The present invention relates to a process for the preparation of an edible dispersion comprising oil and structuring agent, in particular to such dispersions comprising oil and structuring agent as continuous phase and a dispersed phase. The dispersed phase may be an aqueous liquid (thus forming a water-in-oil emulsion) or a solid particulate matter (thus forming a suspension). The invention further relates to the use of micronised fat powder to stabilise oil-containing dispersions.
Edible dispersions comprising oil and structuring agent are well known. Examples of well-known products that substantially consist of such edible dispersions are water-in-oil emulsions, such as for instance margarines and spreads. These edible dispersions typically have an oil phase that is a blend of liquid oil and fat that is solid at normal ambient temperature (20° C.). This solid fat, often also designated as hardstock, acts as structuring agent, and its function is to stabilise the dispersion. For a margarine or spread, ideally the structuring agent has such properties that it should have melted or dissolved at mouth temperature, otherwise the product has a heavy, waxy mouthfeel.
Other known dispersions comprising oil and structuring agent are disclosed in EP-A-775444 and WO 98/47386. Herein the dispersed phase is a dry particulate matter, such as e.g. flour, starch, salt, spices, herbs etc.
Generally, the edible dispersions comprising structuring agent are prepared according to prior art processes that encompass the following steps:
These steps are usually conducted in a process that involves apparatus that allow heating, cooling and mechanical working of the ingredients, such as the churn process or the votator process. The churn process and the votator process are described in Ullmanns Encyclopedia, Fifth Edition, Volume A 16 pages 156-158. Using these techniques excellent dispersions (spreads) having high emulsion stability and good melting properties in the mouth can be prepared.
However, a disadvantage of the known processes is that the process involves a heating step and a cooling step and therefore requires a lot of energy. In a dispersion with for instance 4 wt. % structuring agent the whole weight of the dispersion (100 wt. %) needs to be heated and cooled.
Another disadvantage of the known processes is that the choice of fats that can practically be used as structuring agent is rather limited. If the melting point of the structuring agent is too high the melting properties in the mouth are unsatisfactory. If on the other hand, the melting point is too low, the emulsion stability will be negatively affected. Moreover the amount of saturated fatty acids in the structuring agent is usually relatively high. Saturated fatty acids are a known risk factor for cardiovascular health.
Further disadvantage of the known processes is that the product may deteriorate due to the changes in temperature caused by the heating and cooling step and that heat-sensitive ingredients cannot be incorporated.
Powdered fat is well known in the prior art. It may be prepared according to various processes, known in the art. Micronised fat is also known in the prior art. EP-B-744992 describes the preparation of micronised fat particles by dissolution of gas (carbondioxide) in the fat under pressure and decompressing the mixture in such way that the temperature falls below the solidification point of the fat, so that micronised particles are formed.
EP-A-1238589 describes a method for forming a food product, which contains an emulsion in which the food product in liquid form is contacted with a cryogen so as to cool the liquid product and effect a rapid conversion of the liquid to a solid. A disadvantage of this known process is that still the whole emulsion has to be heated above the melting point of the structuring agent.
It is therefore an object of the invention to provide a process that requires less energy for the preparation of a dispersion comprising the structuring agent. Another object is to provide such a process that allows the use of more types of structuring agent, especially more sorts of hardstock. A further object of the invention is a reduction of the amount of saturated fatty acids in the hardstock. Still a further object of the invention is to provide a process for the preparation of a dispersion that allows the incorporation of heat-sensitive ingredients and/or that avoids deterioration of the emulsion.
One or more of these objects is attained according to the invention that provides a process for the preparation of an edible dispersion comprising oil and structuring agent and one or more of an aqueous phase and/or a solid phase, in which the dispersion is formed by mixing oil, solid structuring agent particles and the aqueous phase and/or the solid phase, wherein the solid structuring agent particles have a macroporous structure of submicron size particles. Preferably, the solid structuring agent particles are at least 50% alpha-polymorph.
According to the invention the heating and cooling step of the emulsion ingredients that is needed in the prior art processes may be omitted or reduced and a stable dispersion can be made.
Preferably, the solid structuring agent particles are at 50% or more alpha-polymorph, more preferably 70% or more alpha-polymorph and most preferably 90% or more alpha-polymorph.
The invention relates to a process for the preparation of a dispersion. A dispersion is herein defined as a system in which two or more phases that are insoluble or only slightly soluble are distributed in one another.
The dispersion may be an emulsion, a suspension or foam or any combination thereof, it may be oil continuous, water continuous or bi-continuous. Preferably the dispersion is oil continuous, more preferably an oil continuous emulsion or oil continuous suspension.
Where a solid phase is present in the dispersion according to the invention, it is preferably a solid phase of dry particulate matter.
Where an aqueous phase is present in the dispersion according to the invention, it is preferably a dispersed aqueous phase.
According to the invention, the dispersion is formed by mixing oil, the solid structuring agent particles and the other phase or phases of the dispersion, such as for example an aqueous phase, a solid phase and/or a gas phase. The mixing of the ingredients may be done in any order, i.e. the ingredients/phases may all be mixed in one mixing step or alternatively the mixing may be executed in more than one step. For instance an oil phase with the structuring agent particles may be mixed and a water phase may be prepared separately and later mixed with the oil phase.
According to the invention, the solid structuring agent particles should have a microporous structure of submicron size particles. An example of a microporous structure according to the invention is shown in
Equivalent good results were obtained for a microporous structure of more bubble-like shape, such as shown in
The microporous structure, may, in the course of the preparation of the dispersion, for instance through the force of a mixer, be broken into submicron particles. The resulting submicron particles will form the structuring network of the dispersion.
The solid fat structuring agent, also denoted as hardstock or hardstock fat, serves to structure the fat phase and helps to stabilise the dispersion.
For imparting to common margarine a semi-solid, plastic, spreadable consistency this stabilising and structuring functionality plays an important role. The crystals of the solid fat form a network throughout the liquid oil resulting into a structured fat phase. The aqueous phase droplets are fixed within the spaces of the lattice of solid fat crystals. In this way coalescence of the droplets and separation of the heavier aqueous phase from the fat phase is prevented.
Generally, fats with a high content of HUH triglycerides show good structuring properties. H denotes a C16-C24 saturated fatty acid residue, such as palmitic acid (C16) or stearic acid (C18) and U denotes an unsaturated C18 fatty acid residue, such as oleic acid (C18:1) or linoleic acid (C18:2). Examples of suitable edible fat structuring agents (hardstock fats) are palm oil partially hydrogenated to a melting point of 44° C. or an interesterified mixture of palm oil and a lauric fat.
Further common ingredients of the fat phase are emulsifiers, such as monoglycerides and lecithin, colouring agents and flavours.
The structuring agent should be added to the dispersion in the form of solid structuring agent particles. Preferably the solid structuring agent particles should have an alpha-polymorph.
The following nomenclature of the polymorphic forms of the structuring agent is used herein:
1. α-polymorph (alpha polymorph): a form that gives only one short-spacing line in the X-ray diffraction pattern near 4.15 Å.
2. β′-polymorph (beta-prime polymorph): a form that gives two short spacing lines near 3.80 Å and 4.20 Å in the X-ray diffraction pattern and also shows a doublet in the 720 cm−1 in the infrared absorption spectrum
3. β-polymorph (beta polymorph): a form that does not satisfy criteria 1. or 2.
See for an explanation of polymorphism and the above definition: Gunstone, F. D.; Harwood, J. L.; Padley, F. B.; The Lipid Handbook, second edition, Chapman and Hall, page 405.
The solid structuring agent particles preferably have an average particle size (D3,2) of 60 micrometer or less, more preferably the solid structuring agent particles have an average particle size of 30 micrometer or less. The average particle size (D3,2) is determined as indicated in the examples.
Preferably the solid structuring agent particles are prepared using a micronisation process. In the micronisation process the solid structuring agent particles are prepared by preparing a homogeneous mixture of structuring agent and liquified gas or supercritical gas at a pressure of 5-40 MPa and expanding the mixture through an orifice, under such conditions that a spray jet is applied in which the structuring agent is solidified and micronised. The liquified gas or supercritical gas may be any gas that may be used in the preparation of food products, for example carbondioxide, propane, ethane, xenon or other noble gases. Carbondioxide and propane are preferred. Carbondioxide is most preferred. Advantages of carbondioxide are that it has a mild (31° C.) critical temperature, it is non-flammable, nontoxic, environmentally friendly and it may be obtained from existing industrial processes without further contribution to the greenhouse effect. It is fairly miscible with oil and is readily recovered owing to its high volatility at ambient conditions. Finally liquid CO2 is the second least expensive solvent after water.
The temperature of the mixture of structuring agent and liquified gas or supercritical gas is preferably such that the mixture forms a homogeneous mixture. Advantageously, the temperature of the mixture of structuring agent and liquified gas or supercritical gas is below the slip melting point of the structuring agent at atmospheric pressure and above the temperature at which phase separation of the mixture occurs. Under such conditions the smallest micronised particles may be obtained.
The pressure and temperature of the mixture of structuring agent and liquified or supercritical gas is preferably such that a large amount of the gas may be dissolved in the structuring agent. The amount dissolved will be determined by the phase diagram of the mixture of structuring agent and liquified or supercritical gas. At higher pressures as well as at lower temperatures more gas will dissolve in the structuring agent.
Preferably the temperature and pressure are chosen such that 10 wt. % or more, more preferably 20 wt. % or more or most preferably 30 wt. % or more of gas is dissolved in the liquid phase. The mixture of structuring agent and liquefied or supercritical gas may contain additional substances, such as for instance oil. We have found that the addition of oil may reduce sintering of the micronised particles of the structuring agent.
The mixture containing structuring agent and liquefied or supercritical gas is depressurised over a small orifice or nozzle, to break up the mixture into small droplets. The break-up of the mixture into droplets can be assisted e.g. by internals inside the nozzle before the orifice to generate a whirl, or by passing a gas at a high flow rate near the orifice.
The mixture is depressurised into a volume where the pressure is higher than, equal to or lower than atmospheric pressure.
We have found that sintering, agglomeration and ripening of micronised particles of the structuring agent will lead to a reduced performance of the particles for structuring the dispersion.
To avoid sintering, agglomeration and/or ripening of the micronised particles, preferably a gas jet is applied in addition to the flow of the spray jet. The additional gas jet is most effective when the gas jet is positioned such that recirculation of material expanded through the orifice is reduced or avoided. Especially advantageous is a position wherein the gas from the gas jet flows essentially tangentially to the flow direction of the spray jet. Most advantageously the gas inlet for the gas jet is positioned behind the exit of the nozzle, see
To further avoid agglomeration and ripening, the spray jet is preferably sprayed into a collection chamber, and a flow of gas having a temperature lower than the slip melting point of the structuring agent is fed into the collection chamber.
Preferably the edible dispersion according to the invention is a water and oil containing emulsion, optionally including a solid phase. The emulsions are preferably oil continuous. Examples of suitable emulsions are table spreads, dressings, soups, sauces, shortenings, cooking oils, frying oils, whipping creams and mayonnaises.
A stable dispersion is herein defined as dispersion that shows an oil exudation of less than 5% after storage for 15 weeks at 15° C., measured according to the method described in the examples.
A further preferred edible dispersion according to the invention is a dispersion of a solid matter, preferably a dry particulate matter, dispersed in a continuous phase of oil and structuring agent. Preferred material for the dry particulate matter is one or more of flour, starch, salt, herbs (e.g. dried herbs), spices and mixtures thereof. Preferably in such dispersions, the amount of solid matter is 30-75 wt. %, more preferably 40-65 wt. % based on total weight of the dispersion.
The amount of structuring agent should be such that a suitably stable dispersion is obtained. When the structuring agent is micronised fat, the amount is preferably 1-20 wt. %, more preferably 4-12 wt. % based on total weight of the dispersion.
Method to Determine Slip Melting Point
The slip melting point of structuring agent is determined in accordance with F. Gunstone et al, The Lipid Handbook, second edition, Chapman and Hall, 1995, page 321, Point 6.2.3, Slip point.
Method to Determine D3,2 of the Particle Size Distribution of Micronised Fat Particles
Low-angle laser light scattering (LALLS, Helos Sympatic) was used to measure the average particle size (D3,2). The fat particles were suspended in water in a quixel flow cuvette with an obscuration factor of 10-20%. The diffraction pattern was measured at 632.8 nm with a lens focus of 100 mm and a measurement range of 0.5-175 μm. Calculations were bases on the Fraunhofer theory.
A full description of the principle of LALLS is given in ISO 13320-1.
Method to Determine D3,3 of Water Droplet Size Distribution in an Emulsion
The water droplet size was measured using a well-known low resolution NMR measurement method. Reference is made to Van den Enden, J. C., Waddington, D., Van Aalst, H., Van Kralingen, C. G., and Packer, K. J., Journal of Colloid and Interface Science 140 (1990) p. 105.
Method to Determine Oil Exudation
Oil exudation is determined by measuring the height of the free oil layer that appears on top of the product. This free oil layer is considered a product defect. In order to measure oil exudation, the product is filled into a scaled glass cylinder of 50 ml. The filling height is 185 mm. The filled cylinder is stored in a cabinet at constant temperature (15° C.). Height measurements are executed every week, by measuring the height of the exuded oil layer in mm with a ruler. Oil exudation is expressed as the height of the exuded oil layer divided by the original filling height and expressed in %. Shaking of the cylinders should be avoided.
Method to Determine Pourability
Pourability for pourable compositions according to the invention is measured according to the standard Bostwick protocol. The Bostwick equipment consists of a 125 ml reservoir provided with a outlet near the bottom of a horizontally placed rectangular tub and closed with a vertical barrier. The tub's bottom is provided with a 25 cm measuring scale, extending from the outlet of the reservoir. When equipment and sample both have a temperature of 15° C., the reservoir is filled halfway with 62.5 ml of the sample after it has been shaken by hand ten times up and down. When the closure of the reservoir is removed the sample flows from the reservoir and spreads over the tub bottom. The path length of the flow is measured after 15 seconds. The value, expressed as cm per 15 seconds is the Bostwick rating, which is used as yardstick for pourability.
A set-up was constructed to dissolve carbon dioxide in the melt and expand the mixture over a nozzle to atmospheric pressure. The micronised product was collected in a drum (6) of 250 liters. The set-up is illustrated in
The micronisation parameters are given in table 2.
Preparation of an Edible Water-in-Oil Emulsion
A pourable margarine was prepared with the composition shown in table 1:
Explanation of table 1:
The balance of all composition to 100% is water
RP 70: Rapeseed oil hardened to a slip melting point of 70° C.
1: Lecithin was hydrolysed soybean lecithin (Bolec MT) obtained from UMZ (Unimills Zwijndrecht, Netherlands)
2: Alcohol-soluble fraction from fractionation of native soybean lecithin with alcohol; Cetinol from UMZ.
The water phase was prepared by adding salt to distilled water and adjusting the pH of distilled water from 7.7 to 4.0 using 5 wt. % citric acid, and heated for 5 minutes in a bath of 60° C. to dissolve the solids. The oil phase was prepared by dissolving the emulsifier ingredients and β-carotene in the total amount of sunflower oil at 15° C. Subsequently the micronised fat powder was added to the oil phase carefully using a spatula and the oil phase was mixed with a Turrax at 22000 rotations per minute (rpm) for 6 minutes. Then the water phase was added to the oil phase and the resulting mixture was mixed with a Turrax for 5 minutes at 23500 rpm in a water bath at having a temperature of 15° C.
The temperature of the mixture in the Turrax increased due to the viscous dissipation. However during the whole experiment the temperature was kept below 20° C. The Turrax (type T50) was delivered by Janke & Kunkel IKA Labortechnik. This type of Turrax is designed to minimise air entrainment.
The emulsion was partly poured into a glass cylinder and partly into a twist off pot of 100 ml and both were containers were stored in a cabinet at 15° C.
Results
The prepared emulsions were tested in accordance with the test methods described herein and the results of the tests are given in table 3. A SEM photograph of the micronised fat powder of example 1 (magnification 250 times) is given in
Comparative Experiment A
Comparative experiment A was conducted as example 1, however the fat micronisation step was modified in that the equilibrium pressure in the autoclave was 5 MPa instead of 15 MPa. Before and during depressurisation over the nozzle the mixture in the autoclave was pressurised with Helium to 15 MPa.
The results are shown in table 3. A SEM-photograph of the micronised fat powder is given in
Comparative Experiment B
Comparative experiment B was conducted as example 1, however the fat micronisation step was modified in that the equilibrium pressure in the autoclave was 10 MPa instead of 15 MPa. Before and during depressurisation over the nozzle the mixture in the autoclave was pressurised with Helium to 15 MPa.
The results are shown in table 2. A SEM-photograph of the micronised fat powder is given in
All powders of example 1 and comparative experiments A and B showed the presence of 100% alpha-polymorph material. The micronised powder according to example 1 has a low particle size (see table 2) and has a macroporous structure of submicron size particles, as is shown in
The results show that the emulsion according to example 1 shows a very low oil exudation, which whereas those of comparative experiments A and B have a high oil exudation and therefore the emulsions are not stable.
Example 1 was repeated, but now instead of fat a mixture of fat and sunflower oil was micronised. The composition of the mixture of fat and oil is shown in table 3. In the preparation of the emulsion a Turrax speed of 8000 rpm was used and the Turrax time was 4 minutes.
All micronised products of examples 2-4 showed the presence of alpha-polymorph material in an amount of 100% and comprised submicron size particles. ‘-’ means not determined. Table 5: Oil exudation (%) of the emulsions of examples 2 to 4 as function of the storage time at 15° C.
Examples 2-4 show that the addition of oil to the structuring agent prior to micronisation leads to a reduction in oil exudation of the emulsion prepared using the micronised structuring agent. The micronised mixtures have a different appearance depending on the amount of oil added.
Micronised fat was prepared according to example 1, fat micronisation using instead as fat rapeseed oil hardened to a slip melting point of 68° C.
A dispersion of solid matter in a fat phase was prepared by first preparing a mixture of 4.6 parts (all parts are weight parts) micronised fat in 4.6 parts sunflower oil and stirring the mixture for 3 minutes at about 18° C. under vacuum. The obtained mixture was added to 49 parts sunflower oil and mixed under vacuum at about 18° C. for 1 minute.
To this mixture was added 41.2 parts flour and 0.6 parts parsley flakes (dried) and the resulting mixture was stirred under vacuum at about 18° C. for 1 minute, 30 seconds. The resulting dispersion was stable for more than one month at room temperature without substantial oil exudation.
A dispersion was prepared with the following composition (wt. % on final product):
The product was prepared by mixing all ingredients at room temperature using an ultraturrax mixing equipment. The product showed no oil exudation for one month.
A dispersion was prepared similar to that of example 6, however using 47.5 wt. % sunflower oil and 2.5 wt. % micronised fat prepared in example 1. The processing was the same. When stored at 5° C. for one month, the product showed minimal oil exudation.
Example 1 was repeated, however instead of Rp70, SF69 (sunflower oil hardened to a slip melting point of 69° C.) was micronised and used as hardstock in the preparation of the emulsion.
To investigate how Ta (Equilibrium autoclave temperature) influences the morphology of the powders after micronisation, three different experiments were performed at Ta=Tm−10° C. (Example 8), Ta=Tm−5° C. (Example 9) and Ta=Tm (Example 10) respectively, with P=180 bar, in which Tm is the melting point of the hardstock, for Rp69 in these example 69° C.
Xray diffraction showed that all micronised powders are in the α polymorph. SEM analysis shows no real differences in morphology within the chosen range of temperatures, although for Tm−10° C. (59° C.) and Tm−5° C. (64° C.) the morphology seems to be a little more brittle than for Tm (69° C.).
Model Emulsions
Model emulsions were prepared using standard conditions and stored at 15° C. and 25° C. In table 6, a summary of the measured oil exudation (O.E.) and Bostwick values (BW) as function of storage time is given.
Results show that at Tm of 59° C. and 64° C., good O.E. and BW values after 9 weeks were achieved. At Tm=69° C. the oil exudation at 25° C. is less favourable.
Enlarged SEM photographs (5000× magnification) of the micronised powders of examples 8, 9 and 10 are shown in
Number | Date | Country | Kind |
---|---|---|---|
03077247 | Jul 2003 | EP | regional |
This application is a continuation of Ser. No. 13/224,550 filed Sep. 2, 2011 now U.S. Pat. No. 8,940,355, which is a continuation of Ser. No. 10/564,944 filed Jun. 20, 2006, now U.S. Pat. No. 8,025,913, which is a 371 of PCT/EP04/06544 filed Jun. 16, 2004.
Number | Name | Date | Kind |
---|---|---|---|
2521219 | Holman et al. | Sep 1950 | A |
2521242 | Mitchell, Jr. | Sep 1950 | A |
2615160 | Baur | Oct 1952 | A |
2815286 | Andre et al. | Dec 1957 | A |
2892880 | McIntire et al. | Jun 1959 | A |
3120438 | Dairy | Feb 1964 | A |
3170799 | Feuge | Feb 1965 | A |
3270040 | Bradshaw | Aug 1966 | A |
3295986 | Saslaw | Jan 1967 | A |
3338720 | Pichel | Aug 1967 | A |
3425843 | Japikse | Feb 1969 | A |
3433650 | Block | Mar 1969 | A |
3528823 | Rossen | Sep 1970 | A |
3607305 | Westenberg | Sep 1971 | A |
3634100 | Fondu et al. | Jan 1972 | A |
3881005 | Thakkar et al. | Apr 1975 | A |
3892880 | Grolitsch | Jul 1975 | A |
4021582 | Hsu | May 1977 | A |
4160850 | Hallstrom et al. | Jul 1979 | A |
4226894 | Gawrilow | Oct 1980 | A |
4232052 | Nappen | Nov 1980 | A |
4234577 | Zilliken | Nov 1980 | A |
4234606 | Gawrilow | Nov 1980 | A |
4288460 | Ciliberto et al. | Sep 1981 | A |
4292338 | Ainger et al. | Sep 1981 | A |
4294862 | Wilke | Oct 1981 | A |
4308288 | Hara et al. | Dec 1981 | A |
4341813 | Ward | Jul 1982 | A |
4366181 | Dijkshoorn et al. | Dec 1982 | A |
4375483 | Shuford et al. | Mar 1983 | A |
4385076 | Crosby | May 1983 | A |
4388339 | Lomneth et al. | Jun 1983 | A |
4390561 | Blair et al. | Jun 1983 | A |
4391838 | Pate | Jul 1983 | A |
4469710 | Rielley et al. | Sep 1984 | A |
4486457 | Schijf et al. | Dec 1984 | A |
4501764 | Gercama et al. | Feb 1985 | A |
4578274 | Sugisawa et al. | Mar 1986 | A |
4591507 | Bodor et al. | May 1986 | A |
4826699 | Soe | May 1989 | A |
4855157 | Tashiro et al. | Aug 1989 | A |
4889740 | Price | Dec 1989 | A |
4917915 | Cain et al. | Apr 1990 | A |
4933192 | Darling et al. | Jun 1990 | A |
4990355 | Gupta et al. | Feb 1991 | A |
5127953 | Hamaguchi | Jul 1992 | A |
5130156 | Bergquist et al. | Jul 1992 | A |
5185173 | Bethke et al. | Feb 1993 | A |
5186866 | Ryuo et al. | Feb 1993 | A |
5302408 | Cain et al. | Apr 1994 | A |
5352475 | Tholl | Oct 1994 | A |
5374445 | Havenstein et al. | Dec 1994 | A |
5391382 | Chappell | Feb 1995 | A |
5429836 | Fuisz | Jul 1995 | A |
5447735 | Miller | Sep 1995 | A |
5451421 | Tanihara et al. | Sep 1995 | A |
5516543 | Amankonah et al. | May 1996 | A |
5620734 | Wesdorp et al. | Apr 1997 | A |
5707670 | Mehansho et al. | Jan 1998 | A |
5858445 | Huizinga et al. | Jan 1999 | A |
5866192 | Uesugi et al. | Feb 1999 | A |
5904949 | Reddy et al. | May 1999 | A |
5916608 | Lanting et al. | Jun 1999 | A |
5916808 | Kole et al. | Jun 1999 | A |
5972412 | Sassen et al. | Oct 1999 | A |
5985350 | Gubler et al. | Nov 1999 | A |
6020003 | Stroh et al. | Feb 2000 | A |
6031118 | van Amerongen et al. | Feb 2000 | A |
6056791 | Weidner et al. | May 2000 | A |
6077558 | Euber | Jun 2000 | A |
6106885 | Huizinga et al. | Aug 2000 | A |
6106886 | van Amerongen et al. | Aug 2000 | A |
6117475 | van Amerongen et al. | Sep 2000 | A |
6117478 | Dubberke | Sep 2000 | A |
6129944 | Tiainen et al. | Oct 2000 | A |
6156370 | Huizinga et al. | Dec 2000 | A |
6159525 | Lievense et al. | Dec 2000 | A |
6171636 | Sassen et al. | Jan 2001 | B1 |
6187578 | Blinkovsky et al. | Feb 2001 | B1 |
6190680 | Sakurada et al. | Feb 2001 | B1 |
6214406 | Reimerdes | Apr 2001 | B1 |
6217920 | van Eendenburg et al. | Apr 2001 | B1 |
6238723 | Sassen et al. | May 2001 | B1 |
6248389 | Biller et al. | Jun 2001 | B1 |
6284302 | Berger et al. | Sep 2001 | B1 |
6312752 | Lansbergen et al. | Nov 2001 | B1 |
6316030 | Kropf et al. | Nov 2001 | B1 |
6322842 | Reddy et al. | Nov 2001 | B1 |
6352737 | Dolhaine et al. | Mar 2002 | B1 |
6395324 | Effey et al. | May 2002 | B1 |
6403144 | El-Khoury et al. | Jun 2002 | B1 |
6423326 | Shapiro | Jul 2002 | B1 |
6423363 | Traska et al. | Jul 2002 | B1 |
6440336 | Weinreich et al. | Aug 2002 | B1 |
6468578 | Bodor et al. | Oct 2002 | B1 |
6531173 | Brooker | Mar 2003 | B2 |
6533252 | Bernard et al. | Mar 2003 | B1 |
6582749 | Merrick et al. | Jun 2003 | B2 |
6616849 | Osajima et al. | Sep 2003 | B1 |
6743450 | Romanczyk, Jr. et al. | Jun 2004 | B2 |
6753032 | Hirokawa et al. | Jun 2004 | B1 |
6800317 | Wester et al. | Oct 2004 | B2 |
6808737 | Ullanoormadam | Oct 2004 | B2 |
6827964 | Wester et al. | Dec 2004 | B2 |
6929816 | Wester | Aug 2005 | B2 |
6986846 | Shekunov et al. | Jan 2006 | B2 |
6986886 | Hammond et al. | Jan 2006 | B2 |
7056949 | Koike et al. | Jun 2006 | B2 |
7118773 | Floeter et al. | Oct 2006 | B2 |
7223435 | Besselink et al. | May 2007 | B2 |
7575768 | Perlman et al. | Aug 2009 | B2 |
7601184 | Tischendorf | Oct 2009 | B2 |
7618670 | Ullanoormadam | Nov 2009 | B2 |
7807208 | Ullanoormadam | Oct 2010 | B2 |
7862751 | Foster et al. | Jan 2011 | B2 |
8124152 | Janssen et al. | Feb 2012 | B2 |
8147895 | Barendse et al. | Apr 2012 | B2 |
8211470 | Kim | Jul 2012 | B2 |
8431370 | ten Brink et al. | Apr 2013 | B2 |
8586122 | McNeill et al. | Nov 2013 | B2 |
8927045 | Barendse et al. | Jan 2015 | B2 |
20010029047 | Liu et al. | Oct 2001 | A1 |
20020034577 | Vogensen et al. | Mar 2002 | A1 |
20020048606 | Zawistowski | Apr 2002 | A1 |
20020076476 | Kuil et al. | Jun 2002 | A1 |
20020132035 | Tamarkin et al. | Sep 2002 | A1 |
20020168450 | Drudis et al. | Nov 2002 | A1 |
20030064141 | Brooker | Apr 2003 | A1 |
20030068425 | Khare | Apr 2003 | A1 |
20030124228 | Goto et al. | Jul 2003 | A1 |
20030124288 | Merziger et al. | Jul 2003 | A1 |
20030165572 | Auriou | Sep 2003 | A1 |
20030203854 | Pischel et al. | Oct 2003 | A1 |
20040076732 | Valix | Apr 2004 | A1 |
20040101601 | Loh et al. | May 2004 | A1 |
20040105931 | Basheer et al. | Jun 2004 | A1 |
20040126475 | Hashizume et al. | Jul 2004 | A1 |
20040166204 | Smith et al. | Aug 2004 | A1 |
20040197446 | Haynes et al. | Oct 2004 | A1 |
20050014158 | Adam et al. | Jan 2005 | A1 |
20050069619 | Bot et al. | Mar 2005 | A1 |
20050069625 | Chimel et al. | Mar 2005 | A1 |
20050123667 | Sakuma et al. | Jun 2005 | A1 |
20050170062 | Burling et al. | Aug 2005 | A1 |
20050175745 | Zawistowski | Aug 2005 | A1 |
20050196512 | Nakhasi et al. | Sep 2005 | A1 |
20050271791 | Wright et al. | Dec 2005 | A1 |
20060019021 | Plank et al. | Jan 2006 | A1 |
20060035871 | Auweter et al. | Feb 2006 | A1 |
20060051479 | Chiavazza et al. | Mar 2006 | A1 |
20060115553 | Gautam et al. | Jun 2006 | A1 |
20060280855 | Van Den Berg et al. | Dec 2006 | A1 |
20070054028 | Perlman et al. | Mar 2007 | A1 |
20070087085 | Sarma et al. | Apr 2007 | A1 |
20070154617 | Lansbergen | Jul 2007 | A1 |
20070254088 | Stewart et al. | Nov 2007 | A1 |
20070286940 | Herzing et al. | Dec 2007 | A1 |
20080089978 | Grigg et al. | Apr 2008 | A1 |
20080187645 | Ekblom et al. | Aug 2008 | A1 |
20080193628 | Garbolino et al. | Aug 2008 | A1 |
20080193638 | McMaster et al. | Aug 2008 | A1 |
20080226786 | Ward et al. | Sep 2008 | A1 |
20080268130 | Bons et al. | Oct 2008 | A1 |
20080274175 | Schramm et al. | Nov 2008 | A1 |
20080317917 | Janssen et al. | Dec 2008 | A1 |
20090022868 | Van Den Bremt et al. | Jan 2009 | A1 |
20090029024 | McNeill et al. | Jan 2009 | A1 |
20090041898 | Garbolino et al. | Feb 2009 | A1 |
20090123633 | Cleenewerck et al. | May 2009 | A1 |
20090136645 | Garbolino | May 2009 | A1 |
20090263559 | Van Horsen et al. | Oct 2009 | A1 |
20100040737 | Radlo et al. | Feb 2010 | A1 |
20100159079 | Qvyjt | Jun 2010 | A1 |
20110070335 | Brugger et al. | Mar 2011 | A1 |
20110244111 | Den Adel et al. | Oct 2011 | A1 |
20110287156 | Perlman | Nov 2011 | A1 |
20110287160 | Dobenesque et al. | Nov 2011 | A1 |
20110311706 | van den Berg et al. | Dec 2011 | A1 |
20110311707 | Bezemer et al. | Dec 2011 | A1 |
20120018535 | Wubbolts et al. | Jan 2012 | A1 |
20130004522 | Dvir et al. | Jan 2013 | A1 |
20130115361 | Floter et al. | May 2013 | A1 |
Number | Date | Country |
---|---|---|
10253193 | Jun 2004 | AR |
2004262853 | Jun 2008 | AU |
2253515 | May 1974 | DE |
3220916 | Dec 1983 | DE |
10253111 | May 2004 | DE |
0505007 | Sep 1992 | EA |
0327225 | Jul 1993 | EA |
0021483 | Jan 1981 | EP |
0041299 | Jan 1983 | EP |
0089082 | Sep 1983 | EP |
0063835 | Apr 1985 | EP |
0237120 | Sep 1987 | EP |
0294692 | Dec 1988 | EP |
0327120 | Aug 1989 | EP |
0393963 | Oct 1990 | EP |
0289069 | Mar 1993 | EP |
0572051 | Dec 1993 | EP |
0775444 | May 1997 | EP |
0780058 | Jun 1997 | EP |
0796567 | Sep 1997 | EP |
0744992 | Oct 1997 | EP |
0898896 | Mar 1999 | EP |
0594152 | Feb 2000 | EP |
1238589 | Sep 2002 | EP |
0962150 | Aug 2003 | EP |
1419698 | May 2004 | EP |
1419811 | May 2004 | EP |
1557090 | Jul 2005 | EP |
1795257 | Jun 2007 | EP |
1815752 | Aug 2007 | EP |
1180545 | Sep 2007 | EP |
1114674 | Sep 2008 | EP |
2016834 | Jan 2009 | EP |
1285584 | Nov 2009 | EP |
2123164 | Nov 2009 | EP |
2181604 | May 2010 | EP |
1197153 | Mar 2011 | EP |
1651338 | May 2011 | EP |
0897671 | Jul 2011 | EP |
1865786 | Nov 2011 | EP |
2243653 | Apr 1975 | FR |
2776167 | Sep 1999 | FR |
1114674 | May 1968 | GB |
1537011 | Dec 1978 | GB |
1538958 | Jan 1979 | GB |
2095966 | Oct 1982 | GB |
2095968 | Oct 1982 | GB |
2177283 | Jan 1987 | GB |
2208296 | Mar 1989 | GB |
2208378 | Nov 1991 | GB |
2292949 | Mar 1996 | GB |
2320175 | Jun 1998 | GB |
5951742 | Mar 1984 | JP |
62239949 | Oct 1987 | JP |
2299544 | Dec 1990 | JP |
2003210107 | Jul 2003 | JP |
WO9308699 | May 1993 | WO |
WO9521688 | Aug 1995 | WO |
WO9638047 | Dec 1995 | WO |
WO9614755 | May 1996 | WO |
WO9619115 | Jun 1996 | WO |
WO9742830 | Nov 1997 | WO |
WO9813133 | Apr 1998 | WO |
WO9847386 | Oct 1998 | WO |
WO9956558 | Nov 1999 | WO |
WO0009636 | Feb 2000 | WO |
W00021490 | Apr 2000 | WO |
WO0021490 | Apr 2000 | WO |
WO0045648 | Aug 2000 | WO |
WO0041491 | Dec 2000 | WO |
WO0100046 | Jan 2001 | WO |
WO0132035 | May 2001 | WO |
WO0143559 | Jun 2001 | WO |
WO0166560 | Sep 2001 | WO |
WO0191569 | Dec 2001 | WO |
WO0178529 | Mar 2002 | WO |
WO02100183 | Dec 2002 | WO |
WO03043430 | May 2003 | WO |
WO03084337 | Oct 2003 | WO |
WO03096817 | Nov 2003 | WO |
WO03103633 | Dec 2003 | WO |
WO2004068959 | Aug 2004 | WO |
WO2004093571 | Nov 2004 | WO |
WO2005014158 | Feb 2005 | WO |
WO2005051089 | Jun 2005 | WO |
WO2005071053 | Aug 2005 | WO |
WO2005074717 | Aug 2005 | WO |
WO2005074726 | Aug 2005 | WO |
WO2006005141 | Feb 2006 | WO |
WO2006066979 | Jun 2006 | WO |
WO2006079445 | Aug 2006 | WO |
WO2006087090 | Aug 2006 | WO |
WO2006087091 | Aug 2006 | WO |
WO2006087092 | Aug 2006 | WO |
WO2006087093 | Aug 2006 | WO |
WO2006134152 | Dec 2006 | WO |
WO2007022897 | Mar 2007 | WO |
WO2007024770 | Apr 2007 | WO |
WO2007039020 | Apr 2007 | WO |
WO2007039040 | Apr 2007 | WO |
WO2007096211 | Aug 2007 | WO |
WO2007096243 | Aug 2007 | WO |
WO2008125380 | Oct 2008 | WO |
WO2009068651 | Jun 2009 | WO |
WO2010053360 | May 2010 | WO |
WO2010060713 | Jun 2010 | WO |
WO2010069746 | Jun 2010 | WO |
WO2010069747 | Jun 2010 | WO |
WO2010069750 | Jun 2010 | WO |
WO2010069751 | Jun 2010 | WO |
WO2010069752 | Jun 2010 | WO |
WO2010069753 | Jun 2010 | WO |
WO2011160921 | Dec 2011 | WO |
Entry |
---|
Garti et al. JAOCS, vol. 75, No. 12 (1998) pp. 1825-1831. |
Nutrition: Today's challenges and opportunities, Leatherhead Food International, Jun. 2008, pp. 1-6, vol. 42 No. 5, US. |
The prilling process with liquid nitrogen, Jet Priller, Jun. 23, 2010, pp. 1-2, ., Linde, US. |
Anna Von Bonsdorff-Nikander, Studies on a Cholesterol-Lowering Microcrystalline Phystosterol Suspension in Oil, Division of Pharmaceutical Technology Faculty of Pharmacy, Feb. 12, 2005, 12, 28-30, 35-44. |
Anonymous, Particle Sizes of Milk Powders Part I, Dairy Products Technolgoy Center Dairy Ingredients Applications Program, Apr. 2000, pp. 1-2, vol. 2 No. 4. |
Belitz et al., Milk and Dairy Products, Food Chemistry, 1999, pp. 470-474 and pp. 497-498XP002264854. |
Charteris et al., Edible table (bio) spread containing potentially probiotic Lactobacillus and Bifidobacterium species, International Journal of Dairy Technology, Feb. 2002, pp. 44-56XP002635276, vol. 55 No. 1. |
Christiansen et al, Cholesterol-lowering effect of spreads enriched with microcrystalline plant sterols in hypercholesterolemic subject, European Journal of Nutrition, 2001, 66-73, 40. |
Christoph et al., Glycerol, Ullmann's Encyclopedia of Industrial Chemistry, 2012, pp. 67-82. NB: only relevant pp. 67-69 and 79., vol. 17, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. |
D. Chapman, The Polymorphism of Glycerides, University Chemical Laboratory Chemical Reviews, Dec. 2, 1961, pp. 433-456, 62. |
De Graaf et al., Consumption of tall oil-derived phytosterols in a chocolate matrix significantly decreases plasma total and low-density lipoprotein-cholesterol levels, British Journal of Nutrition, 2002, pp. 479-488. |
Experimental and Analytical Facilities, Delft University of Technology, Dec. 16, 2005, pp. 41-51. |
Ferguson et al., The Polymorphic Forms or Phases of Triglyceride Fats, Chemical Reviews, 1941, pp. 355-384. |
Fischer, Formulation challenges in Ice Cream Gelling and thickening systems and their applications fruit preparations, Food Ingredients and Analysis International, 2001, pp. 29-31, vol. 23 No. 3. |
Fischer, Improved fruit fibres for modern food processing, Food Ingredients and Analysis International, 2001, pp. 29-31, vol. 23 No. 3. |
Formo et al., Bailey's Industrial Oil and Fat Products, Bailey's Industiral Oil and Fat Products, 1979, pp. 317, 326, 377, 382, 398, vol. 1 4th Edition. |
Formo et al., Composition and Characteristics of Individual Fats and Oils, Bailey's Industrial Oil and Fat Products, 1979, pp. 382-384, vol. 1 4th Edition. |
Gerber et al., Effect of Process-Parameters on Particles Obtained by the Rapid Expansion of Supercritical Solutions, World Congress on Oil Particle Technology, 1998, pp. 1-11XP001080632. |
Gunstone et al., Analytical Methods Slip Point, The Lipid Handbook, 1994, pp. 321-322, 2nd Edition. |
Gunstone et al., Food uses of oils and fats, The Lipid Handbook, 2007, pp. 336-341, 3rd Edition. |
Gunstone et al., Occurrence and characterisation of oils and fats, The Lipid Handbook, 2007, pp. 49-53, 3rd Edition. |
Gunstone et al., Occurrence and Characterisation of Oils and Fats, The Lipid Handbook, 2007, pp. 51, 55, 63, 66, 67, 3rd Edition. |
Gunstone et al., Polymorphism and nomenclature of lipid crystal forms, The Lipid Handbook, 1995, pp. 405, 2nd Edition. |
Gunstone, Lipids in Foods, Lipids in Foods Chemistry, Biochemistry and Technology, 1983, pp. 154. |
Hasenhuettl et al., Starch, Food Emulsifiers and Their Applications, 2007, pp. 274-275, Second Edition. |
Hayes et al, Nonesterified Phytosterols Dissolved and Recrystallized in Oil Reduce Plasma Cholesterol in Gerbils and Humans, The journal of Nutrition, Jun. 1, 2006, 1395-1399, 134 No. 6, US. |
Hui, Bailey's Industrial Oil and Fat Products, Bailey's Industrial Oil and Fat Products, 1996, pp. 484-485, 1-5th edition, US. |
Hydrogenation, Wikipedia, pp. 1-10. |
Interesterified Fat, Wikipedia, pp. 1-4. |
IPRP 1 in PCTEP2011071150, dated Feb. 25, 2013. |
IPRP in PCTEP2009066104, dated Sep. 28, 2010, WO. |
IPRP in PCTEP2009066105, dated Mar. 24, 2011. |
IPRP in PCTEP2011071150, dated Apr. 23, 2013. |
IPRP1 in PCTEP2009066093, dated Jun. 21, 2011. |
IPRP1 in PCTEP2009066098, dated Jun. 21, 2011. |
IPRP1 in PCTEP2009066107, dated Jun. 21, 2011. |
IPRP1 in PCTEP2011070933, dated Jun. 18, 2013. |
IPRP2 in PCTEP2004006544, dated Jan. 3, 2006, WO. |
IPRP2 in PCTEP2006000800, dated Jun. 27, 2007, WO. |
IPRP2 in PCTEP2006000801, dated Mar. 20, 2007. |
IPRP2 in PCTEP2009066095, dated Mar. 24, 2011, WO. |
IPRP2 in PCTEP2009066105, dated Mar. 24, 2011. |
IPRP2 in PCTEP2011065601, dated Sep. 24, 2012, WO. |
IPRP2 in PCTEP2011070948, dated Mar. 11, 2013, WO. |
IPRP2in PCTEP2011071168, dated Sep. 5, 2012. |
IPRP2 in PCTEP2011071397, dated Mar. 21, 2013. |
IRPR2 in PCTEP2011058922, dated Jul. 6, 2012. |
Johansson et al., Water-in-Triglyceride Oil Emulsions. Effect of Fat Crystals on Stability, JAOCS Journal of the American Oil Chemists' Society, 1995, pp. 939-950, vol. 72 No. 8. |
K. Davidsson, Powdered fats for soups and sauces—and a range of other food products, Food Ingredients and Analysis International, 2001, pp. 29-30, 23 (4). |
Lipson et al., Analysis of the Broadening of Powder Lines, Interpretation of X-Ray Powder Diffraction Patterns, 1970, pp. 244-263. |
Lopez et al., Milk fat and primary fractions obtained by dry fractionation 1. Chemical composition and crystallisation properties, Chemistry and Physics of Lipids, Oct. 2006, pp. 17-33, vol. 144, Issue 1. |
Lowe, Experimental Cookery, Experimental Cookery, 1955, pp. 270-273, 4th edition, ., US. |
M. Dervisoglu and F. Yazici, The Effect of Citrus Fibre on the Physical, Chemical and Sensory Properties of Ice Cream, Food Science and Technology International, Apr. 2006, pp. 159-164—with abstract, 12. |
Margarines and Shortenings, Ullmanns Encyclopedia of Industrial Chemistry, 1990, pp. 156-158, vol. A16. |
Micaleff et al., Beyond blood lipids phytosterols statins and omega-3 polyunsaturated fatty acid therapy for hyperlipidemia, Journal of Nutrional Biochemistry, 2009, pp. 927-939; XP026755870, vol. 20. |
Munuklu et al., Particle formation of an edible fat (rapeseed 70) using the supercritical melt micronization (ScMM) process, The Journal of Supercritical Fluids, Apr. 2007, pp. 433-442, vol. 40, Issue 3. |
Munuklu et al., Supercritical Melt Micronization Using theParticles from Gas Saturated Solution Process, American Chemical Society Symposium, 2003, pp. 353-369. |
Nathalie De Cock, Structure development in confectionery products: importance of triacylglycerol composition, Universiteit Gent Faculteit Bio-ingenieurswetenschappen, 2011, pp. 1-72. |
Norizzah et al., Effects of chemical interesterification on physicochemical properties of palm stearin and palm kernel olein blends, Food Chemistry, 2004, pp. 229-235, 86. |
Notice of Opposition from Feyecon Development & Implementation BV in EP06706499, Aug. 30, 2012. |
Notice of Opposition from Kerry Group Services Intl Ltd in EP06706499, Aug. 30, 2012. |
P. Munuklu, Particle formation of edible fats using the supercritical melt micronization process (ScMM), The Journal of Supercritical Fluids, 2007, pp. 181-190, 43. |
Pernetti et al., Structuring of edible oils by alternatives to crystalline fat, Current Opinion in Colloid & Interface Science, Oct. 2007, pp. 221-231, vol. 12, Issues 4-5. |
Ribeiro et al., Zero trans fats from soybean oil and fully hydrogenated soybean oil: Physico-chemical properties and food applications, Food Research International, 2009, pp. 401-410, vol. 42. |
S. P. Kochhar, Influence of Processing on Sterols of Edible Vegetable Oils, Prog Lipid Res, 1983, pp. 161-188, vol. 22. |
Search Report in EP03077247, dated Apr. 7, 2004. |
Search Report in EP05075384, dated Jul. 5, 2005, EP. |
Search Report in EP05075393, dated Jul. 20, 2005. |
Search report in EP06122483, dated Jul. 15, 2008, EP. |
Search Report in EP08172283, dated Jun. 5, 2009. |
Search Report in EP08172284, dated Jun. 4, 2009, EP. |
Search Report in EP08172286, dated May 20, 2009, EP. |
Search Report in EP08172298, dated Apr. 9, 2009, EP. |
Search Report in EP08172300, dated Jun. 5, 2009. |
Search Report in EP08172304, dated May 28, 2009. |
Search Report in EP10166774, dated Dec. 3, 2010. |
Search Report in EP10181979, dated Nov. 17, 2010. |
Search Report in EP10195564, dated May 20, 2011, EP. |
Search Report in EP10195567, dated May 24, 2011. |
Search Report in EP10195650, dated May 4, 2011. |
Search Report in EP10195655, dated Jun. 15, 2011, EP. |
Search Report in EP10196443, dated May 27, 2011. |
Search Report in EP10196444, dated May 25, 2011. |
Search Report in PCTEP2004006544, dated Jan. 28, 2005, WO. |
Search Report in PCTEP2006000800, dated Aug. 2, 2006, WO. |
Search Report in PCTEP2006000801, dated Aug. 11, 2006, WO. |
Search Report in PCTEP2009066093, dated Mar. 17, 2010. |
Search Report in PCTEP2009066095, dated Mar. 23, 2010, WO. |
Search Report in PCTEP2009066098, dated Mar. 17, 2010. |
Search Report in PCTEP2009066104, dated Jan. 14, 2010, WO. |
Search Report in PCTEP2009066105, dated Jan. 28, 2010. |
Search Report in PCTEP2009066107, dated Jan. 12, 2010, WO. |
Search Report in PCTEP2011058922, dated Sep. 15, 2011. |
Search Report in PCTEP2011065601, dated Oct. 21, 2011. |
Search Report in PCTEP2011070933, dated Mar. 21, 2012, WO. |
Search Report in PCTEP2011070948, dated Feb. 9, 2012, WO. |
Search Report in PCTEP2011071150, dated Jan. 30, 2012. |
Search Report in PCTEP2011071168, dated Feb. 9, 2012. |
Search Report in PCTEP2011071282, dated Jan. 25, 2012. |
Search Report in PCTEP2011071397, dated Feb. 9, 2012. |
Shahidi et al., Margarine processing plants and equipment, Edible Oil and Fat Product, Margarine processing plants and equipment, 2005, pp. 502, 518. |
Shurtleff et al., History of Soy Oil Hydrogenation and of Research on the Safety of Hydrogenated Vegetable Oils, SoyInfo Center, 2007, pp. 1-9. |
Starches, Tate & Lyle Product Brochure, 2009, pp. 1-16. |
Strawberry Powder Flavor GA1403, Strawberryflavor.com, 2005, pp. 1. |
The American Heritage Dictionary, 1982, pp. 407, 1225, 2nd College Edition. |
Turk et al., Micronization of pharmaceutical substances by the Rapid Expansion of Supercritical Solutions (RESS): a promising method to improve bioavailability of poorly soluble pharmaceutical agents, The Journal of Supercritical Fluids, Jan. 2002, pp. 75-84, vol. 22 Issue 1. |
Van den Enden et al., A Method for the Determination of the Solid Phase Content of Fats Using Pulse Nuclear Magnetic Resonance, Fette Seifen Anstrichmittel, 1978, pp. 180-186, vol. 80. |
Van den Enden et al., Rapid Determination of Water Droplet Size Distributions by PFG-NMR, Journal of Colloid and Interface Science, Nov. 1990, pp. 105-113, vol. 140 No. 1. |
Van den Enden, A Method for the Determin of the Solid Phase Content of Fats Using Pulse Nuclear Magnetic Resonance, Fette Seifen Anstrichmittel, 1978, 180, 5, US. |
Von Bonsdorff et al., Optimizing the Crystal Size and Habit of β-Sitosterol in Suspension, AAPS PharmSciTech, 2003, pp. 1-8, 4 (3). |
Written Opinion in EP03077247, dated Apr. 7, 2004. |
Written Opinion in EP05075384, dated Jul. 5, 2005. |
Written Opinion in EP05075393, dated Jul. 20, 2005. |
Written Opinion in EP06122483, dated Jul. 15, 2008, EP. |
Written opinion in EP08172283, dated Jun. 5, 2009. |
Written Opinion in EP08172284, dated Jun. 4, 2009, EP. |
Written Opinion in EP08172286, dated May 20, 2009, EP. |
Written Opinion in EP08172298, dated Apr. 9, 2009, EP. |
Written Opinion in EP08172300, dated Jun. 5, 2009. |
Written Opinion in EP08172304, dated May 28, 2009. |
Written Opinion in EP10166774, dated Dec. 3, 2010. |
Written Opinion in EP10181979, dated Nov. 11, 2010. |
Written Opinion in EP10195564, dated May 20, 2011, EP. |
Written Opinion in EP10195567, dated May 24, 2011. |
Written Opinion in EP10195655, dated Jun. 15, 2011. |
Written Opinion in EP10196443, dated May 27, 2011. |
Written Opinion in EP10196444, dated May 25, 2011, EP. |
Written Opinion in PCTEP2004006544, dated Jan. 28, 2005, WO. |
Written Opinion in PCTEP2006000800, dated Aug. 2, 2006, WO. |
Written Opinion in PCTEP2006000801, dated Aug. 11, 2006. |
Written Opinion in PCTEP2009066093, dated Mar. 17, 2010. |
Written Opinion in PCTEP2009066095, dated Mar. 23, 2010, WO. |
Written Opinion in PCTEP2009066098, dated Mar. 17, 2010. |
Written Opinion in PCTEP2009066104, dated Jan. 14, 2010, WO. |
Written Opinion in PCTEP2009066105, dated Jan. 28, 2010. |
Written Opinion in PCTEP2009066107, dated Jan. 12, 2010, WO. |
Written Opinion in PCTEP2011058922, dated Sep. 15, 2011. |
Written Opinion in PCTEP2011065601, dated Oct. 21, 2011. |
Written Opinion in PCTEP2011070933, dated Mar. 21, 2012, WO. |
Written Opinion in PCTEP2011070948, dated Feb. 9, 2012, WO. |
Written Opinion in PCTEP2011071150, dated Jan. 30, 2012. |
Written Opinion in PCTEP2011071168, dated Feb. 9, 2012. |
Written Opinion in PCTEP2011071282, dated Jan. 25, 2012. |
Written Opinion in PCTEP2011071397, dated Feb. 9, 2012. |
Number | Date | Country | |
---|---|---|---|
20150118383 A1 | Apr 2015 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 13224550 | Sep 2011 | US |
Child | 14582483 | US | |
Parent | 10564944 | US | |
Child | 13224550 | US |