OA18799A - Process for preparing fat continuous emulsions low in fat. - Google Patents

Abstract

A process for preparing a low fat water-in-oil emulsion which emulsion comprises water, oil and a hardstock fat. The process involves combining an aqueous phase and a fat phase, wherein the fat phase comprises the hardstock fat and which fat phase is at a temperature such that the fat phase is liquid, followed by subjecting the obtained mixture to high shear mixing effected a high shear mixing device, and. wherein the product exiting the high shear mixing process the product is packed without having been subject to any further mixing or working process.

Description

PROCESS FOR PREPAR1NG FAT CONTINUOUS EMULSIONS LOW IN FAT

Field of invention

The present invention relates to a process for preparing fat-continuous émulsions (such as e.g. spreads and margarines) which émulsions comprise, next to water, the fat components oil and hardstock fat, and which émulsion is low in fat. The process allows the production of low fat spreadable émulsions which do not need strong emulsifiers like polyglycerol polyricinoleate or stabiîisers of the aqueous phase like starch or gélatine.

Background of invention

Edible water-in-oil émulsions, which comprise a continuous fat phase and a dispersed aqueous phase, are well known in the art and include for example margarine.

The fat phase of margarine and similar water-in-oil émulsions is typically a mixture of liquid oil (i.e. fat that is liquid at ambient température) and fat which is solid at ambient températures. The solid fat, also called structuring fat or hardstock fat, serves to structure the fat phase and helps to stabilize the aqueous phase (e.g. in the form of droplets) by forming a fat crystal network. Ideally the structuring fat has such properties that it melts or dissolves at mouth température otherwise the product may hâve a heavy and/or waxy mouthfeel.

Margarine is generally defined as a composition containing at least 80 wt. % fat and about 20 wt. % aqueous phase. In contrast, (spreadable) émulsions containing less than 80 wt. % fat are generally called spreads. Nowadays the terms margarine and spread are sometimes used interchangeably although in some countries the commercial use ofthe terni margarine is subject to certain regulatory requirements.

In the market place margarine is generally sold as one of three principal types of water-in-oil émulsion:

• hard or stick margarine (also referred to as wrappers);

• (typically softer) tub margarine (typically named “spreads)”; and • liquid or pourable margarine.

Wrapper margarines and tub margarines are non-pourable and generally contain a hlgher amount of hardstock fat than liquid or pourable margarines.

There is an interest with at least part of the consumers for low fat spreads, which contain fat in an amount of 50% or less. Manufacturing such fat-continuous low fat spreads (e.g. having fat levels of 15 to 50% by weight) usually requires additional ingrédients next to the usual fatty acid monoglyceride-based emulsifiers, as such fat-continuous low fat spreads are quite unstable.

This instability both créâtes difficulty in manufacturing and in stability over time, especially when the storage is at room température. Such additional ingrédients traditionally incorporated in fatcontinuous low fat spreads are either strong emulsifiers like polyglycerol poiyricinoleate (PGPR) or thickeners of the aqueous phase like starch or other carbohydrate-based thickeners or gélatine or other gelling proteins, or ail of these additional ingrédients together. The use of such additional ingrédients may be undesired for various reasons, e.g when wishing to be able to manufacture fat-continuous low fat émulsions which hâve a ‘‘cleaner label”, i.e. a product déclaration with as few as possible functional ingrédients.

The general process for the manufacture of water-in-oil émulsions, using the votator or churn process, encompasses the following steps:

1. Mixing of the liquid oil, the hardstock fat and the water-phase at a température at which the hardstock fat is definitely liquid;

2. cooling of the mixture under high shear to induce crystallization of the hardstock fat to create an émulsion;

3. formation of a fat crystal network to stabilize the resulting émulsion and give the product some degree of firmness;

4. modification of the crystal network to produce the desired firmness, confer plasticity and reduce the water droplet size.

These steps are usually conducted in a process that involves apparatus that allow heating, cooling and mechanical working of the ingrédients, such as the churn process or the votator process. The churn process and the votator process are described in the Ullmans Encyclopedia, Fifth Edition, Volume A 16, pages 156-158.A disadvantage of such process is that it requires heating up and cooling the whole formulation, e.g. including ail oil and ail water. This costs a lot of energy. Mélangés containing dairy fat next to vegetable fat as set out above can easily be made with such votator process, in which butter fat is melted and added to the total ingrédient mix that is fed to the processing line.

An alternative to the votator or churn process for the manufacture of margarines which is known involves the use of fat powder comprising hardstock fat (i.e. pre-crystallized fat) (WO 2005/014158). The fat powder used in such process is also known as ScMM powder (super critical melt micronisation) or PGSS process (particles from gas saturated solutions). Spreads can be made by blending at ambient or colder température liquid oil, the fat powder and an aqueous phase. This overcomes having to heat and cool the entire formulation. Disadvantages of such process relate e.g. to the need for equipment which is new in margarine and spreads making (pressurizing and handling CO₂, spraying melted fat, handling fat powder), capital expenditure. Also, the method proves to be less attractive for high-fat products (e.g. 70-85%).

A further alternative for making spreads is known e.g. from GB1327511. This reference discloses a process for the préparation of low-calorie spreads by mixing a first liquid (which is at a température of at least 28°C) which consists of a fat phase containing crystallisable material with a second liquid (which is at a température of at most 8°C) which is substantially free from crystallisable material. At least part ofthe second liquid is composed ofthe aqueous phase, and may further contain oils which are liquid at 2°C. The two liquids are fed separately to a high pressure dosing pump, allowing continuous dosing of the liquids.

There is a desire for a process that allows the manufacture of fat-continuous low-fat émulsions (e.g. spreads), with fat levels of between 15 and 50% by weight, which émulsions comprise vegetable oil and hardstock, yet which manufacturing process does not require the use polyglycerol polyricinoleate (PGPR), carbohydrate-based thickeners like starch, or proteinbased gelling agents like gelatin. At the same time, it is desired that the process does not need complex equipment such as is e.g. needed for making the fat powder using the PGSS process.

Summary ofthe invention

It was found that these objectives can be met, at least in part, by a process for making a spreadable, edible water-in-oil émulsion comprising fat in an amount of from 15% to 50%, by weight based on the total émulsion and water in an amount of from 50 to 85%, by weight based on the total émulsion, which process comprises the steps of:

a. preparing an aqueous phase comprising at least water,

b. preparing a fat phase comprising vegetable oil, hardstock fat and fatty acid monoglyceride emulsifier, which fat phase is at a température such that the whole fat phase is liquid, and wherein the température is below 60°C, preferably below 50°C,

c. combining the aqueous phase and the fat phase, and

d. subject such to a high shear mixing process in a high shear mixer having a rotor and a stator, with a résidence time of less than 3 seconds, and sufficient shear to effect émulsification of water droplets in oil having a droplet size d₃.₃of less than 15 micrometer, wherein the product exiting the high shear mixing process the product is packed without having been subject to any further mixing or working process.

Detailed description of the invention “Hardstock” (“hardstock and “hardstock fat” and “hardstock phase” herein hâve the same meaning) is herein to be understood to be an edibie fat that is solid at ambient température as understood by the person skilled in the art.

in order to obtain a fat-continuous émulsion with water droplets of the desired size and the formation of small crystals of hardstock that can stabilise such émulsion and that can give sufficient firmness to the product, the mixing of the combination of aqueous phase and oil with the melted hardstock should go in a swift way, and also the mixing operation should only resuit in a small température increase due to such high shear mixing. Regarding the latter, it is preferred that the high shear device results in a température increase of the émulsion of less than 5°C, more preferably a température increase of the émulsion of less than 3°C, when comparing température of the aqueous dispersion at the inlet and the température of the émulsion at the outlet of the high shear device. It was found that a high shear mixer having a rotor and a stator, which mixer has a résidence time of less than 3 seconds, and sufficient shear to effect émulsification of water droplets in oil having a droplet size D₃.₃ of less than 15 micrometer, can achieve such objectives. Hence, preferably the high shear device in step d, is such high shear mixer. A typical example of a mixer that can achieve the desired objectives is a fluid division mixer (FDM) as marketed by Maelstrom and as is described e.g. in EP1331988, in WO2002/38263, and in WO2013/037605.

In the process according to the invention, combining the aqueous phase and fat phase in step c. is conveniently effected in a continuous way by combining the two streams in-line.

Depending on e.g. the température of the waterphase and/or especially in the case of very low fat levels (around 20-35%) it may be bénéficiai that after combining the aqueous phase and the fat phase the combined stream is subjected to a stirring or mixing operation, with less shear than the high shear mixer. For this reason, it may be preferred in the process according to the présent invention that after combining the aqueous phase and the fat phase the combined mixture in step c. and before subjecting such to a high shear mixing process the combined mixture is subjected to low shear mixer, which low shear mixer effects lower shear than the high shear of step d. The low shear mixer in the in the above is preferably a pin-stirrer (e.g as they are well known and available in margarine and spreads production). Pin stirrers in margarine processing are also known as C-units. Suitable pin stirrers are e.g. those having a residence time of between 15 seconds and 4 minutes, and a speed of between 50 and 300 rpm. With such pin stirrers tip speeds of between 0.5 and 6 m/s are preferred, more preferably between 1 and 4 m/s. It was found that with such stirring or mixing (e.g. by a pin-stirrer) smaller water droplets may be obtained, which may be bénéficiai especially with water températures on the high end of what is claimed, and more in particular for low fat levels (e.g. 20-35%).

In the process according to the présent invention, it proved bénéficiai that the émulsion exiting the high shear mixer is fed to a packaging line to pack the product in individual packs, and not

e.g. first subjecting the mixture from the high shear mixer to further mixing equipment. In particular, it is preferred that in between the high shear mixer and the packaging line the resulting product is not subjected to the effect imparted by stirring, working, or crystallizing equipment.

The amount of hardstock is generally as low as possible (e.g. for reasons of low SAFA) but as high as is needed for achieving the desired émulsion stability and firmness. To achieve a good balance between melting properties and stability, it is preferred the vegetable oil and the hardstock are présent in the émulsion in a weight ratio vegetable oil : hardstock of between 10: 1 to 1: 5.

A convenient way to obtain hardstock fats is by a process which involves hardening of vegetable oils. Partial hardening may give bénéficiai properties with respect to melting behaviour and émulsion stablisation, yet such partial hardening may give rise to the formation of trans-unsaturated fatty acids in the triglycérides of the hardstock fat. Such trans-unsaturated fatty acids in the triglycérides (“trans-fats”) are undesired from a heaîth perspective. Hence, despite their bénéficiai structuring properties it is preferred that in the process according to the présent invention the fat phase ofthe émulsion comprises less than 1% of trans-unsaturated fatty acids in the triglycérides, by weight on the total fat phase of the émulsion, more preferably the émulsion comprises less than 0.5% of trans-unsaturated fatty acids.

Preferably, for reasons of consumer acceptance and the image of being ail natural, the hardstock fat comprises at least 70% (more preferably at least 80%) of triglycéride esters of fatty acids (TAG’s), by weight based on the total hardstock fat.

Although it was found that with the presently claimed process, fat-continuous low fat émulsions with good (émulsion or water droplet) stability can be prepared without using strong emulsifiers like PGPR, it is still required that some fatty acid monoglyceride emulsifier is used. The amount of such is preferably as low as possible, and as high as is needed forforming and keeping the émulsion. Hence, in the présent process, the fatty acid monoglyceride emulsifier is present in an amount of from 0.05 to 2% by weight, based on the total émulsion. Preferably, the fatty acid monoglyceride emulsifier is present in an amount of from 0.1 to 1.5% by weight, based on the total émulsion, more preferably from 0.2 to 1.2% by weight, based on the total émulsion.

As mentioned, the presently claimed process allows the fat-continuous émulsions to be prepared without the need to include PGPR. This is bénéficiai as PGPR may be perceived by consumera as too artificial. Hence, in the process according to the present invention, it is preferred that the émulsion does not contain polygiycerol polyricinoleate.

Total desired fat levels of the émulsions made by the process according to the present émulsion are (for consumer preference) below 50%, but lower may be preferred by some consumes. A minimum of fat is required to allow for the water droplets in fat-continuous émulsions. Following this, it is preferred in the present invention that the émulsion comprises fat in an amount of from 18% to 35%, by weight based on the total émulsion and water in an amount of from 65% to 82%, by weight based on the total émulsion.

It may be desired to include in the low fat émulsions made by the process of the present invention a low amount of high melting fat, as this makes processing a bit more robust. If applied, it is desired to keep this amount as low as possible, as high amounts may lead to grittiness in the mouth and/or undesired fatty acid profiles from a health perspective. A preferred high melting fat in this respect is fuily hardened rapeseed oil, also known as RP70, as rapeseed oil has very long chain fatty acids. Thus, it is preferred that the émulsion in the process according to the present invention comprises 0.1 to 2% of fully hardened rapeseed oil.

Often, émulsions like are subject of the present invention contain a gelling biopolymer such as gelling protein. Gelling proteins are often included in conventionai low fat spreads for stability reasons, but such gelling proteins may negatively impact mouthfeel, and also some of them such as gélatine hâve a négative consumer image linked to e.g. BSE-disease. Thus, it is preferred that in the process according to the present invention, that the émulsion does not comprise a gelling protein. Preferably in the process of the present invention, the émulsion does not contain gélatine.

Often, émulsions like are subject of the present invention contain a gelling biopolymer such as gelling carbohydrate (e.g. starch or a dérivative thereof) for achieving increased stability.

However, it is a distinct benefit of the present invention that the presently claimed process does not need such gelling carbohydrate or carbohydrate based thickener. Thus, for reasons of consumer preference and to hâve product label which is as clean as possible, it is preferred in the present invention that the émulsion in the process according to the present invention does not contain a carbohydrate thickener. Preferably the product produced by the present process does not contain starch or a starch-derivative.

Although the process according to the present invention may yield liquid products or wrappertype margarines, it is preferred that the fat continuous émulsion made by this process is a spreadable émulsion. A spreadable émulsion is an émulsion of the composition as described herein, which furthemnore has a Stevens value of between 30 and 300 gram, when measured at 5°C.

Examples

Methods

Water droplet size distribution of W/Q émulsions

The normal terminology for Nuclear Magnetic Résonance (NMR) is used throughout this method. On the basis of this method the parameters d_3i3 and exp(a) of a lognormal water droplet size distribution can be determined. The d₃,₃ is the volume weighted mean droplet diameter (in microns, in the present case) and e^a (e-sigma) is the standard déviation of the logarithm of the droplet diameter.

The NMR signal (écho height) of the protons of the water in a water -in-oil émulsion are measured using a sequence of 4 radio frequency puises in the presence (écho height E) and absence (écho height E*) of two magnetic field gradient puises as a function of the gradient power. The oil protons are suppressed in the first part of the sequence by a relaxation filter. The ratio (R=E/E*) reflects the extent of restriction of the translational mobility of the water molécules in the water droplets and thereby is a measure of the water droplet size. By a mathematical procedure -which uses the log-normal droplet size distribution - the parameters of the water droplet size distribution D3.3 (volume weighed géométrie mean diameter) and σ (distribution width) are calculated.

A Bruker magnet with a field of 0.47 Tesla (20 MHz proton frequency) with an air gap of 25 mm is used (NMR Spectrometer Bruker Minispec MQ20 Grad, ex Bruker Optik GmbH, DE).

Examples 1, 2 and 3: 20% fat spread, different températures waterphase

Three spreadable edible émulsions were prepared having the recipe as in Table 1.

Examples 1,2 and 3 were of identical composition and identical Processing, except for the température of the waterphase when being combined with the oil phase.

Table 1

Component	Amount (wt % on total)	Phase
Water	76.91	Water phase
Sait	2.5	Water phase
Minors (Potassium Sorbate, EDTA, vitamins)	0.06	Water phase
Palm olein fractionate (single stage dry fractionated palm oleine with lodine Value of 56)	6	Oil phase
Palm oil	14.0	Oil phase
Mono and diglycerides (Dimodan-UJ ex Grindstedt, Denmark; distilled 90% unsaturated monoglyceride of Sunflower Oil))	0.3	Oil phase
Rape70 (fully hydrogenatated Rapeseed oil)	0.22	Oil phase
Flavor, colour & vitamins	0.01	Oil phase

The composition was made by first preparing the water phase in a premix vessel.

The oil phase was made by mixing ail ingrédients for this phase in a second premix vessel.

The water phase and oil phase were then combined in-line and fed directly to the high shear mixer. . The oil phase température at the point of mixing was 43°C 10 (±2). The water phase température at the point of mixing was 5°C (example 1 ), 12°C (example

2) and 19°C (example 3).

This was fed to a 3 liter pin-stirrer operating at 100 rpm, followed by a high shear mixer (operating at 2800 rpm). This mixer was of the type FDM, or fluid division mixer by Maelstrom, similar as in WO 02/38263, with a concentric rotor-stator System with 4 rows of cavities in both 15 rotor and stator, with a total volume of 0.083 liter. The cavities in the rotor and stator were spherical segments which are open on both vertical and horizontal faces. The rotor and stator are based on a stepped conical form so that the diameter of the cône increases from inlet to outlet (about 50 up to 150 mm). The mixer is commercially available from Maelstrom (http://www.maelstrom-apt.com/product-dc50/). The resulting product coming out of the high shear mixer had the appearance of a spread.

Examples 4, 5 and 6: 20% fat spread, different températures waterphase

Three spreadable edible émulsions were prepared having the recipe as in Table 2.

Table 2

Component	Amount (wt % on total)	Phase
Water	77.13	Water phase
Sait	2.5	Water phase
Minors (Potassium Sorbate, EDTA, vitamins)	0.06	Water phase
Palm olein fractionate (single stage dry fractionated palm oleine with lodine Value of 56)	6	Oil phase
Palm oil	14.0	Oil phase
Mono and diglycerides (Dimodan-UJ ex Grindstedt, Denmark; distilled 90% unsaturated monoglyceride of Sunflower Oil))	0.3	Oil phase
Flavor, colour & vitamins	0.01	Oil phase

The composition was made by first preparing the water phase in a premix vessel.

The oil phase was made by mixing ail ingrédients for this phase in a second premix vessel.

The water phase and oil phase were then combined in-line and fed directly to the high shear mixer. The oil phase température at the point of mixing was 43°C (±2). The water phase température at the point of mixing was 5°C (example 4), 12°C (example 5) and 19°C (example 6).

This was fed to a 3 liter pin-stirrer operating at 100 rpm, followed by a high shear mixer (operating at 2800 rpm). This mixer was of the type FDM, or fluid division mixer by Maelstrom, similar as in WO 02/38263, with a concentric rotor-stator system with 4 rows of cavities in both rotor and stator, with a total volume of 0.083 liter. The cavities in the rotor and stator were spherical segments which are open on both vertical and horizontal faces. The rotor and stator are based on a stepped conical form so that the diameter of the cône increases from inlet to outlet (about 50 up to 150 mm). The mixer is commercially available from Maelstrom (http://www.maeistrom-apt.com/product-dc50/). The resulting product coming out of the high shear mixer had the appearance of a spread.

Comparative examples A and B (comparative to examples 2 and 3)

Two spreadable edible émulsions were prepared having the recipe as in Table 3, the différence was in the processing.

Table 3

Component	Amount (wt % on total)	Phase
Water	76.28	Water phase
Sait	2.5	Water phase
Minors (Potassium Sorbate, EDTA, vitamins)	0.06	Water phase
Palm olein fractionate	6	Oil phase
Palm oil	14,0	Oil phase
RP70	0.4	Oil phase
PGPR (polyglycerol ricinoleate)	0.45	Oil phase
Mono and diglycerides	0.3	Oil phase
Fiavor, colour & vitamins	0.01	Oil phase

The composition was made by first preparing the water phase in a premix vessel.

The oil phase was made by mixing ail ingrédients for this phase in a premix vessel.

The water phase and oil phase were then combined in-line and fed directly to the high shear mixer.

The oil phase température at the point of mixing was 43°C (±2). The water phase température at the point of mixing was, 12°C (example A) and 19°C (example B).

This was fed to a high shear mixer (operating at 2800 rpm). This mixer was of the type FDM, or fluid division mixer by Maelstrom, similar as in WO 02/38263, with a concentric rotor-stator System with 4 rows of cavities in both rotor and stator, with a total volume of 0.083 liter. The cavities in the rotor and stator were spherical segments which are open on both vertical and horizontal faces. The rotor and stator are based on a stepped conical form so that the diameter of the cône increases from inlet to outlet (about 50 up to 150 mm). The mixer is commercial!/ available from Maelstrom (http://www.maelstrom-apt.com/product-dc50/). The resulting product coming out of the high shear mixer had the appearance of a spread.

Results

The spreads prepared under the examples as set out above were stored for 1 week at ambient conditions (at a température of about 20°C), and the waterdroplet size 03,3 was measured and the distribution of the droplet size (e-sigma). the results is in tables 4-6.

The spreads as prepared under examples as set out above were also subject to a cycling test, to mimic sub tropical conditions. The protocol for such cyclying C-test was: keeping the product for 2 days at 30^eC, followed by 4 days at 10°C, followed by 1 day at 10°C, followed by stabilization at about 20°C for at least two days.

Table 4

	Example 1	Example 2	Example 3
Water phase température	5	12	19
d3.3 after 1 wk at ambient	2.6	2.6	3.8
E sigma after 1 wk at ambient	2.5	2.0	3.2
^3,3 3ftGr Ccycle	4.0	4.1	6.6
E sigma after C-cycle	2.4	1.8	2.5

Table 5

	Example 4	Example 5	Example 6
Water phase température	5	12	19
d3.3 after 1 wk at ambient	2.4	2.6	3.8
E sigma after 1 wk at ambient	2.3	3.4	4.5
d3r3 after C-	3.9	5.3	7.8

cycle
E sigma after C-cycle	2.30	2.7	6.4

Table 6

	Comparative A	Comparative B
Water phase température	12	19
d3 3 after 1 wk at ambient	2.0	2.4
E sigma after 1 wk at ambient	2.3	2.2
d3.3 after Ccycle	3.9	4.9
E sigma after C-cycle	1.8	1.7

These results show that with the process of the invention very low fat spreads (20% fat) can be made without the need to employ stabilisers such as starch or gélatine and without the need to use strong emulsifiers like PGPR, and yet such émulsions hâve sufficient émulsion stability.

Claims (14)

1. Process for making a spreadable, edible water-in-oil émulsion comprising fat in an amount of from 15% to 50%, by weight based on the total émulsion and water in an amount of from 50 to 85%, by weight based on the total émulsion, which process comprises the steps of:

a. preparing an aqueous phase comprising at least water,

b. preparing a fat phase comprising vegetable oil, hardstock fat and fatty acid monoglyceride emulsifier, which fat phase is at a température such that the whole fat phase is liquid, and wherein the température is below 60°C, preferably below 50°C,

c. combining the aqueous phase and the fat phase, and

d. subject such to a high shear mixing process in a high shear mixer having a rotor and a stator, with a résidence time of less than 3 seconds, and sufficient shear to effect émulsification of water droplets in oil having a droplet size d₃.₃ of less than 15 micrometer, wherein the product exiting the high shear mixing process the product is packed without having been subject to any further mixing or working process.

2. Process according to claim 1, wherein the high shear mixing process is effected by a fluid division mixer.

3. Process according to claim 1 or 2, wherein combining the aqueous phase and fat phase in step c. is effected in a continuous way by combining the two streams in-line.

4. Process according to any of the preceding daims, wherein after combining the aqueous phase and the fat phase the combined mixture in step c. and before subjecting such to a high shear mixing process the combined mixture is subjected to low shear mixer, which low shear mixer effects lower shear than the high shear of step d.

5. Process according to claim 4, which low shear mixer is a pin stirrer.

6. Process according to any of the preceding daims, wherein the émulsion exiting the high shear mixer is fed to a packaging line to pack the product in individual packs.

7. Process according to daim 6, wherein between the high shear mixer and the packaging line the resulting product is not subjected to the effect imparted by stirring, working, or crystallizing equipment.

8. Process according to any of the preceding daims, wherein the vegetable oil and the hardstock are present in the émulsion in a weight ratio vegetable oil : hardstock of between 10: 1 to 1: 5.

9. Process according to any of the preceding daims, wherein the fatty acid monoglyceride emulsîfier is present in an amount of from 0.05 to 2% by weight, based on the total émulsion.

10. Process according to any of the preceding daims, wherein the émulsion comprises fat in an amount of from 18% to 35%, by weight based on the total émulsion and water in an amount of from 65% to 82%, by weight based on the total émulsion.

11. Process according to any of the preceding daims, wherein the émulsion comprises 0.1 to 2% of fully hardened rapeseed oil.

12. Process according to any of the preceding daims, wherein the émulsion does not comprise a gelling protein.

13. Process according to any of the preceding daims, wherein the émulsion does not contain a carbohydrate thickener.

14. Process according to any of the preceding daims, wherein the émulsion does not contain polyglycerol polyricinoleate.