CZ406399A3 - Liquid indigestible oil and process for preparing thereof - Google Patents

Abstract

The liquid formulation comprises a liquid polyol polyester fatty acids having a melting point below 37 ° C and a solid polyol fatty acid polyester with a melting point of at least High: 37 ° C. and the solid polyol polyester fatty acid is solid saturated polyol polyester, solid alternately esterified polyol polyester, polymeric polyol polyester or combinations thereof which are co-crystallized together saturated polyol polyester to form common non-aggregated crystalline particles, typically less than 10 mm. Liquid preparation containing indigestible oil prepares the process of a complete melting process non-digestible oil and solid polyol step polyester while mixing to prevent formation clusters of fluidizing aggregation aggregates preparation.

Description

Liquid indigestible oil and method of preparation

Technical field

The present invention relates to an indigestible oil, the component of which is a solid indigestible oil. Indigestible oil is usually liquid at ambient temperature and storage. The invention also relates to a process for preparing an indigestible oil.

BACKGROUND OF THE INVENTION

There are a number of patents relating to materials that have both physical and taste parameters of triglyceride fats but are not absorbed by the body, or only to a minor extent. These materials are referred to as non-caloric fats, indigestible fats and fat replacers. Such materials are discussed, for example, in U.S. Pat. 4,582,927, Fulcher, Apr. 15, 1986 (malonic fatty esters); 4,582,715, Volpenhein, Apr. 15, 1986 (alpha acetylated triglycerides); and 3,579,548, Whyte, May 18, 1981 (alpha-branched carboxylic acid triglycerides).

One major non-digestible fat is sucrose polyester (i.e., sucrose in which at least eight hydroxyl groups are esterified with a fatty acid). This material and its use as indigestible fat in various food products are described in U.S. Pat. 3,600,186, Mattson, Jul 17, 1971; 4,368,213, Hollenbach et al., Jan. 11, 1983; and 4,461,782, Robbins et al., Jun. 24, 1984.

A problem accompanying the use of liquid indigestible oils, i.e. oils with a melting point below body temperature (37 ° C), is the effect of unwanted passive loss of oil caused by escaping liquid undigested fat through the anal sphincter of the gastrointestinal tract. Regular intake from small to large amounts of completely liquid forms of these polyol polyesters results in this passive loss. U.S. Pat. No. 4,005,195, Jandacek, Jan. 25, 1977, discloses a combination of protruding fat materials, such as solid triglycerides and solid sucrose polyesters, with liquid sucrose polyesters, whereby unwanted losses can be affected.

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U.S. Pat. No. 4,797,300 (Jandacek et al.), January 10, 1989, discloses the use of certain solid sucrose polyesters that bind liquid sucrose polyesters (SPEs) and liquid triglycerides when used in a concentration of 10 to 25 wt. voleji. It has been reported that these solid sucrose polyesters, due to their binding capacity, are excellent agents for preventing passive loss of liquid non-digestible sucrose polyesters and are also useful as a non-caloric solid carrier for liquid digestible and non-digestible oils in semi-solid food products such as baking fats and margarines . The building blocks of Jandacek U.S. Pat. No. 4,797,300 are solid sucrose polyesters wherein the ester groups are short chains of C2-10 saturated fatty acid ester radicals and mixtures thereof and long chains of C20-24 saturated fatty acid ester radicals of a short to long molar ratio of 3: 5 to 5: 3, and the degree of esterification of these sucrose polyesters is 7-8. Jandacek et al. It also describes plastic baking fats and other food products containing 10 to 25 wt. solid SPE.

U.S. Pat. No. 4,005,195 (Jandacek), Jan. 25, 1977, discloses a composition against undesired passive oil loss by adding polyesters as oil loss control agents. . These agents are solid fatty acids (melting point 37 ° C and above), triglyceride sources thereof, and solid polyol fatty acid polyesters. In particular, C10-22 saturated fatty acid polyesters are recommended in an amount of at least 10 wt%, preferably at least 20 wt%.

US 5,306,514 (Letton et al.), Apr. 26, 1994, discloses an edible oil composition comprising a) a liquid, non-digestible oil having a complete melting point below 37 ° C; and b) a solid polyol fatty acid polyester having a complete melting point above 37 ° C; the ratio of components b) to components a) is 1:99 to 9:91. The solid polyol fatty acid polyester comprises (i) a polyol with at least four hydroxyl groups, and at least four hydroxyl groups are esterified and (ii) ester groups including (a) fatty acid radicals selected from the group of C ₁₂ unsaturated fatty acids and higher, C2-12 saturated fatty acids, or mixtures thereof, and (b) C20 saturated fatty acid or higher radicals, in a molar ratio of (a) to (b) of from 1:15 to 1: 1. In solid polyol polyesters, at least 15 wt. C ₂ -based fatty acid radicals, or

- 3 higher. Furthermore, the slope of the SCF profile of mixtures a) and b) for 37 to 21.1 ° C is between 0 and -0.75.

US 5,306,514 (Letton et al.), Apr. 26, 1994, discloses liquid formulations comprising solid polyol polyester fatty acids of complete melting point above 37 ° C, liquid non-digestible oil of complete melting point below 37 ° C, less than 90% by weight. % digestible oil containing less than 5 wt. materials solids at 21 ° C and less than 10% solid filler; wherein the ratio of (A) to (B) is in the range of 1:99 to 9:91 and the liquid formulation has a permanent deformation limit at a maximum pressure of 10 Pa. The solid polyol fatty acid polyester comprises (i) a polyol having at least four hydroxyl groups and at least four hydroxyl groups are esterified, and (ii) ester groups consisting of (a) fatty acid radicals selected from the group C _J2 unsaturated fatty acids and higher C ₂ -i2 saturated fatty acids, or mixtures thereof, and (b) saturated or higher C ₂ radicals in a molar ratio of (a) :( b) in the range of 1:15 to 2: 1. In solid polyol polyesters, at least 15 wt. radicals derived from C ₂₀ saturated fatty acids or higher. Further, the slope of the SCF profile of mixture (A) and (B) for 37 to 21.1 ° C is between 0 and -0.75 and the total amount of (A) and (B) in the formulation is at least 10% by weight. Liquid formulations containing 65 wt. liquid digestible triglyceride oil.

The subject of the present composition is a liquid composition comprising an indigestible oil containing a solid component at ambient temperature, a composition which is liquid at ambient temperature and can be used as an edible indigestible oil satisfying the requirement of low passive loss and having good organoleptic properties in terms of food preparation.

SUMMARY OF THE INVENTION

The liquid composition comprising the non-digestible oil of the present invention comprises a) a liquid polyol fatty acid polyester having a complete melting point below 37 ° C; and b) a solid polyol fatty acid polyester having a complete melting point of at least 37 ° C. Liquid indigestible oil has a consistency (K) at a temperature of 20 to 40 ° C of less than 600 P.sec ^(n_1) , where K is determined from a particular form of force law

Obvious viscosity versus shear friction rate (see Analytical Procedures section) when the friction index (dimensionless) is present. Preferably, the liquid non-digestible oil has a consistency of less than 400 P.sec ⁽ⁿ ' ^{i :)} at 20 to 40 ° C. The liquid composition comprising an indigestible oil comprises a solid polyol fatty acid polyester in the form of small crystalline particles, typically having a largest dimension of less than 30 µm, preferably less than 10 µm, more preferably 1 to 30 µm, even more preferably 1 to 10 µm, most preferably 2 to 2 µm. 5 pm.

The present invention further provides a process for preparing a liquid non-digestible oil comprising a) a liquid polyol fatty acid polyester having a complete melting point below 37 ° C; and b) a solid polyol fatty acid polyester having a complete melting point of at least 37 ° C. The method comprises the step of completely melting the solid polyol fatty acid polyester, rapidly cooling the molten non-digestible oil to crystallization temperature, rapidly crystallizing a substantial portion of the solid polyol fatty acid polyester, and stirring the non-digestible oil composition during the crystallization step to produce a liquid composition containing the non-digestible oil. After the crystallization and stirring steps, a tempering step of the composition for a time sufficient to completely crystallize the solid polyol fatty acid polyester and a step of adding a stabilizing amount of a diluent liquid, typically a liquid polyol fatty acid polyester, to the crystallized non-digestible oil composition may be added.

These preparations can be stored in a liquid state at normal storage temperatures. Conventional storage temperatures are generally not higher than 50 ° C, which are temperatures usually associated with storing and processing the composition in the molten state. The manufacture and storage of the formulation in a liquid state simplifies handling at ambient and storage temperatures, minimizing the effect of higher temperature on the chemical stability of the polyol fatty acid polyester. This leads to higher oxidation stability and higher taste stability of food products containing indigestible oils. This property is particularly advantageous when the non-digestible oil component, the liquid polyol polyester fatty acid, is made from an uncured (non-hydrogenated) oil source, such as unhydrogenated cottonseed oil. The liquid indigestible oil of the present invention can further be used as a carrier for

a number of other ingredients in food products such as flavors, spices and vitamins.

Brief description of the pictures

Figures 1a to 1c show the sucrose octaester monomer, dimer and trimer.

Definition

The term indigestible means that the material is absorbed by a maximum of 70% by weight (preferably 20% by weight or less) of the human digestive tract.

The term liquid means the ability of the formulation to be transported by gravity or by conventional mechanical or pneumatic pumps from the container.

The term ambient temperature is a temperature lower than the lowest initial crystallization temperature of a solid polyol polyester which is a component of an indigestible oil formulation.

The term food refers to any use related to food. The term includes the individual components of the food products and mixtures thereof.

The term containing refers to the components which at the same time comprise the fat composition of the present invention. Thus, the term including includes a stricter expression consisting essentially of and consisting of.

All proportional data are by weight unless otherwise stated.

DETAILED DESCRIPTION OF THE INVENTION

High temperatures and the effect of oxygen on a product containing indigestible oil may lead to its thermal and oxidative degradation. It is therefore preferable not to store non-digestible oils at higher temperatures, such as in heated rail cars and production tanks, or temperatures that are otherwise necessary to maintain the composition in a liquid state.

It is therefore preferable to store and transport the indigestible oils at lower temperatures, i.e. ambient temperatures, and without oxygen, in order to avoid thermal or oxidative degradation and to improve the quality of the preparations containing indigestible oils and the foods containing them. At lower temperatures transport requirements can also be simplified, lower temperatures allow for cheaper and simpler transport devices for non-digestible oil formulations. The ambient temperature for safe transportation and storage is in the range of 5 to 50 ° C, preferably 20 to 40 ° C.

Commercial economical production of liquid, non-digestible oil formulations requires rapid manufacturing and product preparation that can be operated and stored at ambient temperature. Such a process typically must convert the non-digestible oil into a liquid form within 2 h, preferably within 30 min. For commercial reasons, the present indigestible oils have a satisfactory flowability, so that they leak completely due to gravity alone from containers such as railway tankers, truck tankers and production tanks. The present indigestible oils preferably do not adhere to the adhesive forces on the inner walls of the containers. Thus, liquid non-digestible oil is typically capable of flowing from a reservoir and leaving only a relatively thin residual film layer on the inner surface of the containers. Preferably, the indigestible oil is stable even during prolonged storage; that is, it remains in a liquid state, there is no or minimal phase separation or solid crystalline particle deposition.

A. Composition of liquid indigestible oil

A non-digestible oil liquid composition comprising a solid polyol fatty acid polyester having a complete melting point of at least 37 ° C and a liquid polyol fatty acid polyester having a complete melting point of less than 37 ° C can be prepared in a flowable form at ambient storage temperatures. This formulation, even after further processing, including complete re-melting of the solid polyol fatty acid polyester, preferably has a low passive loss and provides foods that contain good organoleptic properties (i.e., mouthfeel). The present liquid non-digestible oil composition comprises 50 to 99 wt%, more preferably 80 to 97 wt%. % and most preferably 85 to 95 wt. of a liquid polyol polyester fatty acid. The present liquid composition with indigestible oil contains 1 to 50 wt.

More preferably 3 to 20 wt. % and most preferably 5 to 15 wt. a solid polyol polyester fatty acid.

The liquid, non-digestible oil formulation typically has a consistency of less than 600 P.sec ^{(n -1)} at 20 to 40 ° C. The liquid preparation of digestible oil preferably has a consistency of less than 400 P.sec ^ '^, more preferably less than 200 P.sec (AD), and most preferably less than 100 P.sec ^{01' 1)} at 20 to 40 ° C.

Mixtures of the solid polyol polyesters of the present invention with liquid non-digestible oils can be further characterized by a relatively flat solids content profile over a wide temperature range, from typical room temperature to body temperature, i.e., between 21.1 and 37 ° C. The slope of the SFC profile is expressed as a change in the percentage of solids in one temperature unit, ° F. The typical slope of the SFC between these two temperatures is between 0 and -0.75. In general, the greater the percentage of C20 or higher saturated fatty acid radicals in the solid polyol polyester, the flatter the slope of the SFC profile. For example, at a content of 30 wt. C ₂ and higher fatty acids typically tend to be between 0 and -0.5; optionally between 0 and-0.3.

Determination of SFC values over a given temperature range can be performed by a method including PNMR (Pulse Nuclear Magnetic Resonance). This technique is known in the art and can be read in J. Amer. Chem. Soc. 55, (1978), 328-31 and in the AOCS Official Method Cd. 19-81, Official Methods and Recommended Practices of The American Oil Chemists Society, 3 ^rd Ed., 1987; works listed in the references.

Solid polyol polyester fatty acids

The present solid polyol fatty acid polyester has a complete melting point at at least 37 ° C (normal body temperature), preferably at least 50 ° C, most preferably at least 60 ° C and at most less than 500 ° C. The solid polyol fatty acid polyester is preferably selected from (i) solid saturated polyol polyesters, (ii) solid alternatively esterified polyol polyesters, (iii) polymer polyol polyesters, and (iv) combinations thereof.

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The polyols used in the solid polyol polyesters of the present invention preferably contain 4 to 12, more preferably 4 to 8, most preferably 6 to 8 hydroxyl groups. Examples of preferred polyols are sugars (monosaccharides, disaccharides and trisaccharides) and sugar alcohols containing 4 to 11 hydroxyl groups. The trisaccharides raffinose and malotriose are examples of sugars containing 11 hydroxyl groups. Preferred sugars and sugar alcohols contain 4 to 8, more preferably 6 to 8 hydroxyl groups. Examples of sugars containing 4 hydroxyl groups are the monosaccharides xylose and arabinose and sugar alcohol erythrite. Suitable polyols containing 5 hydroxyl groups are the monosaccharides galactose, fructose, mannose and glucose, and the sugar alcohol xylite. The 6 hydroxyl groups contain sorbitol. Examples of useful disaccharide polyols are maltose, lactose and sucrose, all containing 8 hydroxyl groups. Examples of other suitable polyols are pentaerythritol, diglycerol, triglycerol, alkyl glycosides and polyvinyl alcohols. A preferred polyol is sucrose.

The average degree of esterification of solid polyol fatty acid polyesters is at least 4 ester groups, i.e. at least 4 hydroxyl groups of the polyols are esterified with a fatty or other organic acid. Polyol polyesters containing 3 or less ester groups are usually digested in (digestion products are absorbed from) the digestive tract similar to conventional triglyceride fats or oils. Polyol esters with 4 or more ester groups are mostly indigestible and therefore not absorbed by the human body. It is not necessary for all hydroxyl groups of the polyols to be esterified, but it is preferred that the polyols contain no more than 3 unesterified hydroxyl groups, preferably at least 95% of the hydroxyl groups are to be esterified. In the case of sucrose polyesters, 7 to 8 hydroxyl groups are typically esterified.

i. Solid saturated polyol polyesters

The solid saturated polyol polyester comprises essentially and preferably only esters of long fatty acid radicals, typically normal, containing at least 14, preferably 14 to 26, more preferably 16 to 24 and most preferably 20 to 24 carbon atoms. Particularly preferred are C22 saturated acid radicals. Saturated long radicals

- 9string can be used in any combination. The average degree of esterification of these solid saturated polyol polyesters corresponds to the esterification of at least 4 hydroxyl groups of the polyol. In the case of sucrose saturated polyesters, 7-8 hydroxyl groups are esterified. Typically, at least 85%, preferably 95% of the hydroxyl groups are esterified.

Examples of suitable long chain saturated fatty acid radicals are tetradecanoate (myristate), hexadacnoate (palmitate), octadecanoate (stearate), eicosanoate (arachidate), docosanoate (behenate), tetracosanate (lignocerate), and hexacosanoate (cerotate). Mixtures of radicals from fully or predominantly hydrogenated vegetable oils containing a large amount of the desired long chain saturated fatty acids are also acceptable as a source of fatty acid radicals for the preparation of solid saturated polyol polyesters. The fatty acid mixtures of these oils should preferably contain at least 30% (preferably at least 50%, most preferably at least 80%) of the desired long chain saturated fatty acid. Suitable oil sources are wholly or predominantly hydrogenated soybean oil, cottonseed oil, palm oil, peanut oil, cereal oil, sunflower oil, sesame oil, low erucic acid rapeseed oil (i.e. canola oil) and high erucic acid rapeseed oil. . These oils are typically hydrogenated to an iodine level of 12 or less, preferably 8 or less.

Examples of solid polyol polyesters useful as solids in the fat compositions of the present invention are sucrose octabehenate, sucrose octastearate, sucrose octapamitate, sucrose heltastearate, xylite pentastearate, galactose pentapalmitate and hepta- and sucrose fatty acid octaesters with soybean oil and rapeseed fatty acids. acids which have been hydrogenated to an iodine level of 8 or less.

Solid saturated polyol polyesters usually crystallize themselves from the liquid formulation to form defined spherulitic particles, at an initial crystallization temperature or below. The initial crystallization temperature is the temperature at which the solid polyol polyester begins to crystallize in the liquid polyol polyester. That is, when a solid saturated polyol polyester is dissolved in a melt containing both solid and liquid polyol polyester, it has a saturated solid polyol polyester

The tendency to form well-defined, highly ordered, substantially spherical crystals, called spherulites, upon cooling to the initial crystallization temperature. In the absence of other solid indigestible oil or oil components, such as alternately esterified polyol polyester and polymeric polyol polyester, normally saturated polyol polyester crystallizes to form spherical particles, so-called spherulites, with a diameter (largest particle size) of 3 µm or more, usually 3 to 32 µm, the size being a function of the initial concentration of the solid saturated polyol polyester in the liquid polyol polyester and the stirring rate applied during the crystallization step. As is evident from the manufacturing process below, rapid cooling during the crystallization step with stirring results in discrete non-spherulitic particles, typically less than 30 µm, preferably less than 10 µm (some of the crystals are very small spherulites). In contrast, slow cooling and lower agitation rates result in slower crystallization and larger spherulitic particles.

When the solid saturated polyol polyester crystallizes together with other polyester components, such as the alternatively esterified and polymeric solid polyol polyester, the solid saturated polyol polyester does not tend to form highly ordered spherulites.

ii. Solid alternating esterified polyol polyesters

The solid, alternatively esterified polyol polyester of the present invention comprises polyol polyesters whose fatty acid radicals forming the ester groups are selected such that the polyol backbone does not contain all simple types of ester groups. In general, these polyol polyesters contain two basic types of ester groups. These are (a) ester groups derived from long-chain saturated fatty acids as described above, and (b) radicals other than those mentioned in (a). When these different ester radicals are introduced into a polyol molecule that already contains long chain saturated fatty acid esters, it causes different esterification of the resulting polyol polyester and also changes its crystalline form, since this type of material forms crystals that pack together during crystallization. The cause of this phenomenon is probably the difference in ester groups, such as different length of ester radicals (ie long against short chains), or other steric factors, eg branched against

- 11 unbranched, saturated against unsaturated, aromatic against aliphatic, etc. Polyol polyesters containing long chains and different ester groups are therefore referred to as solid, alternatively esterified polyol polyesters.

Solid alternately esterified polyol polyesters tend to form asymmetric or irregular molecular structures. It can be assumed that the asymmetric structure of these molecules affects the normal compositional properties of symmetric molecules of solid saturated polyol polyesters during co-crystallization in liquid polyol polyester. This circumstance usually prevents unrestricted three-dimensional growth of solid saturated polyol polyester polymers, induces some limitation, most often causing two-dimensional crystal growth, i.e., the formation of relatively thin platelet particles.

The different groups originate from the acid radicals of selected long chain saturated unsaturated fatty acids, short chain saturated fatty acids, other different fatty acids and mixtures thereof. Preferred different fatty acid radicals are long chain unsaturated fatty acid radicals.

Unsaturated fatty acid radicals, long chain are typically straight chain (i.e. normal) mono- and di-unsaturated, usually 12, preferably C ₂ -26, preferably _{C18. 2} 2, most preferably C ₁₈ . Examples of suitable long chain unsaturated fatty acid radicals for the present solid polyol polyesters are lauroleate, myristoleate, oleate, elaidate, erucate, linoleate, linolenate, arachidonate, eicosapentaenoate. From the viewpoint of oxidative stability, mono- and di-unsaturated fatty acid radicals are preferred.

Saturated fatty acid radicals, short chain are typically normal, usually 12, preferably Ce-N, most preferably C ₈ .i2. Examples of suitable short-chain saturated fatty acid radicals are acetate, butyrate, hexanoate (caproate), octanoate (caprylate), decanoate (caprate) and dodecanoate (laurate).

Other different ester-forming radicals include fatty acid radicals containing at least one hydroxyl group esterified with another fatty or other organic acid. Examples of this type of radicals are 12-hydroxy-9-octadecene.

-12 ricinoleic acid, 12-hydroxy-octadecanoic acid, 9-hydroxy-octadecanoic acid, 9-hydroxy-10,12-octadecanedioic acid, 9,10-dihydroxyoctadecanoic acid, 12,12-dihydroxyicosanoic acid and 18-hydroxy-9,11 13-octadecatrienoic acid (camolenic acid). A preferred hydroxy fatty acid is ricinoleic acid. Its preferred source is castor oil. Other sources of hydroxy fatty acids are hydrogenated castor oil, strontane oil, calendula officinalis seed oil, hydrogenated strofant oil and hydrogenated calendula officinalis seed oil. cress oil, camal oil, mallotus discolor oil and mallotus claoxyloides.

Some examples of solid polyol polyesters of the present invention are sorbitol hexaester containing palmitoleate and arachidate radicals in a molar ratio of 1: 2; rhaphose octaester containing linoleate and behenate radicals in a molar ratio of 1: 3; maltose heptaester containing sunflower oil radicals and lignocerate radicals in a molar ratio of 3: 4; sucrose octaester containing oleate and behenate radicals in a molar ratio of 2: 6; and an octaester of sucrose containing laurate, linoleate and behenate radicals in a molar ratio of 1: 3: 4. The preferred material is sucrose polyester having a degree of esterification of 7 to 8 and whose radicals are derived from C 18 mono- and di-unsaturated alkyls and behenate, in a molar ratio of 2: 6 to 1.5: 6.5.

iii. Solid polymer polyol polyesters

Solid polymer polyol polyesters are formed by polymerizing a polyol polyester monomer to a molecule comprising at least two separate esterified polyol groups linked by a covalent bond between the ester groups of these different polyol moieties. For example, two sucrose octabehenate monomers can be cross-linked between fatty acids to form a polymer. The repeating units of such polymeric polyol polyesters may be the same or different, so that the generic term "polymer" in this context includes the term "copolymer". The number of repeating monomers (or comonomers) forming said polymeric polyol polyester is in the range of 2 to 20, preferably 2 to 12. According to the method of preparation, the polymeric polyol polyesters are usually oligomers containing 2 to 4. · · «« «« «« «« «« «« «« «« «« «« «« «« «« «« « · ·· · ·

- 13 monomer units, ie dimers, trimers or tetramers. The most typical polymeric polyol polyester for the present purposes is a dimer.

If the polyol is sucrose in the polymeric polyester, it is preferably completely esterified with a fatty acid or other ester-forming acid radical. Sucrose, fully esterified polymeric polyesters are shown schematically in Figures 1a, 1b and 1c. At least 15%, preferably at least 45%, more preferably at least 75% and most preferably at least 90% of the hydroxyl groups of a polyol polyester polymer material should be esterified by C ₂ radicals (and longer) unsaturated fatty acids. Suitable polymeric sucrose polyesters have an average molecular weight of 4000 to 60,000, preferably 4000 to 36,000, more preferably 5000 to 12,000.

Suitable long chain saturated fatty acid radicals used to prepare the present polymeric polyol polyesters (and their monomers) are the same as those disclosed for the preparation of solid, alternatively esterified polyol polyesters. In the preparation of these polymeric polyol polyesters, as in the case of solid alternated esterified polyol polyesters, mixed fatty acid radicals from oils containing a significant amount of long chain saturated fatty acids required (i.e. at least 30% by weight, preferably at least 50% by weight) %, more preferably at least 80% by weight).

The polyol polyester material forming the solid non-digestible particles used in the present fat preparations typically contains 0 to 99 wt. % polymeric polyol polyester and 1 to 100 wt. % non-polymerized polyol polyester monomer components, preferably 0 to 90 wt. % polymeric component and 10 to 100% monomer component, more preferably 0 to 70% wt. % polymeric component and 30 to 100% monomer component, most preferably 0 to 50% wt. polymeric components and 50 to 100% monomer component.

2. A process for producing solid polyol fatty acid polyesters

Solid polyol polyesters of fatty acids, including solid saturated polyol polyesters, solid alternatively esterified polyol polyesters, and solid polymer polyol polyesters used in the present invention, can be prepared by known methods.

-14 techniques techniques. Since the preferred solid polyol polyesters for the present purposes are sucrose-based polyesters, the preparation of this type of materials is primarily disclosed.

One method of preparation is the reaction of fatty acyl chlorides with sucrose. In this process, a mixture of acyl chlorides or a fatty acid anhydride and sucrose reacting in one step is used, or the acyl chlorides react successively with sucrose. Another method of preparation is the reaction of fatty acid methyl esters with sucrose in the presence of fatty acid soaps and a basic catalyst such as potassium carbonate. See, e.g., U.S. Pat. 3,963,699, Rizzi et al., June 15, 1975; Nos. 4,518,772c, Volpenhein, May 21, 1985 and 4,517,360, Volpenhein, May 14, 1985, and U.S.S.N. 417,990 Letton, submitted October 6, 1989, all incorporated herein by reference. Methods for preparing polymeric polyol polyesters are described in U.S. Pat. No. 5,451,416, September 19, 1995 (Johnston et al.), Incorporated herein by reference.

In the case of the methyl ester route for the preparation of solid polyol polyesters, the fatty acid methyl esters are mixed in the desired ratio and reacted with sucrose by transesterification to produce sucrose esters of mixed unsaturated / saturated or saturated fatty acids. A preferred embodiment of this process operates with 5 moles of a mixture of mixed unsaturated / saturated or saturated fatty acid methyl esters reacting with sucrose at 135 ° C in the first step to form partial sucrose esters. A further 9 moles of the ester mixture are then added and the reaction is continued at 135 ° C under reduced pressure until the desired degree of esterification is achieved.

If the solid polyol polyester comprises two or more types of polyol polyesters, i.e. solid saturated polyol polyester, solid alternately esterified polyol polyester and polymer polyol polyester, these components may be incorporated into the non-digestible oil formulation separately or alternatively, these components may be prepared and blended beforehand and then incorporated into the digestible oil formulation. If the composition comprises a solid saturated polyol polyester and a solid alternately esterified polyol polyester, it is preferable to prepare the two solid polyesters together in the same esterification reaction. A preferred method of preparation is the esterification of a mixture of polyols with a mixture of alkyl esters of long chain saturated fatty acids (preferably methyl esters), alkyl esters of different fatty acids (preferably methyl esters) selected from alkyl esters of saturated fatty acids

-15 • 4 ** 4

4 · 4 4 4 44 4 4 4 4 • · 4 4 · 4 4 4 4 • 4499 «4 4 · 9 4 44 4 • · 444 4 4 4 4

444 «44 444 44 44 short chain, alkyl esters of long chain unsaturated fatty acids, alkyl esters of different acids and mixtures thereof. In the joint preparation, the polyol hydroxyl groups are completely randomized by the esterification of long-chain saturated fatty acids and radicals of different fatty acids. In order to ensure that some of the solid polyol polyesters are esterified solely by long chain saturated fatty acid radicals, the mixture of radicals must contain a higher proportion of long chain saturated fatty acid radicals over radicals of different acids. For example, sucrose contains 8 esterifiable hydroxyl groups. Depending on the length of the ester chain and other operating conditions, if a significant amount (10% by weight or more) of octanated and hepta-saturated sucrose polyesters is desired, a mixture of methyl esters of long chain saturated fatty acids and methyl esters of long chain unsaturated fatty acids is appropriate. saturated to unsaturated 6: 2 or higher. For example, a preferred solid polyol polyester is used the molar ratio of 6.5: 1.5 ₂ C 2 saturated fatty acid ester to a cotton oil contains about 73% unsaturated components). As a result, the content of 20 mol% of octanated and hepta-saturated sucrose polyesters (as solid saturated polyol polyester) and the remainder (i.e. 80 mol%) of the polyesters are substantially octa- and hepta-substituted, containing a mixture of long chain saturated fatty acid radicals and long chain unsaturated fatty acid radicals (such as a solid, alternatively esterified polyol polyester). An increasing proportion of long chain saturated fatty acid radicals over unsaturated radicals results in a higher proportion of solid polyester converted to saturated polyol polyesters; in contrast, a decreasing proportion of long chain saturated fatty acid radicals over unsaturated radicals results in a lower proportion of solid polyester converted to saturated polyol polyesters.

Mixed fatty acid radicals derived from sources containing a substantial amount of the desired unsaturated or saturated acids can also be used to prepare the present compounds. The mixed fatty acid radicals from oils should contain at least 30 wt. (preferably at least 50 wt.%, most preferably at least 80 wt.%) of the desired unsaturated or saturated acids. For example, instead

Pure C12-26 unsaturated fatty acids can be used with fatty acid radicals from rapeseed or soybean oil. Hardened (i.e. hydrogenated) fatty acids from rapeseed oil can be used instead of pure C-26 ₂ a saturated fatty acid. Advantageously, the higher C ₂ acids (or derivatives thereof - e.g. methyl esters) can be concentrated, eg, by distillation. Oil fatty acids kemelové palm or coconut oil can be used as a source of _C8 _i ₂ acids. An example of the use of source oils in the preparation of the solid polyol polyesters of the present invention is the preparation of a solid sucrose polyester using fatty acids from sunflower oil containing a high proportion of oleic acid and completely hydrogenated high erucic acid rapeseed oil. After complete esterification of sucrose with a mixture (1: 3 parts by weight) of methyl esters of fatty acids derived from these sources, the resulting sucrose polyester will contain unsaturated C ₁₈ radicals and saturated C ₂ radicals higher than 1: 1a.

28.6 wt. of the total amount of fatty acids in the polyester will be C ₂ O and C ₂₂ fatty acids. The higher the proportion of desired unsaturated and saturated fatty acids in the preparation of the solid polyol polyester, the more efficiently the solid polyester formed binds liquid oils.

One method of preparing these materials is to synthesize monomeric polyol polyester according to known methods of esterification, transesterification and / or interesterification and subsequent polymerization of the monomers. The polymerization can be initiated and performed in a number of ways, including, for example, photochemical reactions, reactions with transition metal ions, heat, using free radical initiators such as di-t-butyl peroxide.

Alternatively, polymeric polyol polyesters may be prepared directly by esterification and / or interesterification of polyol materials with polybasic polymerized fatty acids or derivatives thereof. For example, polymeric polyol polyesters can be prepared by reacting the acyl chlorides or anhydrides of the desired esterifying polymeric acids with sucrose, preferably using sequential esterification as described in the preparation of the alternatively esterified polyol polyesters. Polymeric polyol polyesters can also be prepared by reacting methyl esters of the desired polymeric acids with sucrose in the presence of fatty soaps and a basic catalyst, e.g., potassium carbonate,

as also described for the preparation of alternatively esterified polyol polyesters.

Using the above processes for preparing sucrose polyester materials containing both non-polymeric and polymeric fatty acids, the molar ratio of the non-polymeric material to the polymeric polymer is in the range of 2: 6 to 4: 4.

A variety of pre-polymeric fatty acids can be used in the selection of acyl chloride or methyl ester processes for esterifying a polyol with an already polymerized fatty acid. One class of suitable polymerized fatty acids comprises an aliphatic dibasic acid with a long chain C ₂₃ -44. They are usually prepared by polymerizing unsaturated C 14.22 fatty acids. E.g. Linoleic acid can be polymerized by heat to form linoleic acid:

heat

2CH ₃ (CH ₂ ) ₅ CH = CH-CH = (CH ₂ ) ₇ COOH ->

CH ₃ (CH ₂ ) ₅ CH-CH-CH = (CH ₂ ) ₇ COOH

CH ₃ (CH ₂ ) ₅ CH-CH CH- (CH ₂ ) ₇ COOH CH = CH

General examples of polymerizable acids of this type are those containing multiple double bonds (polyunsaturated acids), such as octadecadienic acids containing two double bonds, e.g., linoleic and octedecatrienic acids containing three double bonds, such as linolenic or eleostearic acid. Other common polymerizable C ₁₄ polyunsaturated acids. ₂₂ that can be used to esterify polyols and thus form the present polymeric polyol polyesters are octadecatrienoic acid (e.g., likanic acid), actadectetraenoic acid (e.g., parinarboxylic acid) eicosadienoic acid, eicosatrienic acid (arachidonic acid), 5,13docosadiene. and clupanodonic acid. Mono-unsaturated acids such as oleic, elaidic and erucic acids can also be used in the preparation of appropriately long chain dimeric acids and used as solid polyol polymer particles in the present invention.

Mixed fatty acid radicals from oil sources containing a significant amount of the desired polymerizable poly- or mono-unsaturated fatty acids can be used in the preparation of the polyol polyester polymer materials used in the present invention to form solid particles. The mixed fatty acids from these sources preferably contain at least 30 wt. (more preferably at least 50 wt.%, most preferably at least 80 wt.%) of the desired polymerizable poly- or mono-unsaturated fatty acids.

Illustrative natural sources rich in linoleic acid are soybean oil, cottonseed oil, peanut oil, cereal oil, sesame oil, sunflower oil, safflower oil, linseed oil and perril oil. Oiticic oil is a very good source of Lianic acid and tonic oil contains high concentrations of eleostearic acid. Fish oils such as heryne, menhaden, sardine and salmon are also suitable sources of polymerizable acids, especially higher fatty acids such as arachidonic and clupanodonic acids. Other oils such as tall oil, dehydrated castor oil, olive oil and rapeseed oil also contain a significant amount of suitable unsaturated acids. For example, olive oil contains oleic acid, rapeseed oil erucic acid.

Preferred polybasic polymerizable fatty acids and derivatives thereof for preparing polymeric polyol polyesters include dibasic acids prepared by dimerizing fatty acids or lower fatty acid esters derived from polyunsaturated vegetable oils such as soybean oil or cottonseed oil, and from animal fats such as tallow.

All these types of polybasic polymerizable fatty acids can be prepared by various known techniques in the art. (See Lutton: US 3,353,967, issued November 21, 1967; Goebel: US 2,482,761, published September 27, 1949; Harrison et al., US 2,731,481, issued January 17, 1956 and Barrett et al. US 2,793,219, issued May 21, 1957, all references cited).

As mentioned, a blend of polymerized and unpolymerized polyol polyesters can be prepared by reacting the polyol with both co-polymeric and non-polymeric fatty acid esterifying acids or derivatives thereof. A preferred process for preparing particularly preferred solids

of sucrose polyester materials containing sucrose polyester polymers is the partial polymerization of fractionated or unfractionated rapeseed oil with high erucic acid methyl ester (HEAR) content, curing and reaction with sucrose. Another method of preparing these particularly preferred solid sucrose polyesters is by routinely esterifying the liquid sucrose polyester material with high erucic acid rapeseed fatty acid groups, partially polymerizing the resulting liquid sucrose polyester and curing the resulting polymer material.

3. Liquid polyol polyester fatty acids

A key component of the present composition comprising indigestible oil is a liquid polyol fatty acid polyester having a complete melting point of less than 37 ° C. Liquid indigestible edible oils suitable for use in the present compositions include liquid polyol polyesters (see Jandacek: U.S. 4,005,195, issued Jan. 25, 1977); liquid tricarballylic acid esters (see Hamm: U.S. 4,508,746, issued April 2, 1985); liquid diesters of dicarboxylic acids such as malonic or succinic acid derivatives (see Fulcher: U.S. 4,582,927, issued April 15, 1986); α-branched carboxylic acid liquid triglycerides (see Whyte: U.S. 3,579,548, issued May 18, 1971); liquid ethers and esters containing a neopentyl group (see Minich: U.S. 2,962,419, issued November 9, 1960); liquid fatty polyethers of polyglycerol (see Hunter et al., U.S. 3,932,532, issued January 13, 1976); liquid alkyl glycosides of fatty acid polyesters (see Meyer et al .: U.S. 4,840,815, issued June 20, 1989); liquid polyesters of two ether-linked hydroxypolycarboxylic acids (eg, citric or isocitronic) (see Huhn et al., U.S. 4,888,195, issued December 19, 1988); and liquid esters of epoxidically expanded polyols (see White et al., U.S. 4,861,613, issued August 29, 1989); and liquid polydimethylsiloxanes (e.g., Fluid Silicones from Dow Corning). All of said patents relating to liquid indigestible oils are incorporated by reference.

Preferred liquid indigestible oils are liquid polyol polyesters comprising liquid sugar polyester, liquid sugar alcohol polyester, and mixtures thereof. Preferred sugars and sugar alcohols for the preparation of these liquid polyol polyesters are erythritol,

20-xylitol, sorbitol and glucose, sucrose being particularly preferred. Initial sugar or sugar alcohol for the preparation of liquid polyol polyesters are preferably esterified with fatty acids _of C ₈ .22, most preferably C _{8 8} Ref acids. Suitable natural sources of these acids are fatty acids from cereal oil, cottonseed oil, peanut oil, soybean oil, canola oil (i.e. fatty acids derived from high erucic acid rapeseed oil), sunflower oil, sesame oil, safflower oil, fractionated palm oils, camel oil, coconut oil, tallow fatty acid and lard.

Liquid indigestible polyol polyesters are substances containing a minimum of constituents that are in solid form at body temperature (i.e., 37 ° C). These liquid polyol polyesters typically contain ester groups with a high proportion of C ₁₂ and lower fatty acid radicals or a high proportion of C ₁₈ and higher unsaturated fatty acid radicals. In the case of liquid polyol polyesters having high content of unsaturated _Ci8 or higher fatty acid radicals, at least half the incorporated unsaturated fatty acids. Preferred unsaturated fatty acids are oleic, linoleic and mixtures thereof.

Some examples of specific liquid polyol polyesters suitable for the present invention: sucrose tetraoleate, sucrose pentaoleate, sucrose hexaoleate, sucrose heptaoleate, sucrose octaoleate, hepta and octaesters of soybean oil unsaturated fatty acids, canola oil fatty acids, cottonseed fatty acids cereal oil, peanut oil fatty acids, camel oil, coconut oil fatty acids, glucose tetraoleate, glucose coconut fatty acid esters of soybean oil or unsaturated soybean oil fatty acids, mannose tetraesters of mixed soybean oil fatty acids, oleic acid galactose esters, arabinose linoleic acid tetraesters, xylose tetralinoleate, galactose pentaoleate, sorbitol tetraoleate, sorbitol unsaturated soybean oil fatty acids, pentaoleate xylite and mixtures thereof.

Liquid polyol polyesters suitable for the present compositions can be prepared by a variety of techniques known in the art. These procedures

include: transesterifying the polyol (i.e., sugar or sugar alcohol) methyl, ethyl, or glycerol esters of the respective acids using various catalysts; acylation of the polyol with acyl chloride; acylating the polyol with an acid anhydride; and acylating the polyol directly with the selected acid. (See, e.g., U.S. 2,831,854, 3,600,186, 4,517,360 and 4,518,772, all of which are incorporated herein by reference. All of these patents disclose suitable processes for preparing polyol polyesters.)

4. Other edible fat additives

Liquid preparations containing indigestible oil optionally contain other ingredients, as long as they do not adversely affect the formation of liquid indigestible oil. A variety of ingredients are suitable, provided that they are edible, aesthetically acceptable, and compatible with the other ingredients of the formulation. Additives include edible ingredients, digestible oils and solids, fat-soluble vitamins, fragrances and spices, emulsifiers, spray suppressants, chelating agents, tackifiers, anti-oxidants, antifoams (especially for frying purposes) and the like.

5. Formation of hardened indigestible oils

Under normal circumstances, not under the conditions of the present processes, formulations containing indigestible oils crystallize from a liquid melt to form solidified non-liquid oils upon rapid cooling from the melt temperature to a crystallization temperature of solid polyol polyester or lower (e.g., about 37 ° C) under quiescent conditions. . This solidified non-liquid non-digestible oil contains a proportion of liquid non-digestible oil that virtually all remains in the crystalline matrix of the crystallized solid fatty acid polyol. This matrix provides the required control of passive loss of indigestible oil. The composition and method of preparation of the food preparation should be selected so as to allow a sufficiently rapid cooling of the non-digestible oil from the melt temperature to a lower temperature, especially if the mixture is not stirred while cooling so that the solid polyol fatty acid polyester crystallizes to the desired crystalline form. which allows passive oil loss control. Generally, this cooling rate is from the initial melt crystallization temperature

-224 4 · 44 44 44 4 44 44 4 4 4 4 444 4 4 4 4

444 · 44 444 44 44 to a lowest crystallization temperature (lowest melting point of the solid polyol polyester component) greater than 0.5 ° C / min, more preferably greater than 2.5 ° C / min and most preferably greater than 25 ° C / min. In the case of a polymeric polyol polyester capable of forming suitable crystalline forms to control passive oil loss even at slower cooling rates, a cooling rate of greater than 0.03 ° C / min under rest conditions is sufficient to achieve the desired structure.

When a non-digestible oil composition comprising any solid polyol fatty acid polyester, or a combination of a solid saturated polyol fatty acid polyester, a solid alternately esterified polyol fatty acid polyester and a polymer polyol fatty acid polyester, begins to crystallize (or co-crystallize) the first crystals (or mixed crystals) ) appear as discrete non-aggregated units suspended in liquid polyol fatty acid polyester. Under quiescent cooling conditions, for example, when the indigestible fat has been incorporated into the food product during baking or frying, these discrete non-aggregated units grow as a crystalline continuum and begin to form clusters and small clusters of at least 3 µm in size dispersed in liquid indigestible oil. These small aggregate clusters of particles can form a variety of forms and shapes, including spherical, platelet, fibrous or rod-shaped, or a combination thereof, but typical shapes are spherical and platelet-shaped. Thinner particle aggregates, platelet-like formulations, are more advantageous in terms of more efficient control of the passive loss of the liquid polyol polyester component of the non-digestible oil formulation. The platelet-shaped particles preferably have a thickness of 0.1 µm and less preferably 0.05 µm and less. As the crystallization proceeds, the platelets become larger, forming clusters and larger aggregates of particles, resulting in a porous structure structure capable of retaining a significant amount of liquid polyol polyester. It is believed that such a porous structure has the ability to absorb a significant amount of liquid polyol polyester is the reason why the platelet type of particles provides effective control of passive oil loss and leads to the formation of a solidified non-liquid, indigestible oil.

B. A method of making a liquid composition comprising an indigestible oil

The present invention further provides a process for producing a non-digestible liquid oil comprising a) a liquid polyol polyester of a fatty acid having a complete melting point of less than 37 ° C; and b) a solid polyol polyester of a complete melting point of at least 37 ° C. The process comprises the steps of completely melting an indigestible oil composition comprising solid polyol fatty acid polyester, rapidly cooling the indigestible oil melt to crystallization temperature, rapidly crystallizing at least a substantial portion of the solid polyol fatty acid polyester, and mixing the indigestible oil composition during the crystallization step to form a liquid formulation with indigestible oil. Optionally, after the crystallization and stirring step, the step of tempering the uncovered non-digestible oil preparation for a time sufficient to complete crystallization of all solid polyol fatty acid polyester, the step of adding a stabilizing amount of diluent, typically liquid polyol fatty acid polyester, to the crystallized non-digestible oil preparation , or both.

The present process for preparing a liquid composition with an indigestible oil typically requires at least 5 minutes and generally less than 3 hours, preferably at least 5 minutes generally less than 2 hours, more preferably at least 15 minutes and no more than 30 minutes.

Without wishing to be bound by theory, it is clear that the crystallization of the solid polyol fatty acid polyester described in the present invention is controlled kinetically. As with any kinetically controlled reaction, it can be assumed that a dynamic equilibrium has occurred when the process is stopped. Thus, with further change in reaction conditions, it proceeds, possibly even back. In this way, solid polyol fatty acid polyester also crystallizes to achieve dynamic equilibrium. Dynamic equilibrium occurs when a portion of the solid polyol fatty acid polyester is still dissolved in the liquid polyol polyester, but the bulk has already crystallized, the rate of crystallization of the solid polyol polyester depends on several factors such as the molecular composition of the solid polyol fatty acid polyester polyol fatty acid polyester, crystallized fraction of solid polyol fatty acid polyester relative to the portion dissolved in the liquid polyol fatty acid polyester, and the temperature difference between the initial crystallization temperature of the solid polyol fatty acid

-24 • * 4 4 · 44 4 4 • 44 4 · · 4 · 4 · «4 · · 4 44 ··

4444444 4 4 · 4 4 4 4

4,444,444

444 4 «4 444 44 44 fatty acid polyester and crystallization temperature. At the onset of crystallization, the solid polyol polyester crystallizes at a high rate. As the crystallization progresses, its rate decreases, optionally (preferably) to knule. Then, if the solution is further cooled, the equilibrium is shifted towards further crystallization of the solid polyol polyester from the liquid polyol polyester solution. If only a small portion of the solid polyol fatty acid polyester crystallizes by this low temperature reduction, it can be assumed that in the absence of mixing, the crystals will be formed as discrete non-agglomerated particles suspended in the liquid polyol fatty acid polyester, or will grow on already present particle aggregates. The discrete particles will agglomerate and form small aggregates, typically several µm in size. In the case of crystallization occurring with stirring, the small aggregates formed do not further bond in clusters or to the large matrix of the crystalline aggregate and thereby maintain the fluidity of the indigestible oil.

The present liquid preparation with indigestible oil can be produced on a crystallization and mixing apparatus typically used in the crystallization of fats. Both batch and continuous processes can be used, continuous is more preferred. The basic requirement of the apparatus is the possibility of rapidly cooling the melt of the polyol polyester component mixture to the crystallization temperature and crystallizing a substantial part of the solid polyol fatty acid polyester to a liquid preparation with an indigestible oil.

1. Melting a preparation containing indigestible oil

The first step of the present process is to melt the solid polyol fatty acid polyesters in the liquid polyol polyester at a temperature somewhat higher than the temperature at which the last residue of the solid polyol polymer melts. Preferably, the temperature of the composition is raised to a temperature 10 ° C higher than the complete melting point of the solid polyol fatty acid polyester.

In the molten state, the non-digestible oil formulation is usually transparent and clear. The onset of crystallization of the solid polyol polyester is therefore clearly evident (at and below the crystallization start temperature) since the liquid polyol polyester becomes cloudy and fogged. The "initial crystallization temperature" for the solid polyol fatty acid polyester can be

-25determined in the analytical procedures section below.

2. Crystallization of a solid polyol fatty acid polyester

The next step of the process comprises rapid crystallization of a substantial portion of the solid polyol fatty acid polyester, ie at least 50 wt%, preferably more than 80 wt%, more preferably more than 95 wt%. % and most preferably more than 99 wt. This step further comprises the steps of lowering the temperature of the molten polyol polyester composition to the crystallization temperature of the solid polyol fatty acid polyester and maintaining the composition at this crystallization temperature for a time sufficient to crystallize a substantial amount of the solid polyol polyester. The crystallization temperature is preferably between 25 ° C and 25 ° C lower, preferably 10 ° C lower. If the solid polyol fatty acid polyester comprises two or more different solid polyol fatty acid polyesters, with different initial melting points, the preferred crystallization temperature is lower than the lowest initial melting point of all the components present, preferably at least 5 ° C, more preferably at least 10 ° C. Deň: 32 ° C. The most preferred crystallization temperature of the solid polyol polyester is in the range of storage temperatures for liquid indigestible oils, typically between 15 and 40 ° C. Obviously, at a lower crystallization temperature, the crystallization of the solid polyol polyester is accelerated.

The rapid crystallization step of the solid polyol fatty acid polyester typically takes less than 30 minutes, preferably less than 5 minutes, more preferably less than 30 seconds, most preferably less than 15 seconds. Usually, 15 to 30 seconds is required, depending on the type of crystallization device selected. While this crystallization step can be carried out within 30 min., Additional time is required to perform the other preferred steps.

The process also includes the step of crystallizing the solid polyol fatty acid polyester under stirring at crystallization temperature. The introduction of stirring during crystallization leads to crystallization of the solid polyol fatty acid polyester in the form of discrete crystals and non-aggregated crystal platelets. Stirring of the crystallizing mixture stops the growth of crystals on the already developed crystalline formations which could already be separated from the liquid phase. It is also assumed that small • 4 4 4 4 44 44 • 4 4444 4444

444 44 4 4445

4444444 4 44 44 4 4 • 4444 444 ·

444 44 44 444 44 44

-26Crystalline platelets aggregate into small particle clusters to prevent agitation from further agglomerating into clusters and larger aggregates that would cause the formulation to solidify. During the crystallization step, stirring is performed at a rate of 400 to 8000 s ^-1 , more preferably 500 to 6000 s ^-1 .

The crystallization step can be carried out in a device comprising a heat exchanger equipped with scraping or sweeping of the walls, in a screw heat exchanger or equivalent, in reactors equipped with a stirrer and a wall scraper, in plate and frame heat exchangers, in tube or scraper exchangers. In a suitable apparatus, the formulation can be cooled at a rate of 0.4 to 300 ° C / min, more preferably 0.8 to 150 ° C / min. Examples of suitable devices are Cherry Burrell Votator, Girdler “A” units; Sollich Turbo Temperature; and Groen Model # DR ©, used in the manufacture of margarine and baking fat; and Aasted units for tempering chocolate. A preferred device is a Votetor which comprises a steel shaft rotating in a tube cooled from the outside by a cooling medium. The rotating shaft is equipped with a high speed scraper, which is pushed against the cold outer surface and continuously scraps the crystallizing agent from the inner surface of the tube. References to these common units: Greenwell, B.A., J. Amer. Oil Chem. Soc., March 1981, 206-207; Haighton, A.J., J. Amer. Oil Chem. Soc., 1976, vol. 53, 397-9; Wiedermann, L. H., J. Amer. Oil Chem. Soc., Vol 55, 826-7; Beckett, S.T., ed., Industrial Chocolate Manufacture and Use, Van Nostrand Reinhold, New York, 1988, 185-9. All these documents are incorporated by reference.

A heat exchanger equipped with a wall scraping device is a preferred device for rapid cooling and crystallization of the composition under rapid stirring, typically at a cooling rate of 8 to 300 ° C / min. The temperature of the cooling medium must be sufficiently low to rapidly cool the crystallizing polyol polyester, on the other hand, it must not cause excessive adhesion of the polyol polyester to the cold surfaces of the device. The temperature of the cooling medium is typically in the range of -23 to 20 ° C, more preferably in the range of -6.7 to 7 ° C. Typical cooling medium is liquid ammonia, brine and other cooling mixtures.

The molten oil can also be precooled to a temperature close to the intended initial crystallization temperature as mentioned above before entering the heat exchanger with the wall scraper by means of a separate heat exchanger.

99

9 9

9 9

9 9

9 · 9 · 9

-2799 9 ·

9

Generally, the rate of mixing applied during crystallization must be proportional to the rate of crystallization of the solid polyol polyester. E.g. if the crystallization temperature is significantly lower than the initial crystallization temperature, i.e. the crystallization proceeds very rapidly; high mixing speed should be applied to achieve the desired crystalline form of the platelet particles. Of course, if the crystallization rate is too much above the agitation rate so that large particle aggregates are formed during this, agitation must be continued after both crystallization has slowed and stopped to break up the large aggregates and form a liquid preparation.

After the step of rapid crystallization of the polyol polyester accompanied by stirring, resulting in the formation of discrete non-aggregated crystal particles, it is preferable to continue stirring the crystallized preparation at the crystallization temperature for a time sufficient to recrystallize all solid polyol polyester. Continuous stirring serves to break up the large particle aggregates and other three-dimensional crystalline matrices that are typically formed in the unmixed mixture. This continued mixing prevents the formation of dead zones ”in the crystallization apparatus, which allow the localized formation of the solidified composition. Continuous stirring is typically carried out for 2 s, preferably 5 min, more preferably 10 min. Usually, however, no more than 2 hours, more preferably no more than 30 minutes.

Continuous stirring may be performed at a lower rate than stirring during crystallization. During the continuous mixing step, the stirring speed is in the range of 10 s ^-1 to 8000 s ^-1 . A preferred type of device for the continuous mixing step is any stirred vessel with an outlet, preferably operating in the absence of air and capable of incorporating it into the polyol polyester composition, and equipped with a thermostat. A suitable device for scraping walls containing a drain and an open tank with a stirrer is the Krueter kneading boiler (Beckett,

S.T., ed., Industrial Chocolate Manufacture and Use, Van Nostrand Reinhold, New York, 1988, pp. 183-4). The continuous mixing step may also be carried out in two or more separate parts of the apparatus which includes the stirred heat exchanger. Another suitable mechanical device useful in the mixed crystallization of polyol polyester is the Ross 410 X-3 or the Readco twin screw mixer.

The continuous mixing step may also be performed in a non-mechanical device, such as a static mixer, comprising a tubular section with a plurality of mixing components in series. The product is mixed

0 0 0

0 0 0

0 0 0

0 0 0

0 00

-28 by turbulence and agitation as it passes around stationary mixing blades inside the tubes. Static mixer manufacturers include Komax and Lightnin.

Of course, the continuous agitating step may be carried out in the same apparatus where the previous crystallization under agitation took place, for example, in a Sollich Turbo Tempering turbo-tempering column.

3. Tempering

Optionally, the present process further comprises a tempering step. Tempering consists in lowering the temperature of the crystallized polyol polyester to a tempering temperature that is lower than the intended lowest temperature for storing liquid non-digestible oil and maintaining the composition at this tempering temperature for a time sufficient to crystallize any solid polyol polyester in the composition. The tempering step is preferably carried out in cases where the crystallization temperature is higher than the intended storage temperature of the liquid preparation containing the indigestible oil. In cases where the crystallization temperature is lower than the storage temperature, the tempering step is not necessary. The tempering temperature is preferably 5 ° C, more preferably at least 10 ° C below the intended temperature when using / storing the product with liquid indigestible oil. Typically, the tempering temperature is in the range of 5 to 25 ° C, preferably 5 to 15 ° C.

In order to prevent aggregation of the crystalline particles, it is advantageous to accompany the tempering of the polyol polyester composition by stirring. The tempering step usually takes place for 2 min to 2 h, preferably 2 min to 1 h, more preferably 5 to 20 min. The extent of stirring during tempering is usually the same as in the continuous stirring step, preferably at a rate of 1 s ^-1 , more preferably 25 to 50 s ^-1 . As in the case of continued mixing, no "dead zones" in the mixer must occur in the tempering step, which would lead to local formation of the solidified preparation.

After the tempering step, the composition temperature is preferably adjusted to ambient / storage temperature.

4. Add thinner

• 9 9 9

9 · ·

The present process further optionally comprises the step of adding a certain amount, preferably a stabilizing amount, of a liquid diluent to the crystalline preparation with a polyol polyester, which increases, preferably ensures the stability of the liquid, indigestible oil. The purpose of adding a liquid diluent is to gradually increase the solubility of the solid polyol polyester in the liquid polyester, which promotes the formation of a more fluid formulation. The liquid diluent is preferably added after adjusting the crystallization temperature to ambient temperature during storage, even more preferably after the tempering step. The addition of a diluent reduces, preferably stops the tendency of the solid polyol polyester to crystallize from solution, even causing part of the already crystallized solid polyol polyester to return to the liquid phase. The diluent is added in an amount proportional to the amount of digestible oil to be treated, usually in a ratio of 10: 1 to 0.01: 1, more preferably 2: 1 to 0.01: 1, more preferably 1: 1 to 0.05: 1 and most preferably 0, It was 5 - 1 at the break. The temperature of the diluent added to the liquid indigestible oil is in the range of 5 to 50 ° C, more preferably 10 to 25 ° C. The temperature of the diluent liquid depends on the amount of diluent used, the storage temperature of the liquid non-digestible oil, and other factors, as is known to the skilled person. A preferred diluent is a liquid polyol fatty acid polyester. Other edible oils, preferably indigestible, miscible with the liquid polyol polyester of the liquid indigestible oil formulation, generally lipophilic solvents, may also be used as solvents.

If the liquid formulation with indigestible oil is left unmixed for an extended period of time, it settles and it is likely that small temperature differences will lead to further crystallization of the remaining dissolved solid polyol polyester, which of course results in solidification of the formulation. The introduction of further mixing thus serves to break down the resulting aggregates, which could arise due to the tendency of small particles to form clusters. Mixing thus reduces the consistency of the product.

Thus, the step into the crystalline polyol polyester preparation can be carried out before and after the continuous mixing step of the crystallized preparation. Adding the diluent liquid prior to the continued mixing step will save the time required for further mixing.

· 9

9 9 9

- 30C. Heat sensitive food ingredients

The liquid composition with indigestible oil further optionally comprises heat-sensitive food ingredients such as fat-soluble vitamins and others, flavorings and spices. Food ingredients are in

either particulate or liquid. The particulate food additive can be added to the final digestible oil formulation even during the crystallization steps, but at a temperature that does not adversely affect the effectiveness of the additive.

For example, the present liquid preparations with indigestible oil can be enhanced with vitamins and minerals, in particular by adding fat-soluble vitamins. Fat soluble vitamins are Vitamin A, D, K and E. (See U.S. 4,034,083, Mattson, issued June 5, 1977, incorporated herein by reference).

D. Use of preparations containing indigestible oils

Non-digestible oils that can be incorporated into the present non-digestible oil formulations can be used for frying, e.g. in the preparation of French fried potatoes, potato chips, cornflakes, tortilla chips, frying chickens, fish and preparing kneaded and fried foods (eg pastes of sea crabs). The compositions can be advantageously used as baking fats, cooking oils, frying, salads and corn roasting. The preparations can also be used in food sprays, margarines and spreads. The individual components of the preparations may be mixed prior to use or added separately to foods.

Non-digestible oils can also be used in baked food products, arbitrarily, in the form of mixtures, durable and frozen bakery products. Possible uses are found in the production of foods such as cakes, muffins, savory pastries, wafers, biscuits, pastries, pies, crispy pies, whole bread sticks and pastries, including sandwich buns, chocolate chips, and especially U.S. Pat. No. 4,455,333 to Hong & Brabbs. Baked products may contain fruit, whipped cream and other fillers. Other suitable products for use in the present compositions are bread, rolls, crackers, pretzels, fritters, waffles, ice cream cones and cups, yeast pastries, pizzas and crisp pizzas, and baked flour desserts and baked salty desserts.

··

- 31 »4 · 4

I · · 4

I · 4 ·· ··

The present compositions can also be used as components of the fat content of many other foods such as ice cream, frozen desserts, cheeses, meat, chocolate candies, salad dressings, mayonnaise, margarine, spreads, sour cream, yogurt, coffee cream, cake, roasted nuts and drinks, such as milk shakes.

The present compositions may replace 10 to 100 wt. fats / oils contained in foods. When replacing natural fats in foods containing both fat and non-fat ingredients (eg starch, sugar, non-fat milk solids, etc.) with the present indigestible oil compositions, these solid polyol polyesters include passive loss of indigestible oils during food digestion.

The present compositions can be used in combination with other indigestible fats such as branched chain fatty acid triglycerides, triglycerol ethers, polycarboxylic acid esters, sucrose polyethers, neopentyl alcohol esters, silicone or siloxane oils, and dicarboxylic acid esters. Other suitable materials that can be used to replace fats in combination with the present compositions are medium chain triglycerides, triglycerides containing a combination of medium and long chain fatty acids (as described in EP 0322027, Seiden, issued June 28, 1989, incorporated herein by reference). ), highly esterified polyglycerol esters, acetic fats, plant sterol esters, oxy ethylene pole esters, jojoba esters, fatty acid mono / diglycerides and dibasic short chain mono / diglycerides.

The compositions are particularly useful in combination with certain types of food and beverage ingredients. For example, low calorie foods can be achieved when the present liquid non-digestible oils are used in combination with non-caloric or low caloric sweeteners such as aspartame, saccharin, alitam, thaumatin, dihydrochalcone, acesulfame, and cyclamate.

In combination with the present indigestible fats, a number of ingredients constituting the construction or volume of many food products can also be used. The bulking agents are, for example, indigestible hydrocarbons such as polydextrose, cellulose or cellulose derivatives such as carboxymethylcellulose, carboxyethylcellulose, hydroxypropyl, methylcellulose, hydroxypropylcellulose, methylcellulose and microcrystalline cellulose. Other suitable bulking components are resins (hydrocolloid), starches, dextrins, fermented whey, tofu, maltodextrins, polyols including sugar alcohols such as sorbitol and mannitol, and hydrocarbons such as lactose.

Similarly, food and beverage products using a combination of the present compositions with indigestible oils and dietary fibers can be produced, providing a combination of both benefits. By "dietary fiber" is meant a complex of hydrocarbons resistant to digestion by mammalian enzymes, such as hydrocarbons found in the walls of plant cells and seeds, or hydrocarbons produced by microbial fermentation. Examples of such complexes are bran, cellulose, hemicellulose, pectins, gums and glue, seed extracts and biosynthetic gums. The sources of cellulose fibers are vegetables, fruits, seeds, cereals and biosynthetic fibers (produced, for example, by bacterial synthesis). Commercial fibers such as purified vegetable cellulose, cellulose flour may also be used. Also suitable are natural fibers such as psyllium, citrus skin peels, white citrus peels, beetroot fibers, citrus pulp and bladder membranes, apple pulp and melon peel pulp.

Said dietary fibers may be used in both crude and purified form. Suitable are both dietary fiber (eg cellulose) and composite (eg white citrus skin fibers containing cellulose and pectin), as well as combination fibers (eg cellulose and gum). The pulp can be produced by known techniques in the art.

However, fibers suitable for the present purposes should be tested for compatibility with the other ingredients of the present compositions. E.g. a combination of a sweetener and the present liquid formulation is not suitable unless the benefits of both are specifically desired. The preparation and the combination of possible additives must be used where appropriate and in appropriate amounts.

These indigestible oils bring a number of benefits in the food and beverage industry. They are used alone or in mixtures with edible oils and other ingredients discussed above. The primary benefit of these materials is to reduce the calorie content of foods if partially or even * 4

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4 4

4 4 4 4

444 44 44 completely replace digestible fats. The reduction in caloric content can be further enhanced by the eventual inclusion of low calorie sweeteners, fillers and other indigestible fats in the diet. A further significant reduction in saturated fat consumption can be achieved by replacing saturated fat in the diet with the present indigestible oil formulations. Foods and beverages containing solid indigestible fats instead of animal triglyceride fats also contain less cholesterol, thus digesting these fats leads to lower serum cholesterol and consequently less risk of heart disease. The present compositions with indigestible oils also have suitable organoleptic properties, in particular lack of waxy character.

E. Use of liquid indigestible oil in the production of food and beverages

The present liquid formulations with indigestible oils are used in the production of a variety of different foods and beverages. Due to the manufacturing process of the present compositions, the resulting liquid preparations of indigestible oils, consumed directly or as ingredients of other foods, have a relatively low passive loss. Therefore, it is important first to completely melt the non-digestible oil composition to completely melt the non-digestible oil so that all the crystalline form of the solid polyol polyester is also in a liquid state. It is preferred to melt the formulation to a temperature 10 ° C higher than the complete melting point of the solid polyol fatty acid polyester. The molten non-digestible oil may then be incorporated into the food product or beverage in a manner that allows rapid digestion of the non-digestible oil under quiescent conditions (i.e., without stirring during crystallization). Such a process results in the crystalline structure of a solid polyol fatty acid polyester that provides low passive oil loss.

Alternatively, the liquid, non-digestible oil formulation can be incorporated directly into the food product if further processing ensures complete melting of the formulation and subsequent rapid cooling to provide a structure that affects low passive oil loss. An example of such a process is spraying liquid non-digestible oil onto the surface of the desserts immediately after frying. Because the desserts are still hot, the liquid, indigestible oil will melt completely, even his

The solid polyol polyester component, and upon cooling, will immediately crystallize to form a structure providing low passive oil loss.

If liquid preparations with indigestible oils contain thermosensitive components such as vitamins, the time required to fully melt the product should be kept to a minimum and no unnecessary loss of vitamin activity should be avoided.

F. Analytical Procedures (a) Solid Fat Content

Before determining the SFC, the sample of the liquid preparation or the indigestible liquid / solid fat mixture is heated to a temperature of 60 ° C or higher for at least 30 minutes, or until the sample is fully melted. The molten sample is further tempered at 26.7 ° C for 15 min, at 0 ° C for 15 min, at 26.7 ° C for 15 min, and at 0 ° C for 15 min. After tempering, the solid fat content is determined by pulse magnetic resonance (PNMR) at 10 ° C, 21.1 ° C, 26.7 ° C, 33.3 ° C and 37 ° C, each time after thirty minute equilibration at that temperature. A procedure for determining SFC values by the PNMR method is described in Madison, Hill, J. Amer. Oil Chem. Soc., 55, (1978), 328-31, incorporated herein by reference. Determination of SFC by PNMR is also described in AOCS Official Method Cd. 16-18, Official Methods and Recommended Practices of The American Oil Chemists Society, 3 ^rd , Ed., 1987 (incorporated by reference).

The slope of the SFC profile curve is calculated from the percent solids difference at 21.1 ° C and 37 ° C and dividing this difference by 28.6.

(b) Consistency

The consistency (K) of the indigestible oil is measured at room temperature between 20 and 40 ° C on a Rheometrics pressure rheometer equipped with a cone-plate measurement system. The cone diameter is 4 cm, angle 2 °. The indigestible oil sample is gently applied to the plate and the cone slowly decreases to the sample surface (gap 0.048 mm). Flow measurement with

This is done by programmed shear pressure increase over time. Shear pressure is increased from zero to 500 Pa for 2 min. The applied pressure leads to deformation of the sample (e.g., expands) and the rate of change is referred to as shear rate. From the results, a fluidity curve of the indigestible oil sample is generated by plotting the logarithm of the apparent viscosity versus the logarithm of shear friction. The fluidity curve is then adjusted to the following form of force law:

Obvious viscosity = K (shear friction rate) ' ¹ where the apparent viscosity is expressed in poise (P), shear friction rate in units s' ¹ , K is the consistency in units Ps ⁽ⁿ ' ^,) and ⁿ is the dimensionless shear index. This form of force law is widely used to describe the flow behavior of non-Newtonian materials. On a log-log curve of apparent viscosity versus shear friction rate, the force law has a linear slope with slope (n-1). Shear friction index in

(n) is in the range of 0 to 1. The closer n is to 1, the closer the sample's fluidity approaches Newtonian behavior. The consistency (K) is numerically equal to the apparent viscosity at a shear rate of 1 s ^-1 . The K and n values describe the flowability of the indigestible oil within the specific shear friction values.

(c) Initial crystallization temperature

The initial crystallization temperature is the temperature at which, under test conditions, the sample becomes cloudy within 90 min after reaching and stabilizing this temperature. Turbidity is the first sign of the onset of crystallization.

Equipment:

1. Jacketed cylindrical vessel of 10.16 cm diameter equipped with a stirrer of at least 250 ml capacity. Heating and cooling is carried out by circulating pure colorless liquid through the jacket. Acceptable media include, but are not limited to, water, ethylene glycol, or silicone fluids.

2. Thermometer calibrated in a temperature range of 25 to 100 ° C.

Method:

1. Heat the sample (minimum 250 ml) to 85 ° C in the test vessel and maintain the temperature until all solids have dissolved. Before starting the test, the whole solution must be clear, without any haze.

2. Stir the contents of the container to maintain the same temperature throughout the contents.

3. Cool the contents at a rate of not more than 2.5 ° C / min to a temperature close to the initial crystallization temperature. Note: To avoid crystallisation of the sample on the cooler walls of the vessel, the temperature of the sample must not be lower than the content temperature by more than 5 ° C.

4. Maintain this temperature for 90 minutes, up to the first signs of turbidity (when viewed horizontally through the vessel walls).

5. If turbidity develops within 90 min, repeat heating and cooling the sample as in step 1. Repeat steps 2, 3 and 4 only to change the final temperature of the previous measurement, ie to 2 ° C higher.

6. Repeat the procedure until the temperature at which no turbidity occurs within 90 min. The initial crystallization temperature is the highest temperature at which the sample becomes cloudy within 90 min.

7. If there is no cloudiness during the first temperature search, repeat heating and cooling according to step 1. Repeat steps 2, 3 and 4, only changing the final temperature of the previous measurement, ie to 2 ° C lower. The initial crystallization temperature is the highest temperature at which the sample becomes cloudy within 90 min.

(d) Fatty acid composition in polyol polyesters

The fatty acid composition of the polyol polyesters (FAC) was determined by gas chromatography on a Hewlett-Packard Model S712A, a gas chromatograph equipped with a flame ionization detector, and a Hewlett-Packard Model 17671 A automatic dispenser. The chromatographic procedure is described in Oil Chemists Society, 3 ^rd Ed., 1984, Procedure 1-Ce62 (incorporated by reference).

(e) Distribution of esters in sucrose polyesters

The relative distribution of individual octa-, hepta- and pentaesters, as well as the pooled tetra- to monoesters of sucrose polyesters, can be determined by normal-phase high performance liquid chromatography (HPLC). This method uses columns packed with silica gel to distinguish the polyester sample according to the number of ester groups as mentioned above. Hexane and methyl t-butyl ether are used as mobile phase solvents. The ester groups are quantified using a mass detector (i.e., a scattered light detector and a vaporized sample). The detector response is measured and normalized to 100%. The individual ester groups are expressed in relative percentages.

(f) Complete Melting Point

Perkin-Elmer 7 Series Thermal Analysis System, Model DSC7, manufactured by Perkin Elmer, Norwalk, Connecticut.

Method:

1) The polyol polyester sample is heated to a temperature of at least 10 ° C above the visible dissolution of all solid components and mixed thoroughly.

2) Weigh 10 + 2 mg of sample into a measuring pan.

3) The sample is scanned in a temperature range of at least 10 ° C above the visible dissolution of all solids up to -60 ° C, at a cooling rate of 5 ° C / min.

4) Maintain the sample temperature at -60 ° C for 3 min and then scan again at increasing temperature ranging from -60 ° C to the original temperature (ie at least 10 ° C above visible dissolution of all solids) at heating rate 5 ° C / min.

5) The complete melting point is the temperature where the baseline (ie, the specific temperature line) crosses the line tangential to the trailing edge of the last (highest temperature) endothermic peak.

(g) Solid polyol polyester fatty acid particle size (light microscopy)

• • •

- 38 • ·

The particle size of the solid polyol polyester in the present liquid non-digestible oil formulations is determined at room temperature using a Nikon Microphot video enhanced light microscope (VELM) using Hoffmann Contrast Modulation (HMC) optics as follows:

1. A small amount (i.e. 1-10 mg) of a digestible oil sample with dispersed small polyol polyester particles is applied to a microscope slide and covered. The slide is placed in a microscope.

2. The sample is examined using a HMC 100X objective lens as a standard lens in combination with an eyepiece containing 10X lenses.

3. The microscope is equipped with a video camera and an additional control unit, making it easier to distinguish between the sample and the background.

4. The particle size of the polyol polyester is measured in micrometers.

This procedure allows the resolution of particles of exactly the size corresponding to the VELM resolution (approximately 0.2 to 0.5 µm). Smaller particles can be determined using the Freeze Fracture procedure as shown below.

(Note: The procedure does not require any special sample preparation, only a representative sample. The samples should be melted and cooled in accordance with the environment.)

Reference: Robert Hoffman, “The Modulation Contrast Microscope: Principles and Perfections”, Journal of Microscopy, Vol. 110, Pt 3, August 1977, p. 205-222.

(h) Particle size of solid polyol fatty acid polyester (transmission electron microscopy on a frozen sample section)

The three-dimensional topography of the polyol fatty acid polyesters and their size can be determined by means of transmission electron microscopy on a frozen sample section, ff-t.

Determination procedure:

1. Charge the outer shell of the freezer container with liquid nitrogen and the inner Dewar vessel of the freezer container with liquid ethane (normal melting point -172 ° C). Ethan is allowed to freeze.

-392. A small amount (1 to 2 μΐ) of the indigestible oil sample with dispersed polyol polyester particles is placed in a well of a gold-plated Balzer sample carrier. (Note for too fluid samples, it is advisable to use a gold Balzer plate and another plate to overlap to form a “sandwich” arrangement).

3. When the metal carrier is immersed in a Dewar vessel, most of the frozen ethane melts.

4. Immediately after melting the ethane, the support is pulled out with two tweezers and the sample container containing the sample of indigestible oil is rapidly immersed in liquid ethane.

5. After a few seconds, the sample container is removed from ethane, quickly attached to the tip of the camel hair brush to remove excess ethane, and immediately immersed in liquid nitrogen to keep the sample cold.

6. In liquid nitrogen, the sample is transferred to the JEOL JFD9000C sample carrier and scanned into the JEOL JFD-9000C chamber of the Freeze-fracture unit. The temperature should be maintained at -175 ° C, under a vacuum of at least 1.064x10 ⁴ Pa.

7. Cool the blade to -165 ° C.

8. Cut the sample in a JEOL chamber with a pre-cooled knife.

9. Allow Pt / C to slice the specimen at 45 ^° for 4.5 s, and allow to store C at 90 ⁰ for 25 s to produce a cut replica, at a high voltage of 2500 V and a current of 70 mA.

10. Remove the samples from the Freeze-fracture unit and purify by flushing with chloroform (3x).

11. Place the replica on a 300 mesh copper EM network and examine by electron transmission microscope.

12. Images are recorded on a negative film from which positive copies are then made.

13. The particle size of the polyol polyesters is measured in nm.

Links:

Rash, J. E., Hudson, C. S., Freeze Fracture: Methods, Artifacts, and Interpretations; Haven Press, New York, 1979.

-40Stoinski, Breathnach, Freeze Fracture replication of Biological Tissues; Academic Press, London, 1975.

Steinbrecht, Zierold, Cryotechnics in Biological Elactron Microscopy; Springer-Verlag, Berlin, 1987.

DETAILED DESCRIPTION OF THE INVENTION

The preparation of the present liquid preparations containing indigestible oils is illustrated by the following examples.

Example 1

Solid and liquid sucrose polyester having a fatty acid composition and ester distribution according to Table C for Olean®, manufactured by the Procter & Gamble Company, Cicinnati, Ohio, is mixed in a ratio of 6 parts by weight of solid sucrose polyester to 94 parts by weight of liquid sucrose polyester. The mixture is stirred in the molten state at 68 ° C in a vessel equipped with a thermostat. The molten mixture is then pumped at a rate of 127.3 kg / h through two series-connected chillers containing a salt solution (-1 ° C, brine) of a heat exchanger equipped with a wall scraper, Cherry Burrell Votator Model 3SSHE, operating at 1690 rpm . The temperature of the mixture is reduced from 68 ° C to 21 ° C in 20 s. At the exit of the heat exchanger, a substantial portion of the solid sucrose polyester is crystallized to form small (<10 µm) discrete and non-aggregated crystalline particles. For the most part, the crystallized preparation is passed through an adjustable temperature heat exchanger, usually at 21 ° C, and into a thermostatic vessel equipped with a wall scraper, where it is kept under controlled mixing conditions at 21 ° C for 2 hours. and a depth of 71 cm holds 45.5 kg of the fixture and is equipped with an anchor stirrer rotating at 14 rpm; the material in the container does not include any dead spots.

Physical properties of the finished liquid preparation containing indigestible oil:

Outlet temperature and continuous mixing temperature: 21 ° C

- 40 0 00 0 00 00

000 · 0000

00 0 0000 • 000 00 · · · · · · ·

00 0000

00 00 «00 · 0 friction index: n = 0,6 consistency (21 ° C): 600 Ps ⁽ⁿ ' ¹⁾

Example 2

This example was carried out according to the procedure of Example 1, except for changes in the orifice temperatures of the production equipment, i.e. a heat exchanger equipped with a wall scraper as shown in Table A.

Table A

Temperature at from the exchanger mouth 15.5 ° C Deň: 18 ° C 26.7 ° C 39.4 ° C Consistency (K) 63 60 60 63 friction index (n) 0.6 0.6 0.7 0.5

Example 3

This example was carried out according to the procedure of Example 1, except for changes in the tempering length and in the temperatures at the orifice of the production equipment, i.e. a heat exchanger equipped with a wall scraper as shown in Table B.

Table B

Temperature at estuary Continuous Consistency friction index exchanger mixing (min) (TO) (n) Deň: 18 ° C 30 90 0.5

60 80 0.6 120 62 0.6 15.6 ° C 30 75 0.6 60 75 0.6 120 67 0.6

Table C

Fatty acid composition and ester distribution in Oleanu® components, ie solid sucrose polyester and liquid sucrose polyester

Fatty acid Solid sucrose polyester (wt.%) Liquid sucrose polyester (wt.%) C8 - CIO - - 02 / 0 - 04 / 0 - 06 / 1,2 9.7 07 / 0 0.1 08 / 4.6 5.9 08: 1 3.7 64.5 08: 2 10.9 18.9 08: 3 0 0.2 C20 4.6 0.3 C22 71.7 0.2 C22: l 0.2 -

- 44 • 4 4 4 4 4 4 4

C24 2.8 - Other 0.4 0.2 Distribution of esters % % octa 71.6 78.7 hepta 28.2 21.0 hexa 0.2 0.2 penta <0.1 0.2 lower <0.1 0.1

Industrial applicability

The present invention provides a liquid formulation comprising an indigestible oil. The indigestible oil comprises liquid and solid polyol fatty acid polyesters, wherein the solid polyol fatty acid polyester is in the form of crystalline particles and forms a liquid polyester absorbent structure. This property of the present indigestible oil causes a desirable low passive loss of liquid oil in the digestive tract.

Claims (10)

PATENT CLAIMS Liquid composition comprising a non-digestible oil, characterized in that it preferably contains 50 to 99% by weight of a non-digestible oil. % liquid polyol fatty acid polyester having a complete melting point of less than 37 ° C and preferably 1 to 50 wt. a solid polyol fatty acid polyester having a complete melting point of at least 37 ° C, wherein the solid polyol fatty acid polyester is in the form of crystalline particles; the solid polyol fatty acid polyester is preferably selected from the group consisting of (i) a solid saturated polyol polyester, (ii) a solid, alternatively esterified polyol polyester, (iii) a polyol polyester polymer, and (iv) combinations thereof; most preferably the solid saturated polyol polyester of the fatty acid and the solid alternatively esterified polyol polyester are in the form of co-crystallized particles; and a liquid composition containing indigestible oil has a temperature of 20 to 40 ° C, a consistency of less than 600 P.sec ^(n_1), preferably less than 400 P.sec ^ ^'0th Liquid preparation comprising the non-digestible oil according to claim 1, characterized in that the crystalline particles have a maximum dimension of 1 to 30 µm, preferably 2 to 5 µm. A liquid preparation comprising an indigestible oil according to any one of the preceding claims, wherein the solid saturated polyol polyester is selected from a polyol polyester of a heptasubstituted fatty acid, a polyol polyester of an octasubstituted fatty acid, and mixtures thereof containing C20-24 saturated fatty acid radicals, a solid the saturated polyol polyester is preferably an octa-behenate sucrose polyester; and the solid alternatively esterified polyol polyester is an octa-saturated sucrose polyester; preferably the esters are selected from behenate and a mixture of C18: 1 and C18: 2 unsaturated; more preferably, the solid polyol polyester of a fatty acid has a fatty acid containing a long saturated chain in the ester portion and a fatty acid containing a long unsaturated chain in the ester portion in a ratio of 5: 3 to 7: 1, -45 ···· · · · · < • · · 4 99 99 preferably 6: 2 to 6.5: 1.5; and the solid, alternatively esterified polyol polyester is selected from a polyol polyester of a hepta-substituted alternately esterified fatty acid, a polyol polyester of an octasubstituted alternately esterified fatty acid, and mixtures thereof containing a) long chain saturated fatty acid radicals and b) different fatty acid radicals, which are other than the saturated fatty acid radicals and are selected from the group consisting of i) long chain unsaturated fatty acid radicals, ii) short chain saturated fatty acid radicals, and iii) mixtures thereof; most preferably the solid saturated polyol polyester is sucrose polyester containing at least 5 wt. sucrose octa-behenate, more preferably a solid sucrose polyester having a complete melting point of less than 60 ° C. 4. A process for the manufacture of a liquid composition comprising a non-digestible oil comprising a liquid polyol fatty acid polyester having a complete melting point below 37 ° C and a solid polyol fatty acid polyester having a complete melting point of at least 37 ° C, comprising the steps of: (a) melting an indigestible oil preparation containing liquid polyol fatty acid polyester and solid polyol fatty acid polyester b) crystallizing at least most of the solid polyol fatty acid polyester, preferably if it further comprises crystallization i) lowering the temperature of the molten non-digestible oil to a crystallization temperature lower than the initial crystallization temperature of the solid polyol fatty acid polyester; ii) keeping the non-digestible oil at crystallization temperature for the time necessary to crystallize at least most of the solid polyol fatty acid polyester; and more preferably maintaining the crystallization temperature for a time suitable for complete crystallization of the solid polyol fatty acid polyester; and c) mixing the preparation with indigestible oil during crystallization to form a solid polyol fatty acid polyester in the form of &lt; 99 &gt; 946999999999999 crystalline particles, preferably stirring occurs throughout the crystallization period; wherein the liquid preparation containing the indigestible oil has a consistency of less than 600 P.sec ^{(n -1)} at 20 to 40 ° C, preferably steps b) crystallization and c) stirring is carried out in a heat exchanger equipped with a wall scraper or equivalent . The process of claim 4, wherein the crystallization temperature is 5 ° C or more lower than the initial crystallization temperature of the solid polyol fatty acid polyester. 6. The method according to claim 4 or 5, characterized in that said liquid nondigestible oil composition comprising a at a temperature of 20-40 ° C, a consistency of less than 400 P.sec ^ '^, preferably less than 200 P.sec ^' ^ ¹ more preferably less than 100 p.sec ( ¹ ). The process according to any one of claims 4 to 6, wherein the solid polyol fatty acid polyester has a complete melting point of at least 60 ° C. Process according to any one of claims 4 to 8, characterized in that at least 80% by weight, preferably at least 95% by weight, crystallize in step b). the solid polyol fatty acid polyester, the solid polyol fatty acid polyester preferably crystallizes at a temperature at least 10 ° C lower than the initial crystallization temperature of the solid polyol fatty acid polyester, more preferably when the crystallization comprises cooling the composition from a melting point to a crystallization rate of 100 to 300 ° C / min, most preferably for the entire crystallization within 30 s. Process according to any one of claims 4 to 9, characterized in that in step c) crystallization takes place under stirring at a shear rate of 400 to 8000 s ^-1 , preferably with the addition of a dilution amount. - 47 • 9 9 999999 · 9 9 9 9 99 99 9 9 9 9 9 9 9 · 9 9 9 9 999 99 99 liquid polyol polyester to the crystallizing composition in a ratio of 0.5: 1 to 0.1: 1; most preferably, this step comprises adding a stabilizing amount of diluent after step b) of crystallizing the solid polyol fatty acid polyester. The method of any one of claims 4 to 10, further comprising the step of tempering the liquid composition comprising the non-digestible oil at a temperature below the intended storage and mixing temperature of the composition during said tempering.