CA1326162C - Low calorie fat substitute compositions resistant to laxative side effect - Google Patents
Low calorie fat substitute compositions resistant to laxative side effectInfo
- Publication number
- CA1326162C CA1326162C CA000603934A CA603934A CA1326162C CA 1326162 C CA1326162 C CA 1326162C CA 000603934 A CA000603934 A CA 000603934A CA 603934 A CA603934 A CA 603934A CA 1326162 C CA1326162 C CA 1326162C
- Authority
- CA
- Canada
- Prior art keywords
- fatty acid
- polyester
- composition according
- microfibrils
- fibrils
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
- A23G3/00—Sweetmeats; Confectionery; Marzipan; Coated or filled products
- A23G3/34—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof
- A23G3/346—Finished or semi-finished products in the form of powders, paste or liquids
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
- A23D9/007—Other edible oils or fats, e.g. shortenings, cooking oils characterised by ingredients other than fatty acid triglycerides
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/20—Reducing nutritive value; Dietetic products with reduced nutritive value
- A23L33/21—Addition of substantially indigestible substances, e.g. dietary fibres
- A23L33/25—Synthetic polymers, e.g. vinylic or acrylic polymers
- A23L33/26—Polyol polyesters, e.g. sucrose polyesters; Synthetic sugar polymers, e.g. polydextrose
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/21—Esters, e.g. nitroglycerine, selenocyanates
- A61K31/215—Esters, e.g. nitroglycerine, selenocyanates of carboxylic acids
- A61K31/22—Esters, e.g. nitroglycerine, selenocyanates of carboxylic acids of acyclic acids, e.g. pravastatin
- A61K31/23—Esters, e.g. nitroglycerine, selenocyanates of carboxylic acids of acyclic acids, e.g. pravastatin of acids having a carboxyl group bound to a chain of seven or more carbon atoms
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/70—Carbohydrates; Sugars; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P3/00—Drugs for disorders of the metabolism
- A61P3/04—Anorexiants; Antiobesity agents
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
- A23G2200/00—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF containing organic compounds, e.g. synthetic flavouring agents
- A23G2200/06—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF containing organic compounds, e.g. synthetic flavouring agents containing beet sugar or cane sugar if specifically mentioned or containing other carbohydrates, e.g. starches, gums, alcohol sugar, polysaccharides, dextrin or containing high or low amount of carbohydrate
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
- A23G2200/00—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF containing organic compounds, e.g. synthetic flavouring agents
- A23G2200/08—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF containing organic compounds, e.g. synthetic flavouring agents containing cocoa fat if specifically mentioned or containing products of cocoa fat or containing other fats, e.g. fatty acid, fatty alcohol, their esters, lecithin, paraffins
Abstract
LOW CALORIE FAT SUBSTITUTE COMPOSITIONS
RESISTANT TO LAXATIVE SIDE EFFECT
Abstract of the Disclosure The present invention relates to low calorie fat substitute compositions that are useful as fat replacements in low calorie foods, and as pharmaceutical compositions.
Sucrose fatty acid esters are preferred low calorie fat substitutes. The compositions are highly resistant to an undesirable laxative side effect. These benefits are achieved by formulating compositions comprising a liquid polyol fatty acid polyester, at least about 10% solid low calorie fat substitute by weight of the liquid polyester, and at least about 1% of a cohesive network of polysaccharide fibrils and microfibrils, for example microfibrillated cellulose, by weight of the liquid polyester.
RESISTANT TO LAXATIVE SIDE EFFECT
Abstract of the Disclosure The present invention relates to low calorie fat substitute compositions that are useful as fat replacements in low calorie foods, and as pharmaceutical compositions.
Sucrose fatty acid esters are preferred low calorie fat substitutes. The compositions are highly resistant to an undesirable laxative side effect. These benefits are achieved by formulating compositions comprising a liquid polyol fatty acid polyester, at least about 10% solid low calorie fat substitute by weight of the liquid polyester, and at least about 1% of a cohesive network of polysaccharide fibrils and microfibrils, for example microfibrillated cellulose, by weight of the liquid polyester.
Description
` 1 326 1 6~
LOW CALORIE FAT SUBSTITUTE COMPOSITIONS
RESISTAN~ ~O LAXATIVE SIDE EFFECT
- TEC~NICAL FIELD
The present invention relates to the f~eld of low calor~e fat and oil substitutes. Specif~cally, the invent~on relates to low calor~e fat subst~tute compos~t~ons that contain polysaccharide fibrils and microfibrils such as m~crof~brillated cellulose. The compos~t~ons are partlcularly useful as fat replacements in foods.
BACK~Q1~ OF THE INVENIION
The consumption of large amounts of trtglycer1de fats has been linked to varlous health problems. For example, one of the most common metabollc problems among people today is obesity. Th~s cond~tion ls prlmarily due to ~ngestlon of a greater number of calorles than are expended. Fat ~s the ~ost concentrated form of energy in the d~et, wlth each gram of fat supply~ng approx~mately 9 calor~es, and trtglycer1de fats const~tute about 9O~ of the total fat consumed ln the average dlet.
~he Nattonal Institutes of Health Consensus Development ~` Conference, ~Lo~erlng Blood Cholesterol to Prevent Heart Dlsease~, JA~A, Vol. 253, No. 1~, pp. 2080-2086 (1985), concluded that elevatlon of blood cholesterol levels ~s a ma~or cause of coronary artery d~sease, and recommended a ` reductlon ~n the amount of fat eaten to reduce blosd serum `` cholesterol levels.
Hence, there is a need for ways to reduce the amount of trlglycer~de fats in the d~et, ln order to reduce the health rlsks associated w~th these fats.
Low calor~e fats wh1ch can replace tr~glycerides are descrlbed by Mattson et al. in U.S. Patent 3,600,186. Food i~
.
: ., . - .
` 13261 6?
compositions are disclosed in which at least a portion of the triglyceride content is replaced by a polyol fatty acid ester having at least four fatty acid ester groups with each fatty acid having from 8 to 22 carbon atoms.
U.S. Patent 4,461,~82 to Robbins et al., issued July 24, 1984, discloses baked products contain~ng 1~-60% l~quid polyol polyester and 25-85% microcrystalline cellulose and flour.
Examples given are breads, cakes and wafers.
U.S. Patent 3,954,976 to Mattson et al. describes pharmaceutical compositions for ~nhibiting the absorption of cholesterol comprising effective unit dosage amounts of a polyol fatty acid ester ha~ing at least four fatty acid ester groups.
The esters disclosed in these patents are useful as fat substitutes in low calor~e food products or in pharmaceutlcal ~
composit~ons for controlling hypercholesterolemia. Unfortu-nately, regular ingestion of moderate to high levels of liquid polyol fatty acid`polyesters can produce an undesirable laxat~ve side effect, namely, leakage of the ester through the anal sph~ncter.
U.S. Paten~s 4,005,195 and 4,005,196 to Jandacek et al.
descr~be a method of reducing the undes~rable la~ative side effect through the addition to the liquid polyesters of ant~-anal leakage agents. The anti-anal leakage agents include solid fatty aclds (melting point 37C or higher) and thelr triglycerlde source, and solid polyol fatty acid pol~esters.
Other patents describe the use of microfibrillated cellulose in foods. For example, U.S. Patent 4,341,807 to Turbak et al., issued July 27, 1982, describes food products containing a susp~nsion of microfibrillated cellulose as a thickener, flavor carrier and suspension stabil~zer. Food uses speci~ically taught include fillings, crushes, soups, grav~es, puddings, dips, topp~ngs and other food products.
Turbak, "r~icrofibrillated Cellulose - A New Composition of Commercial Significance," Tappi 1984 Non-Woven Svmposium, page 121, describes the use of microfibrillated cellulose in reduced calorie jams and jellies, reduced calorie foods, and low and reduced calorie spreads.
Neither of the Turbak references suggests that microfibrillated cellulose can be used to reduce laxative side effect of a liquid polyol polyester.
It is an object of an aspect of the present invention to provide low calorie fat substitute compositions that are useful as a replacement for normal triglyceride fats in low calorie foods, and as pharmaceutical compositions.
It is an object of an aspect of the present invention to provide low calorie fat substitute compositions that are resistant to an undesirable laxative side effect.
These and other objects of the present invention 2Q will become evident from the disclosure herein.
All parts, percentages, and ratios used herein are by wei~ht unless otherwise indicated.
SUMMAR~ OF TH~ INVE~TION
The present invention relates to low calorie fat substitute compositions that are useful as fat replacements in low calorie foods, and as pharmaceutical compositions. Sucrose fatty acid esters are preferred low calorie fat substitutes. The compositions are highly resistant to an undesirable laxative side effect. These benefits are achieved by formulating compositions comprising a liquid polyol fatty acid polyester, at least about 10% solid low calorie fat substitute by weight of the liquid polyester, and at least about 1% of a cohesive network of polysaccharide fibrils and microfibrils, for example microfibrillated cellulose, by weight of the liquid polyester.
Other aspects of this invention are as follows:
~1 -3a-A low calorie fat substitute composition comprising a liquid polyol fatty acid polyester, at least about 10%
solid low calorie fat substitute by weight of the liquid fat polyester, and at least about 1% of a cohesive network of polysaccharide fibrils and microfibrils by weight of the liquid polyester.
A low calorie fat substitute composition comprising from about 1% to about 42% by weight liquid polyol fatty acid polyester; from about 1% to about 15% by weight of a cohesive network of polysaccharide fibrils and microfibrils; and from about 43% to about 98% by weight low calorie fat substitute selected from the group consisting of suqar fatty acid polyesters, sugar alcohol fatty acid polyesters, and mixtures thereof, the sugars and sugar alcohols containing from 4 to 8 hydroxyl groups, and each fatty acid group having from about 8 to about 22 carbon atoms, wherein the fat substitute has, at - 100F ~37.8C):
(a) a liquid/solid stability of at least about 50%;
and (b) a solid fat content between about 5% and about 30%.
.
BRIEF DESCRIPTION OF THE ORA~INGS
Figure 1 is a photograph of a network of cellulos~c fibrils and microfibrils taken at SOOX magnification.
Figure 2 is a greatly enlarged representation of what a portion of the net~ork of cellulos~c f~brils and microfibrils is belie~ed to look like in the compositions of the present invention.
DETAILED DESCRIPTION OF THE IN~ENTION
The present i m ention is base~ on the discovery that when a net~ork of polysaccharide fibrils and microfibr~ls is dispersed in a m~xture ~f a `iquld polyol fatty acid polyester and a solid low calorie f-: substitute, the resulting composition is e~en more resistant to laxative side effect than the liquid/solid mixturQ alone. This flnding was unexpected in view of the fact that no laxatlve side effect reductlon is seen in the two-part combination of liquid polyester and fibrils and microfibrils.
The addition of the polysaccharide fibrils and microfibrils is thought to provlde a material of high surface area ~hich ser~es as nucleating SitQS for the prec~pitation of the solid fat substitute, thereby entrapping the liquid polyester in a matrix with a hydrophobic surface. Apparently - the surface of th~ resultant gel has a hlgh contact angle, and watQr is not read~ly abl~ to spread or penetratQ the surface and causQ separat~on of the liquid polyestQr.
A lo~ caloriQ fat-substttute composition according to the present in~ention comprises a liqutd polyol fatty acld poly~st~r; at least about lOX solld lo~ calor~e fat substitute by wetght of thQ liquid polyester; and at least about 1% of a cohesl~e network of polysacchartde fibrils and microfibrils by ~eight of the l~quid polyester. Preferably, the composition comprlses at least about 15X sol~d polyester by weight of the liqutd polyester, and at least about 5% fibrils and microfibrils by weight of the liquid polyester.
A particularly preferred embodiment of the present invention is a composition comprising from about 60% to about 8g% by weight liquid polyol fatty acid polyester, from about 10% to about 25% by weight solid low calorie fat substltute, and from about lX to about 15% by welght of a coheslve network of polysaccharide fibrils and microfibrils. Most preferably, the composition comprises from about 70% to about 80% liquid polyester, from about 15X to about 20% solid fat substitute, and from about 5X to about 10X fibrils and mlcroflbrlls.
L~u~d Polvol Fat~v Ac~d Polvest~rs The liquid polyol fatty 3cld polyesters of the present invention are liquids at bc ~ temperature, l.e., have a melting point of about 3~C j~8.6F) or below. In general, the liquid polyesters are those whlch ara made from unsaturated fatty acids, whereas solid polyesters are substantially saturated.
~ he liquid polyesters comprise sugar fatty ac~d polyesters, sugar alcohol fatty acld polyesters, and mixtures thereof, ths sugars and sugar alcohols contalnlng from 4 to 8 hydroxyl groups. Sugar or sugar alcohol fatty acld polyesters comprise sugars or sugar alcohols, and fatty acids. The term ~sugar~ is used herein ln lts conventional sense as generic to mono- and d~saccharides. The term ~sugar alcohol~ ls also used ln ~ts convent~onal sense as generic to the reduction product of sugars wherein the aldehyde or ketone group has been reduced to an alcohol. The fatty acld ester compounds are prepared by reacting a monosaccharlde, dlsaccharlde or sugar alcahol wtth fatty acids as dlscussed below.
Examples of sultable monosaccharldes are those containlng 4 hydroxyl groups such as xylose, arablnose, and rlbose; the sugar alcohol der~ved from xylose, i.e., xylltol, ls also suitable. The monosaccharlde erythrose ls not suitable for the practlce of this lnventlon slnce lt only contalns 3 hydroxyl groups; however, the sugar alcohol der~ed from .
erythrose, i.e. erythritol, contains 4 hydroxyl groups and is thus suitable. Among S hydroxyl-containing monosacchar~des that are suitable for use herein are glucose, mannose, galactose, fructose, and sorbose. A sugar alcohol derived from sucrose, glucose, or sorbose, e.g., sorb~tol, contains 6 hydroxyl groups and is also suitable as the alcohol moiety of the fatty acid ester compounds. Examples of suitable disaccharides are maltose, lactose, and sucrose, all of wh~ch contain eight hydroxyl groups.
Preferred polyols for prepar~ng the l~qu~d polyesters for use in the present invention are selected from the group cons~sting of erythr~tol, xylitol, sorb~tol, glucose and ; sucrose. Sucrose is espec~ally preferred.
The polyol start~ng malar~al having at least four hydroxyl groups must be esterified on at least four of the -OH-groups with a fatty acid containing from about 8 to about 22 carbon atoms, and preferably from about 14 to about 18 carbon atoms. Examples of such fatty acids ~nclude caprylic, capr~c, lauric, myr~st~c, myr~stoleic, palmit~c, palmitole~c, stear~c, oleic, ric~nole~c, linole~c, l~nolen~c, eleostear~c, arachidic, arachidon~c, behenic, and eruc~c ac~d. The fatty ac~ds can be der~ved from naturally occurrlng or synthetic fatty ac~ds; they can be saturated or unsaturated, including pos~tional or geometrlcal isomers. However, in order to ~ 25 prov~de the llqu~d polyol polyesters of the present invent~on, ; at least about h~lf of the fatty ac~ds lncorporated into apolyester ~olecule must be unsaturated. Ole~c and l~noleic ac~ds, and m~xtures thereof, are espec~ally preferred.
The llqutd polyol fatty ac~d polyesters useful ~n th~s inventlon must contain at least four fatty ac~d ester groups.
Polyol fatty actd polyester compounds that conta~n three or less fatty ac~d ester groups are d~gested in and the products of d~gest~on are absorbed from the intestinal tract much ~n the manner of ordinary triglyceride fats, whereas the polyol .
fatty acid polyester compounds that contatn four or more fatty acid ester grw ps are substant~ally non-dtgesttble and con-sequently non-absorbable by the human body. It is not necessary that all of the hydroxyl groups of the polyol be esterified with fatty acid, but it is preferable that the polyol contain no more than three unester~fied hydroxyl groups, and more preferable that it conta~n no more than two unesterified hydroxyl groups. Most preferably, substantially all of the hydroxyl groups of the polyol are esterifted with fatty acid, i.e., the compound ~s substant~ally completely esterified. The fatty acids estertfied to the polyol molecule can be the same or mtxed (but, as noted above, a substanttal amount of the unsaturated ac~ ester groups must be present to provide li~uidtty).
The foltowing are non-limtttng examples of spectftc li~utd polyol fatty actd polyesters contatntng at least four fatty actd ester groups su~table for use in the present in~ention: sucrose tetraoleate, sucrose pentaoleate, sucrose hexaoleate, sucrose heptaoleate, sucrose octaoleate, glucose tetraoleate, the glucose tetraesters of soybean oil fatty acids (unsaturated), the mannose tetraesters of mixed soybean otl fatty acids, tha galactose tetraesters of oletc acid, the arabtnose tetraesters of ltnoletc actd, xylose tetraltnoleate, galactose pentaoleate, sorbttol tetraoleate, the sorbttol hexaesters of unsaturated soybean o~l fatty actds, xylttol pentaoleate, and m~xtures thereof.
As noted above, htghly preferred polyol fatty actd esters are those ~hcrQln the fatty actds contatn fro~ about 14 to about 18 carbon atoms.
The polyol fatty actd polyesters suttable for use here~n can be prepared by a vartety of methods known to those sktlled in the art. These methods tnclude: transester1ftcat~on of the polyol with methyl, ethyl or glycerol fatty ac~d esters using a vartety of catalysts; acylat~on of the polyol with a -8-~ 132616~
fatty acid chloride; acylation of the polyol with a fatty acid anhydride; and acylation of the polyol with a fatty acid, per se. As an example, the preparation of polyol fatty acid esters is described in U.S. Patent Nos. 2,831,~54, 3,963,699, 4,517,360 and 4,518,772.
Specific, but non-limiting, examples of the preparation of liquid polyol fatty acid esters suitable for use in the practice of this invention are as follows.
Erythritol tetraoleate -- Erythritol and a f~ve-fold ~ lO molar excess of methyl oleate are heated at 180C (356F) under vacuum, with agitation, in the presence of sodium methoxide catalyst over two react~on periods of several hours each. ~he reaction product (predom~nately erythritol tetraoleate) is refined in petroleum ether and crystallized : 15 three times from ceveral volumes of acetone at 1C (34F).
Xylitol pentaoleate -- Xylitol and a five-fold molar excess of methyl oleate in dimethylacetam~de (DMAC) solution - are heated at 180C (356F) for f~ve hours in the presence of sodium methoxide catalyst, under vacuum. During th~s time the DMAC is remoYed by distlllation. The product (predominately xyl~tol pentaoleate) is reflned in petroleum ether solution and, after being freed of petroleum ether, ~s separated as a liquid layer four t~mes from acetone at about 1C (34F) and t~lce from alcohol at about 10C (50F).
Sorbltol hexaoleate is prepared by essentlally the same procedure used to prepare xyl~tol pentaoleate except that sorbltol ~s substituted for xylitol.
Sucrose octaoleate is prepared by substanttally the same procedure as that used to prepare erythr~tol tetraoleate 30 except that sucrose is substituted for erythritol.
Solid Lcw Calor~e Fat Substitutes The low calorie fat substitute composit~ons of the present invention comprise at least about lOX solid low ~1 calorie fat substitute by weight of the llquld polyol fatty acid polyester The sol1d fat substitute can be any of a variety of edible wholly or partlally nondigestlble compounds whlch can replace trlglyceride fats or olls rhe solld fat substitute must be at least part1ally nondlgestlble so that lt can remain ln comblnatlon wlth the ll~uld polyester and the fibrlls and mtcrofibrlls as the compositlon passes through the dlgestlYe tract By ~partially nondlgestible~ ls meant that at least about 30~ of the fat substltutQ ls not dlgQsted or absorbed by the body Preferably the solld fat substltut~ ls at least 70X
- nondlgcstlbla. Most preferably thc solld fat substltutQ ls lOOX nondlg~stlblQ and lt passcs through the dlgostlve system substantlally the sa~a as whon lt was lngQsted.
15A preferred solid fat substltuto for use ln the present lnventlon ls ~ solld polyol fatty acld polyester of thc type descrlbad her inaboYo undcr tho llquld polyester sectlon The solid polyesters ara sollds at body tempcrature l e have a meltlng polnt abovo about 3~C (98 6F) In gencral the solld polyol poly~stors aro est~rlfied wlth more saturated than unsatur~t d fatt~ aclds Theso solld polyesters gancrall~ h~v- ~n lodln~ valuo of about 12 or bolo~
~ yplc~l cxaJplos of sdlblo solld non~absorbablc non-dlgtstl~lo polyol poly~stors us~ful her~1n lnclud~ sucrose octastoarato, sucrosc oct-p-l~ltato sucrosc heptastearate xylltol pcntastoaratc galactos~ pcntapal~ltato and the 11ke satur~tad pol~ol polycstors havlng at least four -OH groups estcr1fled ~lth Clo-C22 saturated fatty aclds.
Anothcr typ~ of solld f~t substltuto useful hereln comprls~s fatty acld ~stors whlch are non-dlgestlble by v1rtue of branching on the~-carbon atom of the fatty acid moiety. Such materials, which are well known in the chemical arts, include, for example, ~-methyl and ~,~-dimethyl C10-Cl8fatty acid esters of lower alcohols such as ethanol and of polyols such as glycerol.
U.S. Patent 2,962,41~ to Minich (polyhydric alcohol fatty acid esters) and European Patent Application 0,254,547 to White (esterified epoxide-extended polyols), published January 27, 1988, disclose fat substitutes which may be - solid or liquid depending on the fatty acid composition.
- Polyol fatty acid ethers can also be made that are solids at body temperature. Other solid fat substitutes are suitable for use herein provided they are solid at body temperature and at least partially nondigestible.
Polvsaccharide Fibrils and Microfibrils The third component of the present low calorie fat substitute compositions is a cohesive network of lS polysaccharide, substantially water-insoluble fibrils and microfibrils. Thls network is shown at a magnification of 500X in Figure 1 and is indicated by numeral 10. At this magnification, only fibrils indicatad by numeral 1~ are vis~ble. The microfibr~ls wh~ch are present in network 10 are vlsible only at magnifications much greater than SOOX.
A representation of what a portion of network 10 is believed to look l~ke, at a magnif~cation much greater than SOOX, is shown in Figure 2. The fibrils which comprise this net~ork are agaln indtcated by numeral 12. The fibrils 12 baslcally const~tute the ~reinforclng rods~ of network 10.
Th~ fibrlls can ~ary in length, but are usually within the range of from about 10 to about 1,000 mlcrons. ~he ma~ority of these fibrlls typlcally have a length of from about 100 to about 250 mlcrons~
Fibrlls 12 are comprised of rope-like bundles of mlcrofibrils. Th~ surface of the flbrils usually has exposed mlcrofibrils whlch are indicated by numeral 14. It is believed that these exposed microflbrlls 14 cause fibrils 12 to adhere together to form network lQ- (It is believed that ~ , ~1 .
this adherence is due to hydrogen bonding between the fibrils and microfibrils.) Although the microfibrils are often st~ll attached to the fibrils, it is belieYed that, in certain instances, unattached microfibrils can form porttons of network 10.
The microfibrils also vary in length, but are generally shorter than the fibrils. Typically, the microfibrils have a length of from about 1 to about 100 microns. Another key difference between the fibrils and microfibrils is their diameter~ Fibrils typically have a diameter of from about 0.1 to about 2 microns. By contrast, microfibrils typically have a diameter of from about 0.025 to about 0.1 microns.
This network of fibrils and microfibrils has a relatively large surface area. Generally, the surface area of this network is greater than about 100 m2/g. Typically, the surface area of this network ranges from about 100 to about ~ 170 m2/g. This relatively large surface area is thought to be - important to the laxative side effect reduction of the present ` in~ention.
~he surface area of the ftbrtls and microfibrils is measured by a Quantasorb instrument (Quantachrome Company, Syosset, N~Y~)~ This measurement in~ol~es a monolayer nitrogen adsorption analysts of a drted sample at three dtfferent parttal pressures, i~e. a three po~nt B.E.T.
an-lysis~ The dried sample is obtatned by drying an aqueous suspension of the fibrtls and microftbrils with ethanol and acetone, followed by critical potnt dry~ng with carbon dtoxtde~ See Dawes, Biologica~l Techn~gues f~r Transmission and Scannino Electron MlcroscoDv (2d~ Edttion 1979), pp.
231-39, which describes techniques for critical point drying of materials.
The polysaccharide fibrils and microfibrtls which form the cohesive network can be obtained from various sources.
Cellulose is a preferred polysaccharide. A preferred source of cellulosic fibrils and microfibrils is microfibrillated cellulose prepared according to the method disclosed in U.S.
Patent 4,3~4,702 to Turbak et al, issued February 22, 1983.
In this method, cellulosic pulp or other unregenerated fibrous cellulose is added to a liquid suspending media which swells the cellulose.
This liquid suspension is repeatedly passed through a small diameter orifice in which the mixture is sub~ected to a large pressure drop (at least 3,000 psi) and a high viscosity shearing action, followed by a high ~iscosity deceleratlng impact. This converts the cellulosic starting material into a suspension of microfibrillated cellulose. See also U.S.
Patents 4,481,076 and 4,481,077 to Herrick, issued November 6, 1984, which disclose other methods for obtaining microfibrillated cellulo~e. Microfibrillated cellulose can also be obtained com~ercially from ITT Rayonier, a subsidiary of the assignee of these patents, as a spray-dried powder or moist cake.
The present in~ention is not limited by the method for making the fibrils and microf~brils. For example, it is thought that materials falling withln the scope of the invent~on can also be made by a process of ball-milling cellulos~c pulp.
Another method for obtaining cellulosic fibrils and m~crofibrils useful in the present inYention is by bacterial fer~entat~on of a sugar contain~ng solution. Particularly suitable sugar containlng solutions include coconut milk (Nata de Coco7Y) or pineapple(Nata de Pinan') solutions A bacteria culture acts on the sugar solution to spin out a mat ot cellulosic f~brils and microfibrils. This mat can then be redispersed in the present composttions to form the desired net~ork of fibrtls and microfibrils.
The polysaccharide fibrils and microfibrils of the in~entlon can also be obtained through appropriate processing ~`
of other polysaccharide fiber sources particularly celluloslc fibers. Such sources include fibrous fruits and vegetables for example orange pulp strawberry pulp apple pulp and food fiber from other sources.
Processing methods capable of produc~ng fibr~ls and microfibrils include other physical separation processes and fermentation processes. Other mater~als for example pectln may be present in the fiber source and these materials would be separated from the fibr~ls and m~crof~br~ls before use.
The polysaccharides can include other polysacchar~dic materials bes~des cellulose~ For example it ls thought that a net~ork of flbr~ls and m~croflbrils for use ~n the present inventlon can be obtained by fungal fermentatlon of a glucose-containing solutton to produce a 1 3-l~nked glucose-based polysaccharide.
Com~osit~ons Made with Preferred Polvesters Certain sugar and sugar alcohol fatty ac~d polyesters as described above ~n the sectton on liquid polyol polyesters have been dlscovered that do not cause a laxat~ve slde effect even at relat~vely lo~ levels of sol~ds. These polyesters are characterized as having the follow~ng propert~es at 100F
(37.~C): (a) a l~u~d/sol~d stab~l~ty of at least about 50X
preferably at least about ~0~; and (b) a solid fat content bet~een about 5X and about 30X. Preferably the polyesters have a vlseos~ty of at least about 1.0 poise more preferably at least about 5.0 polse after 10 minutes of steady shear at a shear rate of 10 seconds-l. The methods of measurtng vlscosltr and l~quid/solid stab~l~ty are descr1bed below in the Analrtlcal Methods sectlon.
These polyesters preferably have a soltd fat content (SFC) at 100F (3~.8C) between about SX and about 25X more preferably between about lOX and about 20X.
Therefore a preferred embodlment of the present lnvention is a lo~ calorie fat subst~tute composlt~on as described hereinabove comprising a liquid polyester; at least about lOX solid low calorie fat subst~tute by we~ght of the liquid polyester; at least about lX polysaccharide fibrils and microfibrils; and additionally comprising a sugar fatty acid polyester or sugar alcohol fatty acid polyester, or m~xtures thereof, having the above-described stability, SFC, and preferably viscosity at 100F t37.8C).
Moreover, compositions can be made that are very res~stant to laxative s~de effect even w~thout the use of sol~d low calor~e fat substitutes, ~f the compos~t~ons conta~n a suff~c~ent amount of the above-descrtbed preferred polyesters. Hence, another embod~ment of the present ` inventlon ~s a low calorle fat substitute composition -~- compr~stng from about lX to about 42X by weight liquid polyol fatty acid polyester; fro~ about lX to about 15X by welght of a cohes~ve network of polysacchartde fibrils and mtcrof~br~ls;
and from about 43X to about 98X by we~ght low calorie fat subst~tute selected from the group consist~ng of sugar fatty ac~d polyesters, sugar alcohol fatty acid polyesters, and mixtures thereof, the sugars and sugar alcohols containing from ~ to 8 hydroxyl groups, and each fatty acid group hav~ng from about 8 to about 22 carbon atoms, wherein the fat substttute has, at 100F (3~.8C): (a) a llquld/sol~d stabll~ty of at least about 50X, preferably at least about ~OX; and (b) a solld fat content between about 5% and about 30X. Preferably the polyesters have a v~scosity of at least about I potse, more preferably at least about 5 po~se, after 10 mtnutes of steady shear at a shear rate oF 10 seconds~l.
Htghly preferred polyesters havlng the above-described properttes are sucrose fatty acld polyesters. Preferred sucrose fatty acid polyesters have the ma~or~ty of their hydroxyl groups esterif~ed with fatty acids. Preferably at least about 85X, and most preferably at least about 95%, of the sucrose fatty acid polyesters are selected from the group consisting of octaesters, heptaesters and hexaesters, and mixtures thereof. Preferably, no more than about 35% of the esters are hexaesters or heptaesters, and at least about 60%
of the sucrose fatty acid polyesters are octaesters. Most preferably, at least about 70% of the polyesters are octaesters. It is also most preferred that the polyesters have a total content of penta- and lower esters of not more ~ than about 3X
-- Preferably at least about 80%, and most preferably at least about 90%, of the fatty acids of the sucrose polyesters are selected from the group consisting of m~xtures of palmitic, stearic, oleic, linole~c, and behenic acids. It is also most preferred that at least about 80X of the fatty acids are selected from the group consisting of mixtures of C16 to C18 fatty acids.
The fatty acids of the sucrose polyesters can be saturated, unsaturated, or mixtures thereof. The unsaturated fatty acids can include positional and geometric isomers (e.g~, Çi~ and trans isomers), or mixtures thereof.
~O More speciflcally, the following is a preferred fatty acid composit~on: from about 9X to about 12X palmitic; from about 35X to about 53X stearic; from about 19X to about 43X
oleic; from about 2X to about 1~X l~nolelc; from about 0% to about 2X linolenic; from about OX to about 2X arachid~c; from about OX to about 10X behenlc; and from about 0% to about 2%
erucic~
Sucrose fatty acid polyesters hav~ng the above-descr~bed liquid/solid stability, solid fat content and v~scosity can be made, for example, by esterifying sucrose with methyl esters of a fully hydrogenated soy oil (Iodlne Value about 1) and a partlally hydrogenated soy oil (Iodine Yalue about 107J, blended in a 57:43 rat~o~
Uses of the Low Calorie Fat Substitute ComDositions The present low calorie fat substitute compositions are useful in a wide variety of food and beverage products. For example, the compositions can be used in the production of baked goods in any form, such as mixes, shelf-stable baked - goods, and frozen baked goods. Possible applicatlons include, but are not limited to~ cakes, browntes, muffins, bar cookies, wafers, biscuits, pastries, pies, pie crusts, and cookies, including sandwich cookies and chocolate chip cookies, particu?arly the storage-stable dual-textured cook~es described in U.S. Patent 4,4~,333 of Hong ~ Brabbs. ~he baked goods can conta~n fruit, cream, or other fillings.
Other baked good uses include breads and rolls, crackers, pretzels, pancakes, waffles, ice cream cones and cups, yeast-ra~sed baked goods, pi~zas and pizza crusts, baked far~naceous snack foods, and other baked salted snacks.
The composit~ons can be used to make shortening and oil products, such as shortenings, margarines, spreads, butter blends, lards, cooklng and frying oils, salad o~ls, popcorn ~o oils, salad dressings, mayonnaise, and other edible oils.
The low calorie fat substitute compositions of the present invent~on can be fortified with vitamins and minerals, particularly the fat-soluble vitamins. The fat-soluble v~ta~ins ~nclude ~itamin A, vitamin D, vitamtn E ~tocopherol), 2s and vltamin K. Four different tocopherols have been identlf~ed (alpha, beta, gamma and delta), all of which are otly, yello~ u~ds, insoluble in water but soluble in fats and o~ls. If deslred, the compos~t~ons can be fortif~ed w~th a recommended dally allowance (RDA), or lncrement or multiple of an RDA, of any of the fat-soluble vitamins or comb~natlons thereof. The present compositlons preferably contaln about 1.1 mg. of Vitamin E as d-alpha tocopheryl acetate per 1000 grams of polyol polyester.
The present compositions are particularly useful in combination with particular classes of food and beverage ingredients. For example, an extra calorie reduction benefit is achieved when the compositions are used with noncaloric or reduced calorie sweeteners alone or in combination with bulking agents. Noncalori~ or reduced calorie sweeteners include, but are not limited to, aspartame; saccharin;
alitame, thaumatin; dihydrochalcones; cyclamates; steviosides;
glycyrrhizins, synthetic alkoxy aromatics, such as Dulcin~ and P-4000~; sucrolose; suosan; miraculin; monellin; sorbitol;
xylitol; talin; cyclohexylsulfamates; substituted imidazolines; synthetic sulfamic acids such as acesulfame, acesul~am-K and n-substituted sulfamic acids; ox~mes such as périlartine; rebaudioside-A; peptides such as aspartyl malonates and succanilic acids; dipept~des; amino acid based sweeteners such as gem-diaminoalkanes, meta-aminoben20ic acid, L-aminodicarboxylic acid alkanes, and amides of certain alpha-aminodicarboxylic ac~ds and gem-diamines; and 3-hydroxy-4-alkyloxyphenyl al~phat~c carboxylates or heterocyclic aromat~c carboxylates;
The composit~ons can be used in combinat~on with other noncaloric or reduced calor~e fats~ Examples of such materials are: fatty alcohol esters of polycarboxylic acids (U.S. Patent 4,508,746 of Hamn, assigned to CPC Internat~onal, Inc~, issued Apr~l 2, 1985); fatty polyethers of polyglycerol (U.S. Patent 3,932,532 of Hunter et al., ass~gned to ICI
Un~ted States, Inc., issued January 13~ 1976) (food use d~sclosed in German Patent 207,07~, issued Feb. 15, 1984));
ethers and ether-esters of polyols contaln~ng the neopentyl ~o~ety (U.S. Patent 2,962,419 of Mln~ch, issued Nov. 29, 1960); fatty alcohol d~esters of dicarboxylic ac~ds such as malonic and succinic acid (U.S. Patent 4,582,927 of Fulcher, assigned to Frito-Lay, Inc., issued April 15, 1986);
tr~glyceride esters of alpha branched chain-alkyl carboxyl k ac~ds (U.S. Patent 3,579,548 of ~hyte, assigned to The Procter . ~ 6amble Co., issued May 18, 1971~; fatty acid diglyceride, .~ .
diesters of dibasic acids (U.S. Patent 2,874,175 ta Feuge et al.); polyorganosiloxanes (European Patent Application 205,273 to Frye); and alpha-acylated glycerides (U.S. Patent 4,582.715 to Volpenhein).
Other partial fat replacements useful in combination with the present compositions are medium chain triglycerides, highly esterified polyglycerol esters, acetin fats, plant sterol esters, N-Oil, polyoxyethylene esters, jojoba esters, mono/diglycerides of fatty acids, mono/diglycerides of o short-chain di~asic acids, silicone oils/s~loxanes (see, e.g., European Patent Application 205,273 of Dow Corp., Simplesse (NutraSweet Co.), Olestrin (Reach Associates), and esterified epoxide-extended polyols (see uropean Patent Application 254,547 of Atlantic Richfield 15 Co.).
Bulk~ng or bodying agents are useful in combination with the present compositions in many foods. The bulking agents can be nond~gestible carbohydrates, for example, polydextrose and cellulose or cellulose derivati~es, such as carboxymethylcellulose, carboxyethylcellulose, hydroxy-propylcellulose, methylcellulose and microcrystall~ne cellulose. Other suitable bulking agents include gums (hydro-colloids~, starches, dextrins, fermented whey, tofu, maltodextr~ns, polyols, including sugar alcohols, e.g.
sorbltol and mannltol, and carbohydrates, e.g. lactose.
Analvt~cal Methods 1. V~scos~tv Measurement A. Sample PreDaration ~he polyol fatty acid polyester sample is heated unt~l it completely melts and is thoroughly mixed. Ten grams of the melted sample is weighed into a preheated 20 ml glass vial.
~he sarple is then allowed to recrystallize at 100F + 5F
(37.8C + 3C) for 24 hours. After the 24 hour time period has elapsed, the sample is taken to the viscometer and the ~ viscosity is measured.
- B. Viscometer Operation Procedure A Ferranti-Shirley plate and cone viscometer (Ferrant~
Electric, Inc., 87 Modular Ave., Commack, NY 11725~ equlpped with a 600 9 torque spring is used for the v~scos~ty measurement. A cone is put into place, and the viscometer temperature is ad~usted to 100F (3~.8C). The chart recorder is calibrated, and the gap between the cone and plate is set.
The cone speed is checked, and the cone and plate temperatures are equilibrated to 100F (3~.8C). The panel controls are set. Sufflcient sampl~ ~s placed between the plate and the cone so that the gap is completely ftlled. The temperature is allo~ed to stabili2e at 100F (37.8C~ for about 30 seconds.
Start the test by selectlng the RPM for 10 seconds l shear rate and record on the strlp chart recorder. Record the shear stress at the maximum value for to and then for two 30-second ~ntervals, followed by every minute thereafter untll the value at 10 minutes ls recorded~ Ylscoslty tpolse) ~ shear stress (dynes/o~2~ dlvlded by shear rate (second-l).
II. Llauld/Solld Stab~litv Measurement A polyol fatty acld polyester sample is heated untll ~t co~pletely ~elts and ~s thoroughly m~xed. The sample ls then poured lnto Becb~n #3 U 062 ~.~ ml tubes to capaclty. The tubes are lrmedlately transferred to a 100F ~ 5F (37.8C
3C) constant te~perature room and allowed to recyrstalll2e undlsturbQd for 2~ hours. The samples are then centrifuged at 60,000 rpe for one hour at 100F (37.8C). The force on the samples ls U6,000 g's. The percent llquld separated ls then measured by comparing the relatlve helghts of the llquid and solld phases. Llquld/solld stablllty (X) ~ 100 x (total volume of sa~ple ^ volume of llquld that separated)/total volu~e of sample.
III. Solid Fat Content Measurement Before determining SFC values, the polyol fatty acid polyester sample is heated to a temperature of 158F (70C) or higher for at least 0.5 hours or unt11 the sample is completely melted. The melted sample is then tempered at a temperature of 40F (~.4C) for at least 72 hours. After ~ tempering, the SFC value of the polyester at a temperature of 100F (37.8C) is determined by pulsed nuclear magnetic resonance (PNMR). The method for determining SFC values by PNMR is described in Madison and Hill, J. Amer. Oil Chem.
Soc., vol 55 (19~8), pp. 328-31 (herein ~ncorporated by reference3. Measurement of SFC by PNMR is also described in A.O.C.S. Official Method Cd. 16-81, Qfficial Methods and Recommended Practice~ of The Ameri~an Oil Chemis~s SocietY, 3rd Edition, 1987.
The following examples are intended only to further illustrate the invention and are not intended to limit the scope of the invention which is defined by the claims.
A sucrose fatty acid polyester composition is prepared by co~bining liquid SUCrOSQ polyester, solid sucrose polyester, and mtcrofibrillated cellulose:
~1 : . , '' ~
Inaredients ~ %
Liquid sucrose polyester* 164 9. 76%
Solid sucrose polyester** 37 9. 17%
Microfibrillated cellulose***15 9. 7Z
*Sucrose octaoleate, iodine value 107 **Mixed hexa-, hepta- and octaesters of sucrose esterified with mixed soybean oil fatty aclds, and hydrogenated to an iodine value of 8 ***Microfibrillated cellulose, ITT Rayonier Forest Products The.solid sucrose polyester is added to the ltquid sucrosa polyester, and the mlxture is heated to about 160-170F (~1-7~C). The mixture is maintained at this temperature for about 15 minutes, with frequent stirring.
~hile continuing to maintain the temperature, the microfibrillated cellulose f~bers are then dispersed in the polyester mixture by slow addition using a standard kitchen mixer set at low speed, to make a uniform dispersion. The composition is then cooled rapidly by placing the mixing bowl into an ice water bath, and mixing at low speed until the dispers~on is agaln uniform. Lastly, the composit~on is placed ~n a sealed glass ~ar and blanketed with nitrogen for storagc.
The compos~tion is very resistant to laxatlve side effect -~ 25 after lngestion.
Three kinds of sucrose fatty acid polyester compositions are made and tested for laxatlve side effect:
` 1326162 Com~ition A
Inaredlents Liqu1d sucrosa polyester~ 94X
Mlcroflbrlllated cellulose~ 6X
ComDosltlon B
Inared~ents Liquld sucrose polyester~ ~6X
Solid sucrose polyester~ 2~%
ComDosit1Qn C:
Insr~D~
Llquld sucrose polycster~ J6X
Solld sucrose polyester~* l~
Mlcrof1brillat d cellulose~ X
~Sucrose oct~oleato lodlne value lO~
~Mlx d hex~- hopt~- ~nd oct~esters of sucrose esterlfl d ~lth ~lxRd soybean oll f~tty aclds ~nd hydrogen~t d to ~n lodlne value of 8 1croflbrlllat t ecllylose IIT R yonler For st Produets Co posltlon A ls found to be lneff etlvc ln laxatlve slde effeet r ductlon L~x~tlvo sldo eff ct ls r duc t ln both Corposltlon 8 ~nd Co~posltlon C but Composltlon C ls found to b~ ~n ~pro~ _ nt over Co~poslt10n B. It ls concluded that the threo p~rt mlxture of llquld sucros- polyester solld sucros- pol~ester and mlcroflbrlllat d cellulose ls more reslstant to l x~tlve slte effect th~n the e~o part mlxture of llquld ~nd solld suc n se polyester and much more reslst~nt than the t~o part mlxture of llquld sucrose polyester and mlcroflbrlll~t t cellulose ,~
ExamDl~ 3 A composition is made as in Example 1, except that the composition contains 46X liquid sucrose polyester, 7%
microfibrillated cellulose, and 47% of a sucrose fatty acid polyester made by esterifying sucrose with methyl esters of a fully hydrogenated soy oil (IV about 1) and a partially hydrogenated soy oil (IV about 107), blended in a 47:53 ratio.
The latter suerose polyester has the following properties:
:;
ViscositY 25.9 poise After 10 min. steady shear at shear rate of 10 seconds~l Liquid/Solid Stability 92.5%
SFC at 100F (3~.8C) 10X
Fattv Acid Co~osition C16 9.8%
C16: 1 lO ` 50.6 C18:1 21.6 C18:2 15.~ ~
C18:3 1.0 Others 1.3 Iod~ne Value 48.6 Ester Distrlbutlon ` Oct~ 89.1X
Hept~ 10.9 Hex~ ~0. 1 ` 20 Pent~ <0.1 Lo~er <0.1
LOW CALORIE FAT SUBSTITUTE COMPOSITIONS
RESISTAN~ ~O LAXATIVE SIDE EFFECT
- TEC~NICAL FIELD
The present invention relates to the f~eld of low calor~e fat and oil substitutes. Specif~cally, the invent~on relates to low calor~e fat subst~tute compos~t~ons that contain polysaccharide fibrils and microfibrils such as m~crof~brillated cellulose. The compos~t~ons are partlcularly useful as fat replacements in foods.
BACK~Q1~ OF THE INVENIION
The consumption of large amounts of trtglycer1de fats has been linked to varlous health problems. For example, one of the most common metabollc problems among people today is obesity. Th~s cond~tion ls prlmarily due to ~ngestlon of a greater number of calorles than are expended. Fat ~s the ~ost concentrated form of energy in the d~et, wlth each gram of fat supply~ng approx~mately 9 calor~es, and trtglycer1de fats const~tute about 9O~ of the total fat consumed ln the average dlet.
~he Nattonal Institutes of Health Consensus Development ~` Conference, ~Lo~erlng Blood Cholesterol to Prevent Heart Dlsease~, JA~A, Vol. 253, No. 1~, pp. 2080-2086 (1985), concluded that elevatlon of blood cholesterol levels ~s a ma~or cause of coronary artery d~sease, and recommended a ` reductlon ~n the amount of fat eaten to reduce blosd serum `` cholesterol levels.
Hence, there is a need for ways to reduce the amount of trlglycer~de fats in the d~et, ln order to reduce the health rlsks associated w~th these fats.
Low calor~e fats wh1ch can replace tr~glycerides are descrlbed by Mattson et al. in U.S. Patent 3,600,186. Food i~
.
: ., . - .
` 13261 6?
compositions are disclosed in which at least a portion of the triglyceride content is replaced by a polyol fatty acid ester having at least four fatty acid ester groups with each fatty acid having from 8 to 22 carbon atoms.
U.S. Patent 4,461,~82 to Robbins et al., issued July 24, 1984, discloses baked products contain~ng 1~-60% l~quid polyol polyester and 25-85% microcrystalline cellulose and flour.
Examples given are breads, cakes and wafers.
U.S. Patent 3,954,976 to Mattson et al. describes pharmaceutical compositions for ~nhibiting the absorption of cholesterol comprising effective unit dosage amounts of a polyol fatty acid ester ha~ing at least four fatty acid ester groups.
The esters disclosed in these patents are useful as fat substitutes in low calor~e food products or in pharmaceutlcal ~
composit~ons for controlling hypercholesterolemia. Unfortu-nately, regular ingestion of moderate to high levels of liquid polyol fatty acid`polyesters can produce an undesirable laxat~ve side effect, namely, leakage of the ester through the anal sph~ncter.
U.S. Paten~s 4,005,195 and 4,005,196 to Jandacek et al.
descr~be a method of reducing the undes~rable la~ative side effect through the addition to the liquid polyesters of ant~-anal leakage agents. The anti-anal leakage agents include solid fatty aclds (melting point 37C or higher) and thelr triglycerlde source, and solid polyol fatty acid pol~esters.
Other patents describe the use of microfibrillated cellulose in foods. For example, U.S. Patent 4,341,807 to Turbak et al., issued July 27, 1982, describes food products containing a susp~nsion of microfibrillated cellulose as a thickener, flavor carrier and suspension stabil~zer. Food uses speci~ically taught include fillings, crushes, soups, grav~es, puddings, dips, topp~ngs and other food products.
Turbak, "r~icrofibrillated Cellulose - A New Composition of Commercial Significance," Tappi 1984 Non-Woven Svmposium, page 121, describes the use of microfibrillated cellulose in reduced calorie jams and jellies, reduced calorie foods, and low and reduced calorie spreads.
Neither of the Turbak references suggests that microfibrillated cellulose can be used to reduce laxative side effect of a liquid polyol polyester.
It is an object of an aspect of the present invention to provide low calorie fat substitute compositions that are useful as a replacement for normal triglyceride fats in low calorie foods, and as pharmaceutical compositions.
It is an object of an aspect of the present invention to provide low calorie fat substitute compositions that are resistant to an undesirable laxative side effect.
These and other objects of the present invention 2Q will become evident from the disclosure herein.
All parts, percentages, and ratios used herein are by wei~ht unless otherwise indicated.
SUMMAR~ OF TH~ INVE~TION
The present invention relates to low calorie fat substitute compositions that are useful as fat replacements in low calorie foods, and as pharmaceutical compositions. Sucrose fatty acid esters are preferred low calorie fat substitutes. The compositions are highly resistant to an undesirable laxative side effect. These benefits are achieved by formulating compositions comprising a liquid polyol fatty acid polyester, at least about 10% solid low calorie fat substitute by weight of the liquid polyester, and at least about 1% of a cohesive network of polysaccharide fibrils and microfibrils, for example microfibrillated cellulose, by weight of the liquid polyester.
Other aspects of this invention are as follows:
~1 -3a-A low calorie fat substitute composition comprising a liquid polyol fatty acid polyester, at least about 10%
solid low calorie fat substitute by weight of the liquid fat polyester, and at least about 1% of a cohesive network of polysaccharide fibrils and microfibrils by weight of the liquid polyester.
A low calorie fat substitute composition comprising from about 1% to about 42% by weight liquid polyol fatty acid polyester; from about 1% to about 15% by weight of a cohesive network of polysaccharide fibrils and microfibrils; and from about 43% to about 98% by weight low calorie fat substitute selected from the group consisting of suqar fatty acid polyesters, sugar alcohol fatty acid polyesters, and mixtures thereof, the sugars and sugar alcohols containing from 4 to 8 hydroxyl groups, and each fatty acid group having from about 8 to about 22 carbon atoms, wherein the fat substitute has, at - 100F ~37.8C):
(a) a liquid/solid stability of at least about 50%;
and (b) a solid fat content between about 5% and about 30%.
.
BRIEF DESCRIPTION OF THE ORA~INGS
Figure 1 is a photograph of a network of cellulos~c fibrils and microfibrils taken at SOOX magnification.
Figure 2 is a greatly enlarged representation of what a portion of the net~ork of cellulos~c f~brils and microfibrils is belie~ed to look like in the compositions of the present invention.
DETAILED DESCRIPTION OF THE IN~ENTION
The present i m ention is base~ on the discovery that when a net~ork of polysaccharide fibrils and microfibr~ls is dispersed in a m~xture ~f a `iquld polyol fatty acid polyester and a solid low calorie f-: substitute, the resulting composition is e~en more resistant to laxative side effect than the liquid/solid mixturQ alone. This flnding was unexpected in view of the fact that no laxatlve side effect reductlon is seen in the two-part combination of liquid polyester and fibrils and microfibrils.
The addition of the polysaccharide fibrils and microfibrils is thought to provlde a material of high surface area ~hich ser~es as nucleating SitQS for the prec~pitation of the solid fat substitute, thereby entrapping the liquid polyester in a matrix with a hydrophobic surface. Apparently - the surface of th~ resultant gel has a hlgh contact angle, and watQr is not read~ly abl~ to spread or penetratQ the surface and causQ separat~on of the liquid polyestQr.
A lo~ caloriQ fat-substttute composition according to the present in~ention comprises a liqutd polyol fatty acld poly~st~r; at least about lOX solld lo~ calor~e fat substitute by wetght of thQ liquid polyester; and at least about 1% of a cohesl~e network of polysacchartde fibrils and microfibrils by ~eight of the l~quid polyester. Preferably, the composition comprlses at least about 15X sol~d polyester by weight of the liqutd polyester, and at least about 5% fibrils and microfibrils by weight of the liquid polyester.
A particularly preferred embodiment of the present invention is a composition comprising from about 60% to about 8g% by weight liquid polyol fatty acid polyester, from about 10% to about 25% by weight solid low calorie fat substltute, and from about lX to about 15% by welght of a coheslve network of polysaccharide fibrils and microfibrils. Most preferably, the composition comprises from about 70% to about 80% liquid polyester, from about 15X to about 20% solid fat substitute, and from about 5X to about 10X fibrils and mlcroflbrlls.
L~u~d Polvol Fat~v Ac~d Polvest~rs The liquid polyol fatty 3cld polyesters of the present invention are liquids at bc ~ temperature, l.e., have a melting point of about 3~C j~8.6F) or below. In general, the liquid polyesters are those whlch ara made from unsaturated fatty acids, whereas solid polyesters are substantially saturated.
~ he liquid polyesters comprise sugar fatty ac~d polyesters, sugar alcohol fatty acld polyesters, and mixtures thereof, ths sugars and sugar alcohols contalnlng from 4 to 8 hydroxyl groups. Sugar or sugar alcohol fatty acld polyesters comprise sugars or sugar alcohols, and fatty acids. The term ~sugar~ is used herein ln lts conventional sense as generic to mono- and d~saccharides. The term ~sugar alcohol~ ls also used ln ~ts convent~onal sense as generic to the reduction product of sugars wherein the aldehyde or ketone group has been reduced to an alcohol. The fatty acld ester compounds are prepared by reacting a monosaccharlde, dlsaccharlde or sugar alcahol wtth fatty acids as dlscussed below.
Examples of sultable monosaccharldes are those containlng 4 hydroxyl groups such as xylose, arablnose, and rlbose; the sugar alcohol der~ved from xylose, i.e., xylltol, ls also suitable. The monosaccharlde erythrose ls not suitable for the practlce of this lnventlon slnce lt only contalns 3 hydroxyl groups; however, the sugar alcohol der~ed from .
erythrose, i.e. erythritol, contains 4 hydroxyl groups and is thus suitable. Among S hydroxyl-containing monosacchar~des that are suitable for use herein are glucose, mannose, galactose, fructose, and sorbose. A sugar alcohol derived from sucrose, glucose, or sorbose, e.g., sorb~tol, contains 6 hydroxyl groups and is also suitable as the alcohol moiety of the fatty acid ester compounds. Examples of suitable disaccharides are maltose, lactose, and sucrose, all of wh~ch contain eight hydroxyl groups.
Preferred polyols for prepar~ng the l~qu~d polyesters for use in the present invention are selected from the group cons~sting of erythr~tol, xylitol, sorb~tol, glucose and ; sucrose. Sucrose is espec~ally preferred.
The polyol start~ng malar~al having at least four hydroxyl groups must be esterified on at least four of the -OH-groups with a fatty acid containing from about 8 to about 22 carbon atoms, and preferably from about 14 to about 18 carbon atoms. Examples of such fatty acids ~nclude caprylic, capr~c, lauric, myr~st~c, myr~stoleic, palmit~c, palmitole~c, stear~c, oleic, ric~nole~c, linole~c, l~nolen~c, eleostear~c, arachidic, arachidon~c, behenic, and eruc~c ac~d. The fatty ac~ds can be der~ved from naturally occurrlng or synthetic fatty ac~ds; they can be saturated or unsaturated, including pos~tional or geometrlcal isomers. However, in order to ~ 25 prov~de the llqu~d polyol polyesters of the present invent~on, ; at least about h~lf of the fatty ac~ds lncorporated into apolyester ~olecule must be unsaturated. Ole~c and l~noleic ac~ds, and m~xtures thereof, are espec~ally preferred.
The llqutd polyol fatty ac~d polyesters useful ~n th~s inventlon must contain at least four fatty ac~d ester groups.
Polyol fatty actd polyester compounds that conta~n three or less fatty ac~d ester groups are d~gested in and the products of d~gest~on are absorbed from the intestinal tract much ~n the manner of ordinary triglyceride fats, whereas the polyol .
fatty acid polyester compounds that contatn four or more fatty acid ester grw ps are substant~ally non-dtgesttble and con-sequently non-absorbable by the human body. It is not necessary that all of the hydroxyl groups of the polyol be esterified with fatty acid, but it is preferable that the polyol contain no more than three unester~fied hydroxyl groups, and more preferable that it conta~n no more than two unesterified hydroxyl groups. Most preferably, substantially all of the hydroxyl groups of the polyol are esterifted with fatty acid, i.e., the compound ~s substant~ally completely esterified. The fatty acids estertfied to the polyol molecule can be the same or mtxed (but, as noted above, a substanttal amount of the unsaturated ac~ ester groups must be present to provide li~uidtty).
The foltowing are non-limtttng examples of spectftc li~utd polyol fatty actd polyesters contatntng at least four fatty actd ester groups su~table for use in the present in~ention: sucrose tetraoleate, sucrose pentaoleate, sucrose hexaoleate, sucrose heptaoleate, sucrose octaoleate, glucose tetraoleate, the glucose tetraesters of soybean oil fatty acids (unsaturated), the mannose tetraesters of mixed soybean otl fatty acids, tha galactose tetraesters of oletc acid, the arabtnose tetraesters of ltnoletc actd, xylose tetraltnoleate, galactose pentaoleate, sorbttol tetraoleate, the sorbttol hexaesters of unsaturated soybean o~l fatty actds, xylttol pentaoleate, and m~xtures thereof.
As noted above, htghly preferred polyol fatty actd esters are those ~hcrQln the fatty actds contatn fro~ about 14 to about 18 carbon atoms.
The polyol fatty actd polyesters suttable for use here~n can be prepared by a vartety of methods known to those sktlled in the art. These methods tnclude: transester1ftcat~on of the polyol with methyl, ethyl or glycerol fatty ac~d esters using a vartety of catalysts; acylat~on of the polyol with a -8-~ 132616~
fatty acid chloride; acylation of the polyol with a fatty acid anhydride; and acylation of the polyol with a fatty acid, per se. As an example, the preparation of polyol fatty acid esters is described in U.S. Patent Nos. 2,831,~54, 3,963,699, 4,517,360 and 4,518,772.
Specific, but non-limiting, examples of the preparation of liquid polyol fatty acid esters suitable for use in the practice of this invention are as follows.
Erythritol tetraoleate -- Erythritol and a f~ve-fold ~ lO molar excess of methyl oleate are heated at 180C (356F) under vacuum, with agitation, in the presence of sodium methoxide catalyst over two react~on periods of several hours each. ~he reaction product (predom~nately erythritol tetraoleate) is refined in petroleum ether and crystallized : 15 three times from ceveral volumes of acetone at 1C (34F).
Xylitol pentaoleate -- Xylitol and a five-fold molar excess of methyl oleate in dimethylacetam~de (DMAC) solution - are heated at 180C (356F) for f~ve hours in the presence of sodium methoxide catalyst, under vacuum. During th~s time the DMAC is remoYed by distlllation. The product (predominately xyl~tol pentaoleate) is reflned in petroleum ether solution and, after being freed of petroleum ether, ~s separated as a liquid layer four t~mes from acetone at about 1C (34F) and t~lce from alcohol at about 10C (50F).
Sorbltol hexaoleate is prepared by essentlally the same procedure used to prepare xyl~tol pentaoleate except that sorbltol ~s substituted for xylitol.
Sucrose octaoleate is prepared by substanttally the same procedure as that used to prepare erythr~tol tetraoleate 30 except that sucrose is substituted for erythritol.
Solid Lcw Calor~e Fat Substitutes The low calorie fat substitute composit~ons of the present invention comprise at least about lOX solid low ~1 calorie fat substitute by weight of the llquld polyol fatty acid polyester The sol1d fat substitute can be any of a variety of edible wholly or partlally nondigestlble compounds whlch can replace trlglyceride fats or olls rhe solld fat substitute must be at least part1ally nondlgestlble so that lt can remain ln comblnatlon wlth the ll~uld polyester and the fibrlls and mtcrofibrlls as the compositlon passes through the dlgestlYe tract By ~partially nondlgestible~ ls meant that at least about 30~ of the fat substltutQ ls not dlgQsted or absorbed by the body Preferably the solld fat substltut~ ls at least 70X
- nondlgcstlbla. Most preferably thc solld fat substltutQ ls lOOX nondlg~stlblQ and lt passcs through the dlgostlve system substantlally the sa~a as whon lt was lngQsted.
15A preferred solid fat substltuto for use ln the present lnventlon ls ~ solld polyol fatty acld polyester of thc type descrlbad her inaboYo undcr tho llquld polyester sectlon The solid polyesters ara sollds at body tempcrature l e have a meltlng polnt abovo about 3~C (98 6F) In gencral the solld polyol poly~stors aro est~rlfied wlth more saturated than unsatur~t d fatt~ aclds Theso solld polyesters gancrall~ h~v- ~n lodln~ valuo of about 12 or bolo~
~ yplc~l cxaJplos of sdlblo solld non~absorbablc non-dlgtstl~lo polyol poly~stors us~ful her~1n lnclud~ sucrose octastoarato, sucrosc oct-p-l~ltato sucrosc heptastearate xylltol pcntastoaratc galactos~ pcntapal~ltato and the 11ke satur~tad pol~ol polycstors havlng at least four -OH groups estcr1fled ~lth Clo-C22 saturated fatty aclds.
Anothcr typ~ of solld f~t substltuto useful hereln comprls~s fatty acld ~stors whlch are non-dlgestlble by v1rtue of branching on the~-carbon atom of the fatty acid moiety. Such materials, which are well known in the chemical arts, include, for example, ~-methyl and ~,~-dimethyl C10-Cl8fatty acid esters of lower alcohols such as ethanol and of polyols such as glycerol.
U.S. Patent 2,962,41~ to Minich (polyhydric alcohol fatty acid esters) and European Patent Application 0,254,547 to White (esterified epoxide-extended polyols), published January 27, 1988, disclose fat substitutes which may be - solid or liquid depending on the fatty acid composition.
- Polyol fatty acid ethers can also be made that are solids at body temperature. Other solid fat substitutes are suitable for use herein provided they are solid at body temperature and at least partially nondigestible.
Polvsaccharide Fibrils and Microfibrils The third component of the present low calorie fat substitute compositions is a cohesive network of lS polysaccharide, substantially water-insoluble fibrils and microfibrils. Thls network is shown at a magnification of 500X in Figure 1 and is indicated by numeral 10. At this magnification, only fibrils indicatad by numeral 1~ are vis~ble. The microfibr~ls wh~ch are present in network 10 are vlsible only at magnifications much greater than SOOX.
A representation of what a portion of network 10 is believed to look l~ke, at a magnif~cation much greater than SOOX, is shown in Figure 2. The fibrils which comprise this net~ork are agaln indtcated by numeral 12. The fibrils 12 baslcally const~tute the ~reinforclng rods~ of network 10.
Th~ fibrlls can ~ary in length, but are usually within the range of from about 10 to about 1,000 mlcrons. ~he ma~ority of these fibrlls typlcally have a length of from about 100 to about 250 mlcrons~
Fibrlls 12 are comprised of rope-like bundles of mlcrofibrils. Th~ surface of the flbrils usually has exposed mlcrofibrils whlch are indicated by numeral 14. It is believed that these exposed microflbrlls 14 cause fibrils 12 to adhere together to form network lQ- (It is believed that ~ , ~1 .
this adherence is due to hydrogen bonding between the fibrils and microfibrils.) Although the microfibrils are often st~ll attached to the fibrils, it is belieYed that, in certain instances, unattached microfibrils can form porttons of network 10.
The microfibrils also vary in length, but are generally shorter than the fibrils. Typically, the microfibrils have a length of from about 1 to about 100 microns. Another key difference between the fibrils and microfibrils is their diameter~ Fibrils typically have a diameter of from about 0.1 to about 2 microns. By contrast, microfibrils typically have a diameter of from about 0.025 to about 0.1 microns.
This network of fibrils and microfibrils has a relatively large surface area. Generally, the surface area of this network is greater than about 100 m2/g. Typically, the surface area of this network ranges from about 100 to about ~ 170 m2/g. This relatively large surface area is thought to be - important to the laxative side effect reduction of the present ` in~ention.
~he surface area of the ftbrtls and microfibrils is measured by a Quantasorb instrument (Quantachrome Company, Syosset, N~Y~)~ This measurement in~ol~es a monolayer nitrogen adsorption analysts of a drted sample at three dtfferent parttal pressures, i~e. a three po~nt B.E.T.
an-lysis~ The dried sample is obtatned by drying an aqueous suspension of the fibrtls and microftbrils with ethanol and acetone, followed by critical potnt dry~ng with carbon dtoxtde~ See Dawes, Biologica~l Techn~gues f~r Transmission and Scannino Electron MlcroscoDv (2d~ Edttion 1979), pp.
231-39, which describes techniques for critical point drying of materials.
The polysaccharide fibrils and microfibrtls which form the cohesive network can be obtained from various sources.
Cellulose is a preferred polysaccharide. A preferred source of cellulosic fibrils and microfibrils is microfibrillated cellulose prepared according to the method disclosed in U.S.
Patent 4,3~4,702 to Turbak et al, issued February 22, 1983.
In this method, cellulosic pulp or other unregenerated fibrous cellulose is added to a liquid suspending media which swells the cellulose.
This liquid suspension is repeatedly passed through a small diameter orifice in which the mixture is sub~ected to a large pressure drop (at least 3,000 psi) and a high viscosity shearing action, followed by a high ~iscosity deceleratlng impact. This converts the cellulosic starting material into a suspension of microfibrillated cellulose. See also U.S.
Patents 4,481,076 and 4,481,077 to Herrick, issued November 6, 1984, which disclose other methods for obtaining microfibrillated cellulo~e. Microfibrillated cellulose can also be obtained com~ercially from ITT Rayonier, a subsidiary of the assignee of these patents, as a spray-dried powder or moist cake.
The present in~ention is not limited by the method for making the fibrils and microf~brils. For example, it is thought that materials falling withln the scope of the invent~on can also be made by a process of ball-milling cellulos~c pulp.
Another method for obtaining cellulosic fibrils and m~crofibrils useful in the present inYention is by bacterial fer~entat~on of a sugar contain~ng solution. Particularly suitable sugar containlng solutions include coconut milk (Nata de Coco7Y) or pineapple(Nata de Pinan') solutions A bacteria culture acts on the sugar solution to spin out a mat ot cellulosic f~brils and microfibrils. This mat can then be redispersed in the present composttions to form the desired net~ork of fibrtls and microfibrils.
The polysaccharide fibrils and microfibrils of the in~entlon can also be obtained through appropriate processing ~`
of other polysaccharide fiber sources particularly celluloslc fibers. Such sources include fibrous fruits and vegetables for example orange pulp strawberry pulp apple pulp and food fiber from other sources.
Processing methods capable of produc~ng fibr~ls and microfibrils include other physical separation processes and fermentation processes. Other mater~als for example pectln may be present in the fiber source and these materials would be separated from the fibr~ls and m~crof~br~ls before use.
The polysaccharides can include other polysacchar~dic materials bes~des cellulose~ For example it ls thought that a net~ork of flbr~ls and m~croflbrils for use ~n the present inventlon can be obtained by fungal fermentatlon of a glucose-containing solutton to produce a 1 3-l~nked glucose-based polysaccharide.
Com~osit~ons Made with Preferred Polvesters Certain sugar and sugar alcohol fatty ac~d polyesters as described above ~n the sectton on liquid polyol polyesters have been dlscovered that do not cause a laxat~ve slde effect even at relat~vely lo~ levels of sol~ds. These polyesters are characterized as having the follow~ng propert~es at 100F
(37.~C): (a) a l~u~d/sol~d stab~l~ty of at least about 50X
preferably at least about ~0~; and (b) a solid fat content bet~een about 5X and about 30X. Preferably the polyesters have a vlseos~ty of at least about 1.0 poise more preferably at least about 5.0 polse after 10 minutes of steady shear at a shear rate of 10 seconds-l. The methods of measurtng vlscosltr and l~quid/solid stab~l~ty are descr1bed below in the Analrtlcal Methods sectlon.
These polyesters preferably have a soltd fat content (SFC) at 100F (3~.8C) between about SX and about 25X more preferably between about lOX and about 20X.
Therefore a preferred embodlment of the present lnvention is a lo~ calorie fat subst~tute composlt~on as described hereinabove comprising a liquid polyester; at least about lOX solid low calorie fat subst~tute by we~ght of the liquid polyester; at least about lX polysaccharide fibrils and microfibrils; and additionally comprising a sugar fatty acid polyester or sugar alcohol fatty acid polyester, or m~xtures thereof, having the above-described stability, SFC, and preferably viscosity at 100F t37.8C).
Moreover, compositions can be made that are very res~stant to laxative s~de effect even w~thout the use of sol~d low calor~e fat substitutes, ~f the compos~t~ons conta~n a suff~c~ent amount of the above-descrtbed preferred polyesters. Hence, another embod~ment of the present ` inventlon ~s a low calorle fat substitute composition -~- compr~stng from about lX to about 42X by weight liquid polyol fatty acid polyester; fro~ about lX to about 15X by welght of a cohes~ve network of polysacchartde fibrils and mtcrof~br~ls;
and from about 43X to about 98X by we~ght low calorie fat subst~tute selected from the group consist~ng of sugar fatty ac~d polyesters, sugar alcohol fatty acid polyesters, and mixtures thereof, the sugars and sugar alcohols containing from ~ to 8 hydroxyl groups, and each fatty acid group hav~ng from about 8 to about 22 carbon atoms, wherein the fat substttute has, at 100F (3~.8C): (a) a llquld/sol~d stabll~ty of at least about 50X, preferably at least about ~OX; and (b) a solld fat content between about 5% and about 30X. Preferably the polyesters have a v~scosity of at least about I potse, more preferably at least about 5 po~se, after 10 mtnutes of steady shear at a shear rate oF 10 seconds~l.
Htghly preferred polyesters havlng the above-described properttes are sucrose fatty acld polyesters. Preferred sucrose fatty acid polyesters have the ma~or~ty of their hydroxyl groups esterif~ed with fatty acids. Preferably at least about 85X, and most preferably at least about 95%, of the sucrose fatty acid polyesters are selected from the group consisting of octaesters, heptaesters and hexaesters, and mixtures thereof. Preferably, no more than about 35% of the esters are hexaesters or heptaesters, and at least about 60%
of the sucrose fatty acid polyesters are octaesters. Most preferably, at least about 70% of the polyesters are octaesters. It is also most preferred that the polyesters have a total content of penta- and lower esters of not more ~ than about 3X
-- Preferably at least about 80%, and most preferably at least about 90%, of the fatty acids of the sucrose polyesters are selected from the group consisting of m~xtures of palmitic, stearic, oleic, linole~c, and behenic acids. It is also most preferred that at least about 80X of the fatty acids are selected from the group consisting of mixtures of C16 to C18 fatty acids.
The fatty acids of the sucrose polyesters can be saturated, unsaturated, or mixtures thereof. The unsaturated fatty acids can include positional and geometric isomers (e.g~, Çi~ and trans isomers), or mixtures thereof.
~O More speciflcally, the following is a preferred fatty acid composit~on: from about 9X to about 12X palmitic; from about 35X to about 53X stearic; from about 19X to about 43X
oleic; from about 2X to about 1~X l~nolelc; from about 0% to about 2X linolenic; from about OX to about 2X arachid~c; from about OX to about 10X behenlc; and from about 0% to about 2%
erucic~
Sucrose fatty acid polyesters hav~ng the above-descr~bed liquid/solid stability, solid fat content and v~scosity can be made, for example, by esterifying sucrose with methyl esters of a fully hydrogenated soy oil (Iodlne Value about 1) and a partlally hydrogenated soy oil (Iodine Yalue about 107J, blended in a 57:43 rat~o~
Uses of the Low Calorie Fat Substitute ComDositions The present low calorie fat substitute compositions are useful in a wide variety of food and beverage products. For example, the compositions can be used in the production of baked goods in any form, such as mixes, shelf-stable baked - goods, and frozen baked goods. Possible applicatlons include, but are not limited to~ cakes, browntes, muffins, bar cookies, wafers, biscuits, pastries, pies, pie crusts, and cookies, including sandwich cookies and chocolate chip cookies, particu?arly the storage-stable dual-textured cook~es described in U.S. Patent 4,4~,333 of Hong ~ Brabbs. ~he baked goods can conta~n fruit, cream, or other fillings.
Other baked good uses include breads and rolls, crackers, pretzels, pancakes, waffles, ice cream cones and cups, yeast-ra~sed baked goods, pi~zas and pizza crusts, baked far~naceous snack foods, and other baked salted snacks.
The composit~ons can be used to make shortening and oil products, such as shortenings, margarines, spreads, butter blends, lards, cooklng and frying oils, salad o~ls, popcorn ~o oils, salad dressings, mayonnaise, and other edible oils.
The low calorie fat substitute compositions of the present invent~on can be fortified with vitamins and minerals, particularly the fat-soluble vitamins. The fat-soluble v~ta~ins ~nclude ~itamin A, vitamin D, vitamtn E ~tocopherol), 2s and vltamin K. Four different tocopherols have been identlf~ed (alpha, beta, gamma and delta), all of which are otly, yello~ u~ds, insoluble in water but soluble in fats and o~ls. If deslred, the compos~t~ons can be fortif~ed w~th a recommended dally allowance (RDA), or lncrement or multiple of an RDA, of any of the fat-soluble vitamins or comb~natlons thereof. The present compositlons preferably contaln about 1.1 mg. of Vitamin E as d-alpha tocopheryl acetate per 1000 grams of polyol polyester.
The present compositions are particularly useful in combination with particular classes of food and beverage ingredients. For example, an extra calorie reduction benefit is achieved when the compositions are used with noncaloric or reduced calorie sweeteners alone or in combination with bulking agents. Noncalori~ or reduced calorie sweeteners include, but are not limited to, aspartame; saccharin;
alitame, thaumatin; dihydrochalcones; cyclamates; steviosides;
glycyrrhizins, synthetic alkoxy aromatics, such as Dulcin~ and P-4000~; sucrolose; suosan; miraculin; monellin; sorbitol;
xylitol; talin; cyclohexylsulfamates; substituted imidazolines; synthetic sulfamic acids such as acesulfame, acesul~am-K and n-substituted sulfamic acids; ox~mes such as périlartine; rebaudioside-A; peptides such as aspartyl malonates and succanilic acids; dipept~des; amino acid based sweeteners such as gem-diaminoalkanes, meta-aminoben20ic acid, L-aminodicarboxylic acid alkanes, and amides of certain alpha-aminodicarboxylic ac~ds and gem-diamines; and 3-hydroxy-4-alkyloxyphenyl al~phat~c carboxylates or heterocyclic aromat~c carboxylates;
The composit~ons can be used in combinat~on with other noncaloric or reduced calor~e fats~ Examples of such materials are: fatty alcohol esters of polycarboxylic acids (U.S. Patent 4,508,746 of Hamn, assigned to CPC Internat~onal, Inc~, issued Apr~l 2, 1985); fatty polyethers of polyglycerol (U.S. Patent 3,932,532 of Hunter et al., ass~gned to ICI
Un~ted States, Inc., issued January 13~ 1976) (food use d~sclosed in German Patent 207,07~, issued Feb. 15, 1984));
ethers and ether-esters of polyols contaln~ng the neopentyl ~o~ety (U.S. Patent 2,962,419 of Mln~ch, issued Nov. 29, 1960); fatty alcohol d~esters of dicarboxylic ac~ds such as malonic and succinic acid (U.S. Patent 4,582,927 of Fulcher, assigned to Frito-Lay, Inc., issued April 15, 1986);
tr~glyceride esters of alpha branched chain-alkyl carboxyl k ac~ds (U.S. Patent 3,579,548 of ~hyte, assigned to The Procter . ~ 6amble Co., issued May 18, 1971~; fatty acid diglyceride, .~ .
diesters of dibasic acids (U.S. Patent 2,874,175 ta Feuge et al.); polyorganosiloxanes (European Patent Application 205,273 to Frye); and alpha-acylated glycerides (U.S. Patent 4,582.715 to Volpenhein).
Other partial fat replacements useful in combination with the present compositions are medium chain triglycerides, highly esterified polyglycerol esters, acetin fats, plant sterol esters, N-Oil, polyoxyethylene esters, jojoba esters, mono/diglycerides of fatty acids, mono/diglycerides of o short-chain di~asic acids, silicone oils/s~loxanes (see, e.g., European Patent Application 205,273 of Dow Corp., Simplesse (NutraSweet Co.), Olestrin (Reach Associates), and esterified epoxide-extended polyols (see uropean Patent Application 254,547 of Atlantic Richfield 15 Co.).
Bulk~ng or bodying agents are useful in combination with the present compositions in many foods. The bulking agents can be nond~gestible carbohydrates, for example, polydextrose and cellulose or cellulose derivati~es, such as carboxymethylcellulose, carboxyethylcellulose, hydroxy-propylcellulose, methylcellulose and microcrystall~ne cellulose. Other suitable bulking agents include gums (hydro-colloids~, starches, dextrins, fermented whey, tofu, maltodextr~ns, polyols, including sugar alcohols, e.g.
sorbltol and mannltol, and carbohydrates, e.g. lactose.
Analvt~cal Methods 1. V~scos~tv Measurement A. Sample PreDaration ~he polyol fatty acid polyester sample is heated unt~l it completely melts and is thoroughly mixed. Ten grams of the melted sample is weighed into a preheated 20 ml glass vial.
~he sarple is then allowed to recrystallize at 100F + 5F
(37.8C + 3C) for 24 hours. After the 24 hour time period has elapsed, the sample is taken to the viscometer and the ~ viscosity is measured.
- B. Viscometer Operation Procedure A Ferranti-Shirley plate and cone viscometer (Ferrant~
Electric, Inc., 87 Modular Ave., Commack, NY 11725~ equlpped with a 600 9 torque spring is used for the v~scos~ty measurement. A cone is put into place, and the viscometer temperature is ad~usted to 100F (3~.8C). The chart recorder is calibrated, and the gap between the cone and plate is set.
The cone speed is checked, and the cone and plate temperatures are equilibrated to 100F (3~.8C). The panel controls are set. Sufflcient sampl~ ~s placed between the plate and the cone so that the gap is completely ftlled. The temperature is allo~ed to stabili2e at 100F (37.8C~ for about 30 seconds.
Start the test by selectlng the RPM for 10 seconds l shear rate and record on the strlp chart recorder. Record the shear stress at the maximum value for to and then for two 30-second ~ntervals, followed by every minute thereafter untll the value at 10 minutes ls recorded~ Ylscoslty tpolse) ~ shear stress (dynes/o~2~ dlvlded by shear rate (second-l).
II. Llauld/Solld Stab~litv Measurement A polyol fatty acld polyester sample is heated untll ~t co~pletely ~elts and ~s thoroughly m~xed. The sample ls then poured lnto Becb~n #3 U 062 ~.~ ml tubes to capaclty. The tubes are lrmedlately transferred to a 100F ~ 5F (37.8C
3C) constant te~perature room and allowed to recyrstalll2e undlsturbQd for 2~ hours. The samples are then centrifuged at 60,000 rpe for one hour at 100F (37.8C). The force on the samples ls U6,000 g's. The percent llquld separated ls then measured by comparing the relatlve helghts of the llquid and solld phases. Llquld/solld stablllty (X) ~ 100 x (total volume of sa~ple ^ volume of llquld that separated)/total volu~e of sample.
III. Solid Fat Content Measurement Before determining SFC values, the polyol fatty acid polyester sample is heated to a temperature of 158F (70C) or higher for at least 0.5 hours or unt11 the sample is completely melted. The melted sample is then tempered at a temperature of 40F (~.4C) for at least 72 hours. After ~ tempering, the SFC value of the polyester at a temperature of 100F (37.8C) is determined by pulsed nuclear magnetic resonance (PNMR). The method for determining SFC values by PNMR is described in Madison and Hill, J. Amer. Oil Chem.
Soc., vol 55 (19~8), pp. 328-31 (herein ~ncorporated by reference3. Measurement of SFC by PNMR is also described in A.O.C.S. Official Method Cd. 16-81, Qfficial Methods and Recommended Practice~ of The Ameri~an Oil Chemis~s SocietY, 3rd Edition, 1987.
The following examples are intended only to further illustrate the invention and are not intended to limit the scope of the invention which is defined by the claims.
A sucrose fatty acid polyester composition is prepared by co~bining liquid SUCrOSQ polyester, solid sucrose polyester, and mtcrofibrillated cellulose:
~1 : . , '' ~
Inaredients ~ %
Liquid sucrose polyester* 164 9. 76%
Solid sucrose polyester** 37 9. 17%
Microfibrillated cellulose***15 9. 7Z
*Sucrose octaoleate, iodine value 107 **Mixed hexa-, hepta- and octaesters of sucrose esterified with mixed soybean oil fatty aclds, and hydrogenated to an iodine value of 8 ***Microfibrillated cellulose, ITT Rayonier Forest Products The.solid sucrose polyester is added to the ltquid sucrosa polyester, and the mlxture is heated to about 160-170F (~1-7~C). The mixture is maintained at this temperature for about 15 minutes, with frequent stirring.
~hile continuing to maintain the temperature, the microfibrillated cellulose f~bers are then dispersed in the polyester mixture by slow addition using a standard kitchen mixer set at low speed, to make a uniform dispersion. The composition is then cooled rapidly by placing the mixing bowl into an ice water bath, and mixing at low speed until the dispers~on is agaln uniform. Lastly, the composit~on is placed ~n a sealed glass ~ar and blanketed with nitrogen for storagc.
The compos~tion is very resistant to laxatlve side effect -~ 25 after lngestion.
Three kinds of sucrose fatty acid polyester compositions are made and tested for laxatlve side effect:
` 1326162 Com~ition A
Inaredlents Liqu1d sucrosa polyester~ 94X
Mlcroflbrlllated cellulose~ 6X
ComDosltlon B
Inared~ents Liquld sucrose polyester~ ~6X
Solid sucrose polyester~ 2~%
ComDosit1Qn C:
Insr~D~
Llquld sucrose polycster~ J6X
Solld sucrose polyester~* l~
Mlcrof1brillat d cellulose~ X
~Sucrose oct~oleato lodlne value lO~
~Mlx d hex~- hopt~- ~nd oct~esters of sucrose esterlfl d ~lth ~lxRd soybean oll f~tty aclds ~nd hydrogen~t d to ~n lodlne value of 8 1croflbrlllat t ecllylose IIT R yonler For st Produets Co posltlon A ls found to be lneff etlvc ln laxatlve slde effeet r ductlon L~x~tlvo sldo eff ct ls r duc t ln both Corposltlon 8 ~nd Co~posltlon C but Composltlon C ls found to b~ ~n ~pro~ _ nt over Co~poslt10n B. It ls concluded that the threo p~rt mlxture of llquld sucros- polyester solld sucros- pol~ester and mlcroflbrlllat d cellulose ls more reslstant to l x~tlve slte effect th~n the e~o part mlxture of llquld ~nd solld suc n se polyester and much more reslst~nt than the t~o part mlxture of llquld sucrose polyester and mlcroflbrlll~t t cellulose ,~
ExamDl~ 3 A composition is made as in Example 1, except that the composition contains 46X liquid sucrose polyester, 7%
microfibrillated cellulose, and 47% of a sucrose fatty acid polyester made by esterifying sucrose with methyl esters of a fully hydrogenated soy oil (IV about 1) and a partially hydrogenated soy oil (IV about 107), blended in a 47:53 ratio.
The latter suerose polyester has the following properties:
:;
ViscositY 25.9 poise After 10 min. steady shear at shear rate of 10 seconds~l Liquid/Solid Stability 92.5%
SFC at 100F (3~.8C) 10X
Fattv Acid Co~osition C16 9.8%
C16: 1 lO ` 50.6 C18:1 21.6 C18:2 15.~ ~
C18:3 1.0 Others 1.3 Iod~ne Value 48.6 Ester Distrlbutlon ` Oct~ 89.1X
Hept~ 10.9 Hex~ ~0. 1 ` 20 Pent~ <0.1 Lo~er <0.1
Claims (23)
1. A low calorie fat substitute composition comprising a liquid polyol fatty acid polyester, at least about 10% solid low calorie fat substitute by weight of the liquid fat polyester, and at least about 1% of a cohesive network of polysaccharide fibrils and microfibrils by weight of the liquid polyester.
2. A composition according to Claim 1 comprising at least about 15% solid fat substitute by weight of the liquid polyester.
3. A composition according to Claim 1 comprising at least about 5% fibrils and microfibrils by wight of the liquid polyester.
4. A composition according to Claim 1 comprising from about 60% to about 89% by weight liquid polyol fatty acid polyester, from about 10% to about 25% by weight solid fat substitute, and from about 1% to about 15% by weight fibrils and microfibrils.
5. A composition according to Claim 4 comprising from about 70% to about 80% liquid polyester, from about 15% to about 20% solid fat substitute, and from about 5% to about 10%
fibrils and microfibrils.
fibrils and microfibrils.
6. A composition according to Claim 1 wherein the liquid polyol fatty acid polyester is selected from the group consisting of sugar fatty acid polyesters and sugar alcohol fatty acid polyesters, and mixtures thereof.
7. A composition according to Claim 6 wherein the liquid polyester is a sucrose fatty acid polyester.
8. A composition according to Claim 1 wherein the solid fat substitute is selected from the group consisting of sugar fatty acid polyesters and sugar alcohol fatty acid polyesters, and mixtures thereof.
9. A composition according to Claim 8 wherein the solid fat substitute is a sucrose fatty acid polyester.
10. A composition according to Claim 1 wherein the cohesive network of fibrils and microfibrils has a surface area of from about 100 to about 170 m2/g.
11. A composition according to Claim 1 wherein the polysaccharide fibrils and microfibrils are cellulosic fibrils and microfibrils.
12. A composition according to Claim 11 wherein the fibrils and microfibrils comprise microfibrillated cellulose.
13. A composition according to Claim 1 wherein the polysaccharide fibrils and microfibrils are obtained by bacterial or fungal fermentation of a sugar-containing solution.
14. A composition according to Claim 1 additionally comprising a low calorie fat substitute selected from the group consisting of sugar fatty acid polyesters, sugar alcohol fatty acid polyesters, and mixtures thereof, the sugars and sugar alcohols containing from 4 to 8 hydroxyl groups, and each fatty acid group having from about 8 to about 22 carbon atoms, wherein the fat substitute has, at 100°F (37.8°C):
(a) a liquid/solid stability of at least about 50%; and (b) a solid fat content between about 5% and about 30%.
(a) a liquid/solid stability of at least about 50%; and (b) a solid fat content between about 5% and about 30%.
15. A low calorie fat substitute composition comprising from about 1% to about 42% by weight liquid polyol fatty acid polyester; from about 1% to about 15% by weight of a cohesive network of polysaccharide fibrils and microfibrils; and from about 43% to about 98% by weight low calorie fat substitute selected from the group consisting of sugar fatty acid polyesters, sugar alcohol fatty acid polyesters, and mixtures thereof, the sugars and sugar alcohols containing from 4 to 8 hydroxyl groups, and each fatty acid group having from about 8 to about 22 carbon atoms, wherein the fat substitute has, at 100°F (37.8°C):
(a) a liquid/solid stability of at least about 50%; and (b) a solid fat content between about 5% and about 30%
(a) a liquid/solid stability of at least about 50%; and (b) a solid fat content between about 5% and about 30%
16. A composition according to Claim 15 wherein the liquid polyester is a sucrose fatty acid polyester.
17. A composition according to Claim 15 wherein the low calorie fat substitute is a sucrose fatty acid polyester.
18. A composition according to Claim 15 wherein the cohesive network of fibrils and microfibrils has a surface area of from about 100 to about 170 m2/g.
19. A composition according to Claim 15 wherein the polysaccharide fibrils and microfibrils are cellulosic fibrils and microfibrils.
20. A composition according to Claim 19 wherein the fibrils and microfibrils comprise microfibrillated cellulose.
21. A composition according to Claim 15 wherein the polysaccharide fibrils and microfibrils are obtained by bacterial or fungal fermentation of a sugar-containing solution.
22. A food composition comprising non-fat ingredients and fat ingredients, wherein up to about 100% of the total fat ingredients is a composition according to Claim 1.
23. A food composition comprising non-fat ingredients and fat ingredients, wherein up to about 100% of the total fat ingredients is a composition according to Claim 15.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US21180288A | 1988-06-27 | 1988-06-27 | |
| US211,802 | 1988-06-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1326162C true CA1326162C (en) | 1994-01-18 |
Family
ID=22788421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000603934A Expired - Fee Related CA1326162C (en) | 1988-06-27 | 1989-06-26 | Low calorie fat substitute compositions resistant to laxative side effect |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US5006360B1 (en) |
| EP (1) | EP0352907B1 (en) |
| JP (1) | JP2804091B2 (en) |
| AU (1) | AU626552B2 (en) |
| CA (1) | CA1326162C (en) |
| DE (1) | DE68914742T2 (en) |
| DK (1) | DK319589A (en) |
| HK (1) | HK117196A (en) |
| IE (1) | IE62783B1 (en) |
| MY (1) | MY106082A (en) |
| NZ (1) | NZ229720A (en) |
| PH (1) | PH26707A (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8829833D0 (en) * | 1988-12-21 | 1989-02-15 | Unilever Plc | Low-calorie food products |
| EP0434164A3 (en) * | 1989-12-21 | 1993-01-13 | Unilever N.V. | Frying-fat composition |
| ATE147587T1 (en) * | 1990-07-20 | 1997-02-15 | Unilever Nv | EDIBLE COMPOSITION CONTAINING FAT |
| WO1992007475A1 (en) * | 1990-10-31 | 1992-05-14 | The Procter & Gamble Company | Calcium fortified sauces |
| US5230913A (en) * | 1991-03-01 | 1993-07-27 | Nabisco, Inc. | Fat mimetic having mineral core with fatty coating |
| US5366753A (en) * | 1991-03-29 | 1994-11-22 | Curtice-Burns, Inc. | Fat substitute compositions having reduced laxative effects at low levels of inclusion |
| US5294451A (en) * | 1991-03-29 | 1994-03-15 | Curtice-Burns, Inc. | Fat substitute compositions having reduced laxative effects |
| ES2146350T3 (en) | 1991-06-25 | 2000-08-01 | Danisco Finland Oy | LOW CALORIE FAT SUBSTITUTE. |
| DE69212836T2 (en) * | 1991-09-03 | 1997-02-20 | Procter & Gamble | USE OF HYDROPHOBIC SILICA TO LIMIT OR PREVENT PASSIVE OIL LOSS |
| JPH0568478A (en) * | 1991-09-17 | 1993-03-23 | Daicel Chem Ind Ltd | Agent for improving water retention of fat and oil composition |
| US5492715A (en) * | 1994-03-31 | 1996-02-20 | Greenland; Frederick A. | Dual function fruit concentrate sweetener and fat substitute and method of making |
| DE19628324A1 (en) * | 1996-07-13 | 1998-01-15 | Hocepro Gmbh I G | Cellulose fibrils |
| JP2003512343A (en) | 1999-10-15 | 2003-04-02 | ダニスコ カルター アメリカ，インコーポレイテッド | Method for direct esterification of sorbitol with fatty acids |
| US6361817B1 (en) | 1999-12-17 | 2002-03-26 | Bestfoods | Low calorie nut butters |
| KR101040446B1 (en) * | 2002-04-19 | 2011-06-09 | 맷슨 테크놀로지, 인크. | System for depositing a film onto a substrate using a low vapor pressure gas precursor |
| ATE541562T1 (en) * | 2002-06-17 | 2012-02-15 | Taro Pharmaceuticals Usa Inc | IBUPROFEN SUSPENSION |
| US20040097427A1 (en) * | 2002-08-13 | 2004-05-20 | The Iams Company | Method for controlling hairballs |
| WO2005076829A2 (en) * | 2004-02-05 | 2005-08-25 | Taro Pharmaceuticals U.S.A., Inc. | Stable loratadine spill resistant formulation |
| KR20090004838A (en) * | 2005-08-01 | 2009-01-12 | 씨피 켈코 유에스, 인코포레이티드 | Low-sediment acidic protein beverages |
| CA2839353C (en) * | 2011-06-23 | 2016-01-26 | The Procter & Gamble Company | Sucrose polyesters |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE207070C (en) * | ||||
| US2831854A (en) * | 1955-05-24 | 1958-04-22 | Procter & Gamble | Method for preparing fatty esters of non-reducing oligosaccharides in the presence of an amide |
| US2874175A (en) * | 1955-10-04 | 1959-02-17 | Reuben O Feuge | Process for making fatty acid diglyceride, diesters of dibasic acids |
| US2962419A (en) * | 1957-05-20 | 1960-11-29 | Heyden Newport Chemical Corp | Dietetic compositions |
| US3600186A (en) * | 1968-04-23 | 1971-08-17 | Procter & Gamble | Low calorie fat-containing food compositions |
| US3579548A (en) * | 1968-05-10 | 1971-05-18 | Procter & Gamble | Triglyceride esters of alpha-branched carboxylic acids |
| US3932532A (en) * | 1973-06-01 | 1976-01-13 | Ici United States Inc. | Ethers of polyglycerol |
| US3954976A (en) * | 1973-12-14 | 1976-05-04 | The Procter & Gamble Company | Pharmaceutical compositions for inhibiting absorption of cholesterol |
| US3963699A (en) * | 1974-01-10 | 1976-06-15 | The Procter & Gamble Company | Synthesis of higher polyol fatty acid polyesters |
| IE44458B1 (en) * | 1976-02-12 | 1981-12-02 | Procter & Gamble | Compositions for treating hypercholesterolemia |
| US4005195A (en) * | 1976-02-12 | 1977-01-25 | The Procter & Gamble Company | Compositions for treating hypercholesterolemia |
| US4005196A (en) * | 1976-02-12 | 1977-01-25 | The Procter & Gamble Company | Vitaminized compositions for treating hypercholesterolemia |
| US4374702A (en) * | 1979-12-26 | 1983-02-22 | International Telephone And Telegraph Corporation | Microfibrillated cellulose |
| US4304768A (en) * | 1980-03-31 | 1981-12-08 | General Foods Corporation | Low-calorie foods |
| US4378381A (en) * | 1980-10-31 | 1983-03-29 | International Telephone And Telegraph Corporation | Suspensions containing microfibrillated cellulose |
| US4341807A (en) * | 1980-10-31 | 1982-07-27 | International Telephone And Telegraph Corporation | Food products containing microfibrillated cellulose |
| US4461782A (en) * | 1982-02-16 | 1984-07-24 | The Procter & Gamble Company | Low calorie baked products |
| US4481076A (en) * | 1983-03-28 | 1984-11-06 | International Telephone And Telegraph Corporation | Redispersible microfibrillated cellulose |
| US4508746A (en) * | 1983-06-20 | 1985-04-02 | Cpc International Inc. | Low calorie edible oil substitutes |
| US4518772A (en) * | 1983-06-23 | 1985-05-21 | The Proctor & Gamble Company | Synthesis of higher polyol fatty acid polyesters using high soap:polyol ratios |
| US4517360A (en) * | 1983-06-23 | 1985-05-14 | The Procter & Gamble Company | Synthesis of higher polyol fatty acid polyesters using carbonate catalysts |
| US4582927A (en) * | 1984-04-04 | 1986-04-15 | Frito-Lay, Inc. | Synthetic cooking oils containing dicarboxylic acid esters |
| JPS61113601A (en) * | 1984-11-07 | 1986-05-31 | Ajinomoto Co Inc | Cellulosic macerated material and production thereof |
| US4582715A (en) * | 1984-12-04 | 1986-04-15 | The Procter & Gamble Company | Acylated glycerides useful in low calorie fat-containing food compositions |
| CA1300425C (en) * | 1985-06-10 | 1992-05-12 | Cecil L. Frye | Fat and oil replacements as human food ingredients |
| EP0236288B1 (en) * | 1986-02-20 | 1993-12-15 | The Procter & Gamble Company | Low calorie fat materials that eliminate laxative side effect |
| DE3788661T2 (en) * | 1986-02-20 | 1994-05-19 | Procter & Gamble | Low calorie fat products with improved taste. |
| US4861613A (en) * | 1986-07-25 | 1989-08-29 | Arco Chemical Technology, Inc. | Non-digestible fat substitutes of low-caloric value |
| US4774095A (en) * | 1986-12-16 | 1988-09-27 | The Procter & Gamble Company | Filling-containing, dough-based products containing cellulosic fibrils and microfibrils |
| EP0290216A3 (en) * | 1987-05-06 | 1990-05-30 | The Procter & Gamble Company | Polyol fatty acid polyesters for treating duodenal ulcers |
| US4925692A (en) * | 1988-11-07 | 1990-05-15 | Dow Corning Corporation | Food composition containing a siloxane polymer and a particulate silica |
-
1988
- 1988-06-27 US US07211802 patent/US5006360B1/en not_active Expired - Lifetime
-
1989
- 1989-06-23 DE DE68914742T patent/DE68914742T2/en not_active Expired - Fee Related
- 1989-06-23 EP EP89306407A patent/EP0352907B1/en not_active Expired - Lifetime
- 1989-06-26 IE IE207089A patent/IE62783B1/en not_active IP Right Cessation
- 1989-06-26 NZ NZ229720A patent/NZ229720A/en unknown
- 1989-06-26 CA CA000603934A patent/CA1326162C/en not_active Expired - Fee Related
- 1989-06-27 DK DK319589A patent/DK319589A/en not_active Application Discontinuation
- 1989-06-27 PH PH38868A patent/PH26707A/en unknown
- 1989-06-27 MY MYPI89000866A patent/MY106082A/en unknown
- 1989-06-27 JP JP1165133A patent/JP2804091B2/en not_active Expired - Lifetime
- 1989-06-27 AU AU37072/89A patent/AU626552B2/en not_active Ceased
-
1996
- 1996-07-04 HK HK117196A patent/HK117196A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0352907A2 (en) | 1990-01-31 |
| DK319589D0 (en) | 1989-06-27 |
| US5006360A (en) | 1991-04-09 |
| AU3707289A (en) | 1990-01-04 |
| IE892070L (en) | 1989-12-27 |
| DK319589A (en) | 1989-12-28 |
| NZ229720A (en) | 1992-01-29 |
| EP0352907B1 (en) | 1994-04-20 |
| MY106082A (en) | 1995-03-31 |
| PH26707A (en) | 1992-09-15 |
| HK117196A (en) | 1996-07-12 |
| JP2804091B2 (en) | 1998-09-24 |
| DE68914742T2 (en) | 1994-09-29 |
| US5006360B1 (en) | 1992-04-28 |
| IE62783B1 (en) | 1995-02-22 |
| JPH02109956A (en) | 1990-04-23 |
| EP0352907A3 (en) | 1991-08-07 |
| AU626552B2 (en) | 1992-08-06 |
| DE68914742D1 (en) | 1994-05-26 |
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