April 5, 1949. G. L. BAKER 2,466,146 EDIBLE GELLING COMPOSITION CONTAINING IRISH MOSS EXTRACT, LOCUST BEAN GUMAND AN EDIBLE SALT . Filed April 12, 1947

Gzezze. Z2%rINVENTOR,

Patented Apr. 5, 1949 2,466,146

UNITED STATES PATENT of FICE 2,466,146 EDIBLE GELLING COMPOSITION CONTAIN INGRSE MOSS EXTRACT, LOCUST BEAN GUM, AND AN EDIBLE SALT George L. Baker, Newark, Del, assignor to Krim Ko Corporation, Chicago, Ill., a corporation of Applicationlinois April 12, 1947, serial No. 741,116 4. Claims. (C. 99-13) 2 The present invention pertains to the art of prepare gelling compositions substantially com preparing elastic gels and refers particularly to posed of Irish moss gelose which can be used the preparation of novel gelling compositions in lieu of animal gelatine or fruit or vegetable substantially derived from the sea-plant Irish pectinates. A particular objective of the inven OSS, 5 tion is to prepare an Irish moss gelose product In the accompanying drawing, made from which will produce elastic, , strong, and form photographs, forming a part of this specification retaining gels suitable for food purposes, i. e. and to which reference should be had in con salads and desserts, over a wide range of soluble nection therewith, Figure 1 illustrates two gels Solids content. This invention has led to the made from different compositions, one incor O discovery of a three-element gelling composition porating the present invention and the other a functioning in a superior manner to known com different composition; and in Figure 2 the same positions in the gelling field. This novel com gels are illustrated with like weights resting on position produces Irish moss gels of desired elas their tops, - ticity, strength and form-retention greatly in A potentially useful and hitherto relatively 5 excess of the additive effects predictable from neglected gelling agent is gelose, or carragheenin, the performance of the several component ele the active colloidal substance contained in Irish ments when used alone or in pairs. moss or Chondrus crispus, a member of the In its simplest form the new composition com Gigatinaceae. prises (1) a source of gelose or carragheenin Although widely known for many years it has 20 particles whose surface charges may be neu heretofore been regarded principally as a thicken tralized by suitable cations to permit maximum ing substance or stabilizing agent. Various absorption of water medium; (2), a colloid sub expedients have been Suggested for improving stance of high natural viscosity and neutral the physical properties, particularly the gel reaction whose degree of polymerization and forming capacity of Irish moss extractive. One water absorption are substantially unaffected by Such suggested expedient is to implement the heat; and (3) a Source of neutralizing cations, gelatinizing action through the action of certain For the gelose element it is preferred to take ions, notably potassium, which have been shown the refined aqueous whole extract of the Irish to induce gel formation. moss plant, although it is known that alcohol The added cations are only effective up to the 30 precipitated or selectively-extracted Irish moss point of complete neutralization of the negative fractions, agar-agar, and various other sources of or anionic charge carried by the carragheenin sol active gelose principle may be employed. When particles. At this point carragheenin manifests the normal negative charge on the colloidal par the normal full potential in gelatinizing power. ticles of the Irish moss Sol is sufficiently neu Anything less than this is subnormal perform 35 tralized by the appropriate cations, imbibition ance. Anything more than this would be thought of the dispersing medium is rapid, predisposing to increase the gelling power, but this is not the system to gel formation. the case. Potassium and similar cations, there For the neutral high polymer or colloidal fore, merely bring about the degree of gelatiniza addition-agent locust bean gum has been found tion of which the colloid is already inherently 40 to be eminently satisfactory, but the invention is capable; they do not increase the gelling power. not limited to this substance inasmuch as a num Apart from this technical distinction, there is ber of other neutral high polymers will also meet the further very practical observation that even the above-stated qualifications in various degrees. the best cation-induced Irish moss gels lack Starch and carboxymethylcellulose compounds elasticity comparable to pectin gels. The yield 45 are in this category and while not nearly as ing, non-cohesive, and essentially brittle char valuable as locust bean gum in developing acter of the Irish moSS gel is not altered in any elasticity and form-retention, the two most de important particular by the gel-inducing ions. sired physical characteristics, they do exhibit a Elastic, strong, form-retaining gels such as those capacity to aid in expanding the normal gelling needed by the manufacturing confectioner for 50 strength of the gelose. The relative value of the slab Or cutting operations have not been obtain naturally high polymers in increasing gel strength able in the past with Irish moss, of moss gelose is shown by the following com An outstanding object of this invention is to parative figures upon sugar gels containing. 4.0%

2,466,146 3 4. soluble solids which were made by similar pro 1% potassium chloride decreases the viscosity to cedure at pH 3.5: 3400 centipoises. If the temperature is reduced to 4.4° C. in the case of this last system the Control, 0.6% Irish moss gelose extract plus 0.2%: viscosity is increased to 5500 centipoises, but no KCl ------10 s gelation occurs. High polymers added to control gel: It may be shown similarly that Irish moss ex 0.4% locust bean gum ------83, tracts alone form only colloidal dispersions at 0.4% high viscosity sodium 26 C., in a concentration of 0.6 to 1% gelose, carboxymethyl-cellulose ------25 due to the lack of sufficient favorable cations for 1.0% corn starch ------24 gelation. Wiscosity of a 0.6% dispersion of com 0.4% gum karaya ------19 mercial extract will be about 90 centipoises at pH 0.4% gum tragacanth ------14 6.5 at 26° C. Viscosity will increase to 920 centi 0.4% potassium carboxymethylcellulose - 12 poises as the temperature is lowered to 44° C. 0.4% low viscosity sodium carboxyl Upon standing at this latter temperature of pH methylcellulose ------12 6.5 for a sufficient period of time gel tendencies 0.4% gum arabic ------12 will be exhibited and a weak gel may form. A 0.4% guar flour ------11 1% dispersion of gelose will have a viscosity of While members of the above group aid in 250 centipoises at pH 6.5 at 26° C. and will form increasing the strength of gelose gels, none, other a weak gel at 4.4° C. Increased acidity will de than locust bean gum, imparts the desired de 20 crease the viscosity of this latter dispersion so gree of elasticity and form-retention. ... that it has a viscosity of only 58 centipoises at pH For the source of the gel-inducing ion potas 3.5 at 26° C. and no gel will form at 4.4° C. sium chloride, which is commercially available in However, it is known that certain cations, not pure form and quite cheap, may be used. Where ably potassium, induce gelation. A 0.6% dis greater resistance to acidic conditions is required 5 persion of Irish moss extract containing 0.2% the potassium ion may be employed in combina KCl will form a 40% soluble solids sugar gel with tion with the anion component of a relatively a strength of 12.5 g. per cm. at pH 3.5 at 26° C. weak Organic acid, exemplary of which are using a plunger 2.1 cm. in diameter for breaking acetic, citric, lactic, malic, and tartaric acids. the gel surface and a 6-ounce tumbler as con These provide a relatively strong buffer reaction tainer. Further increments of potassium chlo and help to reduce the aggressive hydrolytic ride up to 1.2% KCl will increase the strength of action manifested by acids on the gelose factor, the 40% soluble solids gels to a maximum at pH especially in the presence of Substantial heat, 5.6. More than 1.2% potassium chloride will but tend to reduce gel strength. Potassium cause a decrease in gel strength. The gelose gel citrate gels were found to have about two-thirds 3 5 obtained by the addition of potassium chloride the strength of potassium chloride gels of equiva is non-elastic, brittle, and easily shattered by the lent potassium content at similar pH values. application of excess pressure. While potassium salts are preferred, salts of cal The two-element system composed of 0.4% cium, magnesium, and a number of other cations locust bean gum and 0.6% Irish moss gelose ex will function with varying degrees of effective U tract in water solution will not gel. It forms eSS, only a viscous solution at pH 5.65, having a vis By bringing the aforementioned three ele cosity of 400 centipoises at 26° C. When acid is ments, gelose-high polymer-cation together in a added the viscosity is lowered. A system contain common gel System a number of surprising ing 39% cane sugar in addition to the combina effects is obtained, the most remarkable of which tion of 0.4% locust bean gum and 0.6% Irish is the substantial increase in the elasticity of noSS gelose extract in the absence of sufficient the gelose gels. Gel-strength and form-retention favorable cation will not produce a gel satisfac are also greatly improved. The betterments in tory for practical usage. At a room temperature these characteristics are of a magnitude greater of 26 C. a soft gel only, one which has no meas than can be accounted for by the additive effects urable strength, will form at pH 5.6. Addition of the components acting independently of each of a Small increment of acid causes liquification. other and can only be explained on the hypothesis At 4.5 C. these proportions of gum and moss that a multiple synergy or expansion of gelling gelose plus sugar form a gel with a strength of capacity has been established by the three ele 9 g. per cm. at pH 6.1. Increasing the acidity ments acting in unison. 55 decreased gel strength until at pH 3.7 an unmeas For example, it is easily demonstrated that urable gel form was produced. These gels were locust bean gum is devoid of gel-forming sticky products which would not support them capacity in the concentrations employed. A 0.4% Selves when removed from the container. Upon Solution has a viscosity of 75 centipoises at pH doubling the proportions of Irish moss gelose and 5.15 at 26° C. Potassium salt decreases rather locust bean gum, a 40% soluble solids sugar gel than increases the viscosity and the probability was produced which had a strength of 28 g. per of gelation; 0.25% potassium chloride reducing cm. at pH 5.5 and a temperature of 26° C. This the viscosity to 62 centipoises at pH 5.00. While gel was a very cloudy, sticky product which was a 1% solution is much more viscous, it does not gel even with sugar. A 1% solution of locust 65 difficult to remove from the container, but when bean gum, two and one-half times the preferred removed it partially retained its form. It exhib concentration, containing 40% cane sugar, does ited 38.2% Sag, when sag was measured with a not gel even at 4.4 C., but is very viscous. It modified form of instrument known as a "Ridgel has a viscosity of 6700 centipoises at 26° C. and ineter' described on page 441 of the June 1944 pH 5.22. Decreasing the temperature to 4.4° C., 70 issue of Food Industries, but its sag, while con the viscosity is increased to 8000 centipoises. siderable, is not a true measure of elasticity. Its Again, potassium salts decrease viscosity; 0.2% gel-like form seems to hold together as a result potassium chloride decreases the viscosity to 6600 of adhesive characteristics rather than as a true centipoises at 26° C., 0.4% potassium chloride gel System. Upon tripling the above proportions decreases the viscosity to 5700 centipoises, and s of moss extract and gum, a 40% soluble solids

BEST AVAILABLE COPY 2,466,146 . product was obtained which had a strength of citrate, and 0.2% citric acid in addition to the 58 g. per cm. at pH 5.4. While a very sticky,

water and sugar. The sodium citrate and citric rough-surfaced product, and one which was dific acid are present in order to obtain the desired, cult to remove from the glass at 26 C., this prod acidity. m uct exhibited a fair degree of form-retention s Gel No. 2 of Figure 1 is representative of the and a sag of 20.6%. It also was an adhesive ordinary Irish moss extract gel as known to the product rather than a true gel. The eating qual art. It contained 1.0% moss extract, 1.2% potas ity of the product was poor on account of exces sium chloride, 0.2% sodium citrate, 0.2% citric sive stickiness due to the high proportion of acid in addition to the water and sugar. coloidal ingredients. Upon varying the propor O Both gels were made according to identical tion of locust bean gum from 0.4% to 2.0% while procedures: holding the percentage of moss extract constant Initial volumes were equal, they were evapo at 0.6%, an increasingly more viscous, gummy, rated by boiling for the same time to the same product was obtained, but no gel was produced. Weight, they were poured, cooled, and allowed to Upon varying the proportion of Irish moss gelose 5 set at 26° C. for 24 hours before measurement. extract from 0.6% to 3.0% while holding the Figure 2 of the drawing further illustrates the percentage of locust bean gum extract constant difference in elasticity of the two gels. When at 0.4%, the product, while in the container, 20-gram weights of identical dimensions were showed increasing resistance to the plunger of placed on the tops of these gels, the surface of the gel-strength apparatus, but, when removed gel No. 1 in contact with the weight was de from their containers, the products were gummy, 20 pressed. The drawing shows that only about sticky, shapeless masses. % of the weight was visible, when viewed from Only when all three elements, a seaplant gelose, the side, while the surface of gel No. 2 was de a heat-resistant high polymer, and a favorable pressed to a negligible degree and practically all cation, coexist in one system do we have the pre of the weight was visible. Thus it is demon ferred results of the present invention. When strated that whereas the breaking strength of the three elements are present, high viscosities the two gels was the same, the sag, which is an are found at all temperatures above that of gela indication of the inherent elasticity was much tion due to the presence of the highly viscous greater when all three essential elements, moss locust bean gum. Wiscosities increase much more gelose, gum, potassium ion were present than rapidly as the temperature of gelation is ap when only two were employed. proached with this novel composition than when The elasticity of a true gel system of gels only geose and electrolyte are present. Prob formed from the new composition may be varied ably as a result of the high viscosity gel-forma by modifying the proportion of locust bean gum. tion from the liquid state is gradual and not Without the gum the sag of a 40% soluble solids abrupt as is the case when only gelose and elec gel at pH 4 containing 1% moss and 0.2%KCl trolyte are used. The most logical explanation amounted to about 2% and the breaking strength for slower gelation appears to be that the highly of 40 g. per cin... With 10% gun in the new viscous locust bean gum slows down the normal composition, when the novel three-element sys colloidal movement of the Irish moss extract due 4) ten comprised 1.2% of the total weight of gel, to the presence of less free water at higher than the Sag was increased to 8%; with 20% gum the normal temperatures and allows a gradual com Sag amounted to about 13%, and with 30% gum bination of potassium ion with the negatively the Sag increased to about 19%. Probably about charged Irish moss gelose. This gradual transi 25% to 35% gum will be preferred for most uses. tion from Sol to gel allows a fibrillar structure to 5. The Sag can be increased, of course, for instance be built up which occludes or interlaces locust upon having 50% gum in the three-element sys bean gun fibrils in such a fashion as to give resil ten the sag will be increased to over 30%. iency to the gel. The net result of this slow The gels formed in the three-element system transition probably accounts for the unexpected do not exhibit the fragility and the brittleness and high degree of elasticity in the resulting gels. characteristics of the Irish moss gel. Instead The strength of the gels formed in this manner they are strongly resilient and form-retaining are also substantially greater than would be Without being tough. These qualities have been expected or could be predicted from the perform heretofore found principally in fruit pectinate ance of the elements acting independently of gels. Whereas gel No. 1 in Figures 1 and 2, as each other or in pairs as two-element Systems, s 5 an example of the product made with the new for instance, gun-naoSS gelose, InoSs geose-elec composition, was easily removed from its con trolyte, or gum-electrolyte. By binding part of tainer, gel No. 2 was difficult to remove and its the water of the dispersing medium the gum prac surface was easily ruptured or disfigured; the tically eliminates the free or unbound water figures show gel No. 2 to exhibit such a rupture phase characteristic of moSS gels and thus gives 60 on the lower right-hand side as viewed in Figure not only a much stronger and more rigid struc 2. The new gelling composition of this invention ture, but one, while having a moist Surface, with produces gelose gels which are sufficiently rigid little or no tendency toward "bleeding' or syne to permit of their being cut from precast slabs resis upon Subsequent cooling and contraction and handled with a moderate degree of severity of the gel fibrils. 5 without excessive breakage. The unusual elasticity which is exhibited by The gels prepared with the gelling composition the gels formed in the three-element system is of this invention are heat reversible, i. e. they demonstrated in the accompanying figures of the may be reliquified by heating and subsequently drawing wherein Figure shows two 40% soluble regelled On cooling. The importance of this Solids sugar gels each having a gel-strength of 70 property will be best understood in connection 54 g. per cm. of plunger surface. . with the problem of manufacturer's trimmings. Gel No. 1 in Figure 1 is representative of the Or 'scrap.' This material, when made from the innovatory preferred three-element system. It new composition, merely needs to be remelted contained 0.6% Irish moss extract, 0.4% locust and recast, thereby avoiding waste. 8 bean gum, 0.4% potassium chloride, 0.2% sodium 5 The new gels made from the composition en 2,466,146 BEST AVAILABLE COPY 7 8 bodying this invention may be prepared with The sugar and gel composition are mixed dry water alone or with water in combination with and when ready to prepare the gel the 70 pounds sugars or glycols in low as well as high concen of prune juice are added slowly with stirring and trations. Sugar gels may be made with any boiled at 216 F. Such mixture is then poured desired content of sugar or sugars from 0% up 5 into molds and this makes a gel of approximately to the saturation point of the dominant Crystal 40% solids content, allowing for evaporation of lizable sugar in the mixture. The percentage of water during cooking. The amount of soluble the new composition, gelose-viscous polymer solids in the gel may be varied at will by chang- . cation which must be present in a gel in order ing the amount of added sugar and final boiling to provide a uniform breaking strength, 40 g. O temperature. per cm2 when using a plunger 2.1 cm. in diameter The net result of the several coacting Substances and a standard 6-ounce jelly glass, and a uniforn herein described is to produce gels of which Irish elasticity, about 18% to 20% sag, varies with moss gelose is the major colloid ingredient, which the soluble solids content of the gel, thus at pH 4 are much more elastic and stronger than any the following approximate amounts are required: moss-gelose gels heretofore produced, these im Percent composition required for various soluble provements being accomplished at a considerable Saving of colloid materials since less of the gelling solid jellies agent is needed to produce a gel of the required 5% soluble solids-1.68% composition rigidity. 20% soluble solids-1.50% composition The permissible ranges of amounts of ingre 40% soluble solids-1.24% composition dients by weight which may comprise the novel 60% soluble solids-0.98% composition composition are Irish moss extract 40 to 60%, All of the sugar gel products have excellent locust bean gum 20 to 40%, and potassium chlo eating qualities. ride 15 to 30%. The gelling composition of this invention op I claim: erates over a broad pH range which takes in the 1. A composition containing in approximate normal acidity range of many non-acid and proportion by weight of Irish moss extract 50%, mildly-acid fruit and vegetable raw materials. locust bean gum 33%% and potassium chloride The preferred range is from pH 3.5 to pH 7.0. At 16%%, said composition being capable of form the more acid levels, below pH 4, it is desirable ing a strong and elastic gel solely by applying to employ the buffering form of the electrolyte water and heat thereto sufficient to dissolve and referred to earlier in this disclosure, e. g. potas disperse the ingredients and then cooling the same sium citrate. At the higher pH levels an inor to gelling temperature, the gel product having ganic salt, such as potassium chloride, may be strength and elasticity of greater magnitude than used. Gels may be made with the new composi can be accounted for by the additive effects of tion of the pH range 2.0 to 10. the locust bean gun and the potassium chloride Non-acid and mildly-acid gel products, which on the Irish moss extract. may be made with the composition of this inven 2. The composition set forth in claim 1, in the tion include: apple, cider and wine gels, peach, form of a dry powder. pear and plum juice gels, banana, cocoanut, sweet 3. An edible gel made from a composition con potato, mint, spiced gels, and a variety of aspics. taining Irish moss extract, locust bean gum and In the practical embodiment of the present an edible water-soluble salt of the group consist invention the following proportions of the several ing of potassium acetate, potassium citrate, potas materials by weight are employed and blended sium chloride, and potassium acid tartrate which in a suitable grinder or mixing machine to pro imparts strength and elasticity to the gel of vide a dry gelling composition of uniform appear greater magnitude than can be accounted for by ance and composition; purified whole dried ex the additive effects of the locust bean gum and tract of Irish moss 12 parts, locust bean gum 8 the salt components acting independently of each parts, and potassium chloride 5 parts. This is other on the Irish moss extract. our basic dry gelling composition to which sugars 4. The gel presented in claim 3 characterized and other substances may be added. by a relatively low melting point and ability to Another example is purified whole dried extract reset upon cooling. of Irish moss 9 parts, locust bean gum 6 parts, GEORGE. L. BAKER. potassium citrate 5 parts. 4. A typical gel mix incorporating the edible gel 5 s REFERENCES CITED composition of this invention, containing 50% The following references are of record in the Irish moss extract, 33%% locust bean gum, and file of this patent: 16%% potassium chloride is: UNITED STATES PATENTS Pounds 60 Gelling composition.------1.0 Number Name Date Sugar ------22.0 1946,649 Thomas et al. ------Feb. 13, 1934 Prune juice (18% soluble solids).------700 2,427,594 Frieden et al.------Sept. 16, 1947