed herein, the phrase "Iodine Affinity" or "I.A." refers to a standard type of test employed with starches. More particularly, said test involves a potentiometric titration in which an aqueous solution of calcium chloride is used as a solvent for /the starch. Such a solvent has been found to be. mos helpful when tests are conducted on modified starches such as the hydrolyzates employed here. The test procedures are described in detail in Methods in Carbohydrate Chemistry, Volume IV, pages 161-165 (1964).

Within the initially described' D.E. range of 15 to 45, it is particularly preferred to employ those corn starch hydrolyzates which have a D.E. value of from 18 to 30. Within the subsequently described lower D.E. range of 5 to 15, and having an I.A. of less than 1.0, it is particularly preferred to employ those corn starch hydrolyzates which have an, I.A. of less than 0.5. The aforesaid preferred groups of hydrolyzates produce low calorie sweeteners which have the optimum desirable properties heretofore enumerated. Such sweeteners also minimize and often eliminate the disadvantageous' features of the prior art.

Turning to the artificial or non-nutritive sweeteners, it is generally . referred to use a mixture of two or more, al • to employ a cyclamate and a saccharin, especially a mixture of the respective sodium salts. When such mixtures are prepared, the weight ratio of the cyclamate to the saccharin will vary in accordance with the sweetness desired. Within this broader range, it has been found that a weight ratio of from about 10:1 to about 2:1 is preferable. In addition to the aforesaid mixtur of the respective sodium salts, other specific mixtures include calcium cyclamate and sodium saccharin, sodium cyclamate and calcium saccharin, and a mixture of the respective calcium salts The sweetness of each of the non-nutritive sweeteners relative to that of sucrose is known. For example, sodium cyclamate has a sweetness about 30 times that of sucrose, and sodium saccharin is about 500 times as sweet as sucrose. Naturally, in order to prepare a composition wherein the sweetness is equivalent to that of sucrose on an equal volume basis, these relative sweetnesses are a significant factor. However, full consideration must also be given to the particular corn starch hydrolyzate employed and to such other ingredients as may be added.

In general, the low calorie sweeteners of this invention comprise from about 85 to about 100 parts by weight of the hydrolyzate and from about 1 to about 10 parts by weight of the non-nutritive sweetener. In this regard preferred compositions are those wherein the weight ratio of hydrolyzate to non-nutriti sweetener is from about 12:1 to about 22:1.

Another desirable property of the low calorie sweeteners of this invention is their relatively low density. The bulk density of sugar is about 54 pounds per cubic foot. As compared to such a figure, the sweeteners of this invention have a bulk density of from about 3 to about 30 pounds per cubic pounds per cubic foot.

The bulk density figures presented herein refer to a semi-packed density believed to be similar to that which would be found in a package of material on the shelf of a retail store after normal handling. In one method of calculating such density, a tared 250 ml. graduate is filled to a predetermined volume with the material in question. The net weight of the contents is measured, and the filled graduate is then tapped 25 times in such a manner that its base squarely contacts a flat, firm but padded surface. The rise and fall of the graduate between taps is about 1 inch. The volume after tapping is observed, and the bulk density is then calculated. It will naturally be understood that other and different known methods can as readily be used to calculate said bulk density.

A process for preparing the low calorie sweeteners of this invention comprises first making an aqueous solution of the hydrolyzate . and the non-nutritive sweetener. Generally, the non-nutritive sweetener is first dissolved in water, and, if the hydrolyzate is a corn syrup, it can then be added directly to the solution. On the other hand, if said hydrolyzate is. a corn syrup solid it should first be reconstituted to a corn syrup. Alternatively, the initial solution of the non-nutritive sweetener can be made sufficiently dilute to yield a workable solution upon direct addition of a corn syrup' solid thereto.

The resultant aqueous solution is thoroughly mixed to assure complete and uniform dispersion of the components. Then, if desired, said solution can be further treated to produce a stable foam. As illustrative, the aforesaid mixing can be continued to produce such a foam, or foaming can be achieved by aeration of the solution. Another procedure for foaming in ploy a whipping aid or agent. Such a material can be added to the solution just prior to preparation of the foam or can be; in corporated in the initial solution with the non-nutritive sweet ener. Whipping agents are known in the prior art and include gums, caseinates and other water-dispersible edible proteinn.

The solution of the non-nutritive sweetener and the hydrolyzate, as such or in the form of a stable foam, is then dried to a glass. If a spray drying technique is employed the resultant glass is obtained in the form of individual globules. On the other hand, vacuum drying yields a glass in the form of a layer or matrix of globules in a foam. The particular vacuum equipment can be a tray drier, a continuous belt, a tunnel drier or a drum drier. It should be noted that the layer or matrix of globules can also be obtained by employing a drum drier at atmospheric pressure. It will be understood that the atmospheric procedure requires the use of relatively high pressure steam in the drums (e.g. as high as 80 or more psi) .

The glass product is then subjected to any conventional method of particle size reduction, and such particles ar then classified to obtain the specifically desired size. In general, useful compositions are those wherein particles pass through a U.S. Standard 14 mesh screen and are retained on a U.S. Standard 100 mesh screen. In the especially preferred compositions, particles pass through a 20 mesh screen and are retained on a 60 mesh screen.

Still another advantageous feature of the low calorie sweeteners of this invention is their relative insensitivity to pH. Many prior art sweeteners, particularly where employed in beverages such as tea with lemon, have been found to cause a clouding of the beverage or the formation of an unsightly pre test in iced tea. When 1.5 grams of a sweetener of this invention is dissolved in 150 ml. of iced tea, the solution is free of cloudiness or precipitation, even upon addition of citric acid to a pH of about 3.2.

Perhaps the most significant feature of the low calorie sweeteners of the invention is their similarity of appearance to sugar. Other sweeteners of the prior art have shown some degree of resemblance to sugar, but the instant sweeteners can readily be distinguished from these with the naked eye. As is recog-nized by those skilled in the art, sugar and the presently available substitute sweeteners, are crystalline in nature. It has already been noted herein, that, during the preparation of the products of this invention, the solution or stable foam is dried to a glass. After particle size reduction and classifi-cation, the desired product is obtained as amorphous particles in the form of a glass. However, it is found that the amorphous products of this invention more closely resemble the visual appearance of the crystalline table sugar than do the crystalline substitute sweeteners which are known.

It will be recognized by those skilled in the art that a wide variety of other materials can be incorporated into the low calorie sweeteners of this invention. Such other materials comprise those which are known as processing aids or specific property improvers. For example, certain botanical gums, such as propylene glycol alginate, are known to facilitate drying.

Further, the sweeteners of this invention can contain flavor improvers, flow conditioners, bulking agents and additives to decrease properties such as caking and hygroscopicity . Among the known additives which are so useful are lactose, mannitol, dextrins, other starch derivatives and gums, and the like. question and upon the teachings of the art with respect to any given additive.

The invention will be more readily understood by refer ence to the following detailed examples of low calorie sweeteners and the preparation thereof. Such examples are for purposes of illustration only and are not to be construed as limiting the scope of the invention in any manner.

Unless otherwise specified, all parts, proportions and percentages hereinafter set forth are by weight.

Example 1 A slurry is formed by adding about 405 parts of sodium cyclamate, about.155 parts of sodium saccharin and about 9355 parts of a corn syrup solids hydrolyzate to about 6000 parts of water. The hydrolyzate has a D.E. of 24. The slurry is agitate to give a uniform distribution of materials therein.

The slurry is then dried with a double drum vacuum drier using about 2 to about 15 psi steam pressure and about 25 to about 30 inches Hg vacuum. Roll clearance and roll speed are adjusted to give desired density and appearance. A sheetlike material is discharged from the drums of the drier and is conveyed by a vibrating conveyer to a rotary roller crusher where particle size reduction occurs. After the size reduction, the material is screened using conventional screening equipment. The rotary roller crusher is adjusted to give the maximum amount of material which will pass through a U.S. Standard 20 mesh screen and be retained on a U.S. Standard 60 mesh screen. The material retained on the 20 mesh screen is returned to the rotary crusher, and the undersize particles which pass through the 60 mesh screen are recycled to the slurry. Generally, the amount of undersize. material is cpntrolled at below about 10% particle size is determined in the manner previously described. The 250 ml. graduate is loosely filled to 200 milliliters with the material. The net weight of this quantity of sweetener is about 15.6 grams. The volume after tapping is about 120 milliliters indicating a bulk density of about 8.12 pounds per cubic foot.

The caloric content of the sweetener is determined to be about 14% of that of an equal volume of sugar. The sweetness of two teaspoonfuls (1.78 grams) of the sweetener of this example dissolved in 150 milliliters of water, coffee or tea is found to be equal to the sweetness of 2 teaspoonfuls (12 grams) of sugar dissolved in a like quantity of water, coffee or tea. One gram of the composition of this example dissolves in 100 grams of wate at 70 °F. in about 20 seconds.

The material of this example is amorphous but has the white, shiny, crystalline appearance of granulated table sugar. It is suitable for use as a low calorie table-sweetener.

Example 2 About 12000 parts of corn syrup (9600 parts on a dry basis) having a D.E. of about 29, about 320 parts of sodium cyclamate and about 132 parts of sodium saccharin are mixed in a colloid mill to. insure a thorough distribution of compounds throughout the viscous medium. During mixing the temperature is held at from about 90°C. to about 95°C. because lower temper- . atures tend o increase the viscosity, and higher temperatures tend to impart undesired color to the product.

The mixture is cooled to about 60°C. and transferred to a double drum vacuum drier. The product discharges from the drums of the drier in the form of relatively thin, white, shiny sheets. The sheets are fed to a crusher to reduce the particle ■ size fraction, having particles larger than a U.S. Standard 20 mesh screen, is withdrawn and held for subsequent recycle to the crusher. The undersize fraction, having particles smaller than a U.S. Standard 60 mesh screen, is held for recycle to the mixing step.

The desired fraction which remains is withdrawn and found to have a bulk density of about 9 pounds per cubic foot. Said desired fraction is submitted to a taste panel and is found to have the appearance of sugar, and to produce an equivalent sweetness in water, coffee or iced tea. One gram of the desired fraction dissolves in 150 ml. of water at 70°F. in about 20 seconds, and the caloric content as compared to an equal volume of sugar is about 14%. When two teaspoonfuls of the desired fraction are added to 150 ml. of clear iced tea and the pH is lowered to about 3.2 with citric acid, the solution remains clear and free of a precipitate, thus indicating the sweetener is relatively insensitive to pH. The sweetener prepared herein is a suitable low calorie substitute for table sugar.

Following the detailed procedures of Examples 1 and 2, other low calorie sweeteners of this invention are prepared from the materials as hereinafter indicated.

Example 3 Material Parts Corn starch hydrolyzate (15 D.E.) 9564 Sodium cyclamate , 243 Sodium saccharin 93 Gum arabic 100 Caloric content as compared with sugar -- 17% Example 4 Material Corn starch hydrolyzate (25 D.E.) Sodium cyclamate Sodium saccharin Propylene glycol alginate Caloric content as compared with sugar — 15% Example 5 Material Corn starch hydrolyzate (15 D.E.) Sodium cyclamate Sodium saccharin .

Guar gum Caloric content as compared with sugar — 14% Example 6 Material Corn starch hydrolyzate (29 D.E.) Sodium cyclamate Sodium saccharin ( Propylene glycol alginate Carboxymethyl cellulose Caloric content as compared with sugar — 20% Example 7 Material Corn starch hydrolyzate (30 D.E.) Sodium cyclamate Sodium saccharin Gum tragacanth Caloric content as compared with sugar. — 18% Example 8 Material Corn starch hydrolyzate (24 D.E.) Calcium cyclamate Sodium saccharin Caloric content as compared with sugar Example 9 Material Corn starch hydrolyzate (18 D.E.) Sodium cyclamate Sodium saccharin Mono and diglycerides (derived from edible fats and oils) Caloric content as compared with sugar Example 10 Material Corn starch hydrolyzate (20 D.E.) Sodium cyclamate Sodium saccharin Hydrolyzed caseinate Caloric content as compared with sugar Example 11 Material Corn starch hydrolyzate (19 D.E.) Sodium cyclamate Sodium saccharin The bulk density of the product obtained is found to be 8 pound per cubic foot. However, by adding a bulking agent such as bu d t n r lactose1 r h drol zed starch 3 ounds er mixed with 20 pounds of one of the bulking agents just noted. The resultant material has a bulk density of only 6 pounds per cubic foot.

Each of the above sweeteners is found to have the desirable physical characteristics and appearance heretofore described.

Example 12 About 405 parts of sodium cyclamate, about 155 parts of sodium saccharin and about 9370 parts of a corn syrup solids hydrolyzate are added to about 9000 parts of water. The hydro-lyzate has a D.E. of 12.3 and an I. A. of 0.083. These materials are then agitated to produce a clear, aqueous solution.

Said solution is dried with a single-nozzle, vertical, co-current spray drier. Pressure and temperature are adjusted t give a product having desired density and appearance. The dried product is in the form of glass beads or globules which are conveyed to a crusher for particle size reduction. The reduced material is then screened as described in Examples 1 and 2. The resultant product is found to display the sought-after appearanc and physical characteristics. Its caloric content as compared with an equal volume of sugar is about 15%.

Example 13 Following the procedures just described in Example 12, the hydrolyzate employed is in the form of corn syrup solids having a D.E. of 10.3 and an I. A. of 0.065. The caloric content of the resultant sweetener composition is about 14% of that of a equal volume of sugar.

The low calorie sweetener compositions of this inventi were evaluated organoleptically . A trained panel tasted samples the same quantity of table sugar. In each instance a majority of the panel was unable to detect a difference and determined that sweetness was substantially equivalent.. Similar comparison tests were run with other liquids such as coffee and tea, but the panel did not detect any perceptible or recognizible difference in sweetness.

While the invention has been described with regard to certain specific embodiments, it is not so limited. It is to be understood that variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention.

Claims (1)

1. 0-2338 85 parts by weight of a corn starch hydrolyzate selected from the group consisting of hydrolyzates having a D.E. of from about 15 to about 45/ and hydrolyzates having a D.E. of from about 5 to about 15 and an I.A. of less than 1.0, and up to about 10 parts by weight of non-nutritive sweetener; said composition having a bulk densit of up to about 30 pounds per cubic foot, and having a sweetness equivalent to that of sugar on ah equal .volume basis. • J i : 2. A composition .as defined in Claim 1 comprising from about 85 to about' 100 parts by weight of said corn starch hydrolyzate and from about 1 to about 10 parts by weight of said non-nutritive sweetener. 3. A composition as defined in Claim 1 wherein said hydrolyzate is a corn syrup. 4. A composition as defined in Claim 1 wherein said hydrolyzate is a corn syrup solid. 5. A composition as defined in Claim 1 wherein said . , composition . has . a bulk density of from about 3 to about 30 pounds , per cubic foot. . 6. A composition as defined in Claim 1 wherein said non-nutritive sweetener is selected from the group consisting of cyclamates, saccharins and mixtures thereof. t 7. A composition as defined in Claim 6 wherein said non-nutritive sweetener is a mixture of . sodium cyclamate and sodium saccharin. 0-2338 r 9. A composition as defined in Claim 1 wherein the corn starch hydrolyzate has a D.E. of from about 15 to about 45. 10. A composition as defined in Claim 9 wherein th corn starch hydrolyzate has a D.E. of from 18 to 30. 11. A composition as defined in Claim 10 wherein the bulk density is from about 5 to about 11 pounds per cubic foot. 12. A composition as defined in Claim 11 wherein said non-nutritive sweetener is a mixture of sodium saccharin and sodium cyclamate. 13. A composition as defined in Claim 1 further characterized as being amorphous. 14. A composition as defined in Claim 1 further comprising a minor amount of a flow conditioner. 15. A composition as defined in Claim 1 wherein the corn starch hydrolyzate has a D.E. of from about 5 to about 15 and. an I.A. of less than 1.0. 16. A composition as defined in Claim 15 wherein said I. A. is less than 0.5. 17. A composition as defined in Claim 16 wherein .the bulk density is from about 5 to about 11 pounds per cubic foot. 18. A composition as defined in Claim 17 wherein said non-nutritive sweetener is a mixture of sodium saccharin and sodium. cyclamate. 19. A process which comprises preparing an aqueous solution of a corn starch hydrolyzate selected from the group consisting of hydrolyzates having a D.E. of from about 15 to 0-2338 about 15 and an I. A. of less than 1.0, and non-nutritive sweetener, drying said solution to a glass, subjecting said glass to particle size reduction and classifying the resultant particles 20. A process as defined in Claim 19 wherein the solution is spray dried. 21. A process as defined in Claim 19 wherein the solution is drum dried. 22. A process as defined in Claim 21 wherein the drum drying is carried out under vacuum. 23. A process as defined in Claim 19 wherein the classified particles are those which pass through a U.S. Standard 14 mesh screen and are retained on a U.S. Standard 100 mesh screen. 24. A process as defined in Claim 19 wherein the classified particles are those which pass through a U.S. Standard 20 mesh screen and are retained on a U.S. Standard 60 mesh screen. 25. A process as defined in Claim 19 wherein a stable foam is produced from the aqueous solution and subjected to said drying. 26. A process as defined in Claim 25 wherein a whipping agent is employed in the production of said stable foam. 27. A process as defined in Claim 19 wherein the hydrolyzate is a corn syrup and the non-nutritive sweetener is selected from the group consisting of cyclamates, saccharins P.A. 283^2/2 28. A process as defined in Claim 19 wherein the hydrolyzate is a corn syrup solid and the non-nutritive sweetener is selected from the group consisting of cyclamates, saccharine* and mixtures thereof. 29. A process as defined in Claim 19 wherein said solution is prepared with from about 85 to about 100 parts by weight of the hydrolyzate and from about 1 to about 10 parts by weight of the non-nutritive sweetener, the latter being a mixture of sodium saccharin and sodium cyclamate. 39· A low carlorie sweetener and process for preparing same, substantially as hereinbefore described and with reference to any of the examples. DATED THIS 20th day of June, 1967· WXtfm- 2EDEK & SPISBACH P.O.BOX 33116 TEL AVIV ATTORNEYS FOR APPLICANTS.