WO2019154883A1 - Composition de remplissage pour produits alimentaires enrobés - Google Patents
Composition de remplissage pour produits alimentaires enrobés Download PDFInfo
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- WO2019154883A1 WO2019154883A1 PCT/EP2019/052947 EP2019052947W WO2019154883A1 WO 2019154883 A1 WO2019154883 A1 WO 2019154883A1 EP 2019052947 W EP2019052947 W EP 2019052947W WO 2019154883 A1 WO2019154883 A1 WO 2019154883A1
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- WIPO (PCT)
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- filling composition
- weight
- coating material
- amount
- food product
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Classifications
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L13/00—Meat products; Meat meal; Preparation or treatment thereof
- A23L13/03—Coating with a layer; Stuffing, laminating, binding, or compressing of original meat pieces
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L13/00—Meat products; Meat meal; Preparation or treatment thereof
- A23L13/60—Comminuted or emulsified meat products, e.g. sausages; Reformed meat from comminuted meat product
- A23L13/65—Sausages
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- A—HUMAN NECESSITIES
- A22—BUTCHERING; MEAT TREATMENT; PROCESSING POULTRY OR FISH
- A22C—PROCESSING MEAT, POULTRY, OR FISH
- A22C13/00—Sausage casings
- A22C13/0013—Chemical composition of synthetic sausage casings
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L13/00—Meat products; Meat meal; Preparation or treatment thereof
- A23L13/40—Meat products; Meat meal; Preparation or treatment thereof containing additives
- A23L13/42—Additives other than enzymes or microorganisms in meat products or meat meals
- A23L13/424—Addition of non-meat animal protein material, e.g. blood, egg, dairy products, fish; Proteins from microorganisms, yeasts or fungi
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L13/00—Meat products; Meat meal; Preparation or treatment thereof
- A23L13/40—Meat products; Meat meal; Preparation or treatment thereof containing additives
- A23L13/42—Additives other than enzymes or microorganisms in meat products or meat meals
- A23L13/426—Addition of proteins, carbohydrates or fibrous material from vegetable origin other than sugars or sugar alcohols
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L13/00—Meat products; Meat meal; Preparation or treatment thereof
- A23L13/60—Comminuted or emulsified meat products, e.g. sausages; Reformed meat from comminuted meat product
- A23L13/62—Coating with a layer, stuffing or laminating
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L17/00—Food-from-the-sea products; Fish products; Fish meal; Fish-egg substitutes; Preparation or treatment thereof
- A23L17/70—Comminuted, e.g. emulsified, fish products; Processed products therefrom such as pastes, reformed or compressed products
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L17/00—Food-from-the-sea products; Fish products; Fish meal; Fish-egg substitutes; Preparation or treatment thereof
- A23L17/75—Coating with a layer, stuffing, laminating, binding or compressing of original fish pieces
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
- A23P20/00—Coating of foodstuffs; Coatings therefor; Making laminated, multi-layered, stuffed or hollow foodstuffs
- A23P20/10—Coating with edible coatings, e.g. with oils or fats
Definitions
- the present invention relates to filling compositions for use in a coated food product, as well as coated food products comprising the filling composition.
- the filling compositions are particularly suitable for use in the extrusion filling of coated food products, such as sausages.
- Synthetic coatings for food products are well known in the art. Synthetic coatings are typically made from cellulose, though collagen and even plastics may also be used. A disadvantage of these coating materials is that they tend to confer an unnatural and unappealing texture to the outside of a food product and, in some cases, the coating is inedible. This means that synthetic coatings often have to be removed from the food product before consumption, particularly where an imperceptible coating is desirable such as with a skinless sausage. This also adds to the risk of food contamination due to added handling of the food product.
- Alginate is an edible anionic polymer which is made up of two different uranic acid monomers, namely guluronic acid (G-blocks) and mannuronic acid (M-blocks).
- G-blocks guluronic acid
- M-blocks mannuronic acid
- Alginate is commonly used to form sausage casings as part of a process in which a solution of alginate is extruded through a circular die around a food product and subsequently treated with calcium chloride (see e.g. WO 2016/027261 ). During this process, the alginate solution undergoes a gelification process in which matrices of cross-linked alginate chains form.
- the M-blocks form linear molecular chains (M-M-M-M), whilst the G-blocks form folded structures (G-G-G-G). Alternating regions consisting of M- and G-chains form the fundamental alginate structure, which can vary with seaweed type and seasonal climate.
- Synthetic coatings are typically added to a filling composition for a coated food product by extrusion.
- both a coating material and a filling composition must exhibit suitable properties for successful extrusion.
- the viscosity can be controlled, since too high or two low viscosity can impede extrusion of the coating material onto the filling composition.
- the filling composition it is essential that the mixture is not too mushy or too firm, as this can also reduce the efficiency of the extrusion process, and in some instances render extrusion impossible.
- the consistency of the filling composition must be adequate for the subsequent processing to which an extruded product is typically subjected, e.g. strengthening of the casing material by immersion in a strengthening solution and/or cooking of the product in a water bath.
- Filling compositions for food products such as sausages will often comprise water in an amount of greater than 20 %, and animal matter in an amount of less than 60 % by weight of filling composition, particularly where the sausages are for production on a large economic scale. Given the relatively high moisture content of these products, these filling compositions can be quite soft. However, some consumers prefer a sausage with a firmer texture.
- a filling composition and a synthetic coating material are compatible with one another, in particular that good adhesion is observed between the filling composition and the coating material on extrusion of a coated food product. If good adhesion is not achieved then bubbles can form under the coating material during cooking, as a result of the moisture that is driven from the filling composition. This is particularly the case when the coated food product is cooked at high temperature e.g. by frying in oil. Bubble formation can be visually unappealing to consumers, as well as enhancing perception of the casing material during eating. In severe cases, the coating material can split, thereby damaging the structural integrity and appearance of the product.
- the present invention is based on the unexpected discovery that, by adding a combination of modified starch, protein extender and fibre to a filling composition for a coated food product having a high moisture content, a filling composition may be prepared which is readily extrudable with a synthetic casing material and which also exhibits desirable properties on eating.
- the present invention provides filling composition for a coated food product, said filling composition comprising, by weight of the filling composition:
- a method for preparing the filling composition of the present invention comprises combining:
- the present invention provides a coated food product which comprises: a filling composition of the present invention; and a synthetic coating material.
- a method for preparing a coated food product comprises: applying a coating material to a filling composition of the present invention.
- a coated food product obtainable by said method is also provided.
- the present invention provides a kit comprising: protein extender, modified starch and fibre; and instructions for preparing a filling composition or coated food product of the present invention.
- a filling composition of the present invention in a coated food product; and the use of a combination of protein extender, modified starch and fibre for improving the extrusion and/or cooking and/or texture properties of a filling composition which comprises water and animal matter.
- an apparatus for preparing a coated food product.
- the apparatus comprises a tank in which a filling composition of the present invention is held; and a coating device for coating the filling composition with a coating material.
- the present invention is based on the discovery that many of the problems previously encountered with preparing coated food products having a filling composition with a high moisture content may be overcome by adding a combination of modified starch, protein extender and fibre to the filling composition.
- modified starch Such coating materials display excellent extrusion, processing and eating properties.
- the compositions may be successfully extruded and processed, whilst still providing a pleasing texture to the consumer on eating.
- the modified starch is preferably a heat-sensitive modified starch.
- Heat-sensitive modified starches are starches in which particular properties are only activated at a certain temperature. In the present case, the heat-sensitive starches are preferably activated to become firmer at certain temperatures. This has the advantage that the filling composition remains soft during extrusion, but firms up on cooking.
- the heat-sensitive modified starches that are used in the present invention are activated at a temperature of greater than 50 °C, preferably greater than 60 °C, and more preferably greater than 70 °C.
- the heat-sensitive modified starches may be activated at a temperature of lower than 120 °C, preferably lower than 110 °C, and more preferably lower than 100 °C.
- the heat- sensitive modified starches may be activated at a temperature in the range of from 50 to 120 °C, preferably from 60 to 110 °C, and more preferably from 70 to 100 °C.
- the modified starch may be derived from potato, maize, tapioca or wheat.
- Modified starches derived from potato, maize (e.g. waxy maize) or tapioca are particularly suitable for use in the filling compositions of the present invention.
- the modified starch may be starch in which -OH groups have been modified, e.g. esterified or etherified. It will be appreciated that modified starches typically have some, and not all, of the -OH groups modified.
- -OH groups in the starch may have been esterified to give a group having the formula: - OC(0)Ri, where Ri is selected from Ci_ 6 alkyl groups. Preferably, Ri is a methyl group. Esterification may be carried out using acetic anhydride or vinyl acetate.
- -OH groups in the starch may have been etherified to give a group having the formula: -OR 2 , where R 2 is a C 1-6 alkyl group or a C 1-6 hydroxyalkyl group. Preferably, R 2 is a hydroxy propyl group. Etherification may be carried out using propylene oxide.
- the modified starch is starch which has been crosslinked, e.g. using a phosphate compound (e.g. sodium trimetaphosphate or phosphorus oxychloride) or an anhydride (e.g. adipic anhydride).
- a phosphate compound e.g. sodium trimetaphosphate or phosphorus oxychloride
- an anhydride e.g. adipic anhydride
- modified starches used in the filling compositions of the present invention may be modified at their -OH groups and cross-linked.
- Preferred modified food starches for use in the present invention include: • acetylated distarch adipate (EU food additive E1422, a cross-linked starch having esterified -OH groups; e.g. derived from waxy maize such as that sold under the tradename PurityTM HPC);
- acetylated starch (EU food additive E1420, a starch having esterified -OH groups; e.g. derived from tapioca starch such as that sold under the tradename ElastitexTM)
- Modified starches may be used in the filling composition in an amount of at least 3.5 % by weight, preferably at least 4 % by weight, and more preferably at least 4.5 % by weight of the filling composition. Modified starches may be used in a total amount of up to 9.5 % by weight, preferably up to 8.5 % by weight, and more preferably up to 7.5 % by weight of the filling composition. Thus, the filling composition may comprise modified starches in a total amount of from 3.5 to 9.5 % by weight, preferably from 4 to 8.5 % by weight, and more preferably from 4.5 to 7.5 % by weight of the filling composition.
- the filling composition may optionally comprise unmodified starch.
- the unmodified starch may be derived from potato, maize, tapioca or wheat.
- the unmodified starch is derived from potato.
- An example of a preferred unmodified starch for use in the filling composition of the present invention is a potato-derived starch sold under the tradename N- Hance®.
- Unmodified starches may be used in the filling composition in an amount of at least 0.75 % by weight, and preferably at least 1.25 % by weight of the filling composition. Unmodified starches may be used in a total amount of up to 4 % by weight, preferably up to 3.5 % by weight, and more preferably up to 3 % by weight of the filling composition. Thus, the filling composition may comprise unmodified starches in a total amount of from 0 to 4 % by weight, preferably from 0.75 to 3.5 % by weight, and more preferably from 1.25 to 3 % by weight of the filling composition.
- the ratio of modified starch to unmodified starch in the filling composition may be greater than 1 : 1 , preferably greater than 1 .25 : 1 , and more preferably greater than 1.5 : 1.
- the ratio of modified starch to unmodified starch in the filling composition may be up to 10 : 1 , preferably up to 8 : 1 , and more preferably up to 5 : 1.
- the ratio of modified starch to unmodified starch in the filling composition may be from 1 : 1 to 10 : 1 , preferably from 1.25 : 1 to 8 : 1 , and more preferably from 1.5 : 1 to 5 : 1.
- Protein extenders are also used in the filling composition of the present invention. Protein extenders enhance the protein content of the filling composition. Without wishing to be bound by theory, it is believed that the use of protein extenders, at least in part, improves the textural eating properties of the filling composition for the consumer, as well as enhancing the extrusion properties of the filling composition.
- the protein extender used in the filling composition may be derived from soya beans.
- the protein extender may be a soya isolate or a soya concentrate.
- soya concentrate is prepared by removing the fat and water-soluble non-protein components from soya beans.
- soya concentrate may contain some carbohydrates and fibre.
- Soya isolates are prepared by removing all non-protein components from soya beans, and this are substantially carbohydrate and fibre free.
- Protein extenders may be used in the filling composition in an amount of at least 2 % by weight, preferably at least 2.5 % by weight, and more preferably at least 3 % by weight of the filling composition. Protein extenders may be used in the filling composition in a total amount of up to 7 % by weight, preferably up to 6 % by weight, and more preferably up to 5 % by weight of the filling composition.
- the filling composition may comprise protein extenders in a total amount of from 2 to 7 % by weight, preferably from 2.5 to 6 % by weight, and more preferably from 3 to 5 % by weight of the filling composition. It will be appreciated that these amounts relate to the protein extender that is added to the filling composition during its preparation, and do not include proteins that are added to the filling composition as part of the animal matter.
- Fibre is also used in the filling composition of the present invention. It is believed that the fibre, at least in part, improves the structure of the filling composition‘emulsion’ so that it may be readily extruded. Surprisingly, this effect may be achieved without compromising the eating properties perceived on consumption of the filling composition.
- the fibre may be derived from wheat or soya beans. Particularly preferred is fibre derived from soya beans.
- Fibre may be used in the filling composition in an amount of at least 1 % by weight, preferably at least 1.5 % by weight, and more preferably at least than 2 % by weight of the filling composition. Fibre may be used in the filling composition in a total amount of up to 4.5 % by weight, preferably up to 4 % by weight, and more preferably up to 3.5 % by weight of the filling composition.
- the filling composition may comprise fibre in a total amount of from 1 to 4.5 % by weight, preferably from 1.5 to 4 % by weight, and more preferably from 2 to 3.5 % by weight of the filling composition. It will be appreciated that these amounts relate to the fibre that is added to the filling composition during its preparation, and do not include fibre that has been added to the filling composition as part of the animal matter.
- the ratio, by weight, of protein extender to fibre may be greater than 0.8 : 1 , preferably greater than 1 : 1 , and more preferably greater than 1.2 : 1.
- the filling composition comprises animal matter.
- the animal matter may comprise red meat (e.g. beef, lamb, goat or bison), pork, poultry (e.g . chicken or turkey), fish or combinations thereof.
- the animal matter is shredded, minced, pureed or in the form of a paste in the filling composition.
- Animal matter may be used in the filling composition in an amount of at least 20 % by weight, preferably at least 25 % by weight, and more preferably at least 30 % by weight of the filling composition.
- Animal matter may be used in a total amount of up to 60 % by weight, preferably up to 50 % by weight, and more preferably up to 45 % by weight of the filling composition.
- the filling composition may comprise animal matter in a total amount of from 20 to 60 % by weight, preferably from 25 to 50 % by weight, and more preferably from 30 to 45 % by weight of the filling composition.
- Water may be used in the filling composition in an amount of at least 30 % by weight, preferably at least 35 % by weight, and more preferably at least 40 % by weight, by weight of the filling composition. Water may be used in an amount of up to 60 % by weight, preferably up to 55 % by weight, and more preferably up to 50 % by weight of the filling composition.
- the filling composition may comprise water in an amount of from 30 to 60 % by weight, preferably from 35 to 55 % by weight, and more preferably from 40 to 50 % by weight of the filling composition. It will be appreciated that these amounts relate to the water that is added to the filling composition during its preparation, and do not include water that has been added to the filling composition as part of the animal matter.
- Particularly preferred filling compositions comprise animal matter, water, protein extender, starch (modified and, if used, unmodified) and fibre in a combined total amount of at least 90 % by weight, preferably at least 94 % by weight, and more preferably at least 96 % by weight of the filling composition.
- the filling composition will generally comprise further ingredients, such as flavourings (synthetic or natural, e.g. herbs), seasonings, breadcrumbs, oats, vegetable matter, additives etc.
- flavourings synthetic or natural, e.g. herbs
- seasonings seasonings
- breadcrumbs breadcrumbs
- oats vegetable matter
- additives etc.
- the filling composition may comprise a calcium compound or a phosphate compound, and preferably both. The use of these components is believed to improve binding of the coating material to the filling composition.
- Suitable calcium compounds include CaCh, calcium lactate or calcium acetate, with calcium lactate particularly preferred.
- Calcium compounds may be used in the filling composition in an amount of at least 0.1 % by weight, preferably at least 0.15 % by weight, and more preferably at least 0.2 % by weight of the filling composition. Calcium compounds may be used in a total amount of up to 0.5 % by weight, preferably up to 0.4 % by weight, and more preferably up to 0.3 % by weight of the filling composition.
- the filling composition may comprise calcium compounds in a total amount of from 0.1 to 0.5 % by weight, preferably from 0.15 to 0.4 % by weight, and more preferably from 0.2 to 0.3 % by weight of the filling composition.
- Suitable phosphate compounds include sodium tripolyphosphate (STPP).
- Phosphate compounds may be used in the filling composition in an amount of at least 0.01 % by weight, preferably at least 0.05 % by weight, and more preferably at least 0.1 % by weight of the filling composition.
- Phosphate compounds may be used in a total amount of up to 0.35 % by weight, preferably up to 0.30 % by weight, and more preferably up to 0.25 % by weight of the filling composition.
- the filling composition may comprise phosphate compounds in a total amount of from 0.01 to 0.35 % by weight, preferably from 0.05 to 0.30 % by weight, and more preferably from 0.1 to 0.25 % by weight of the filling composition.
- the ratio of calcium compounds to phosphate compounds in the filling composition is preferably greater than 1 : 1 , and more preferably greater than 1.5 : 1 by weight.
- the filling composition of the present invention may be prepared by a method in which the animal matter, water, protein extender, modified starch and fibre are combined.
- the method for preparing the filling composition comprises the step of combining the dry components (e.g . protein extender, modified starch and fibre), and combining the liquid components (e.g. animal matter and water), and subsequently combining the dry components with the liquid components.
- the dry components may be premixed before they are combined with the liquid components and/or the liquid components may be premixed before they are combined with the dry components.
- the method of preparing the filling composition may comprise the step of mixing the components of the filling composition.
- Methods of mixing are known in the art. Mechanical mixing methods are preferably used. Suitable devices for carrying out mechanical mixing are readily available.
- the filling composition will generally be prepared at a temperature of from 0 to 30 °C, preferably from 2 to 20 °C, and more preferably from 4 to 15 °C.
- the filling composition is preferably prepared in batches.
- the filling composition may be used as the filling in a coated food product.
- the coated food product is preferably a coated moulded food product, in which the ingredients have been processed (e.g. by chopping, shredding or grinding the ingredients).
- Coated moulded food products include burgers, kebabs and sausages.
- the coated food product is a sausage, such as a meat sausage. Skinless meat sausages are particularly preferred. Skinless meat sausages are intended to mimic the sensory attributes of traditionally prepared hotdog sausages.
- the coated food product may be a raw, partially cooked or cooked food product.
- the filling composition is, at least partially, covered by a coating material.
- the coating material may cover at least 50 %, preferably at least 70 %, and more preferably at least 90 % of the surface area of the coated food product. Most preferably, all of the surface area of the coated food product is covered with the coating material.
- the coating material may have a thickness of at least 50 pm, preferably at least 100 pm, and more preferably at least 150 pm.
- the coating material may have a thickness of up to 300 miti, preferably up to 250 pm, and more preferably up to 200 pm.
- the coating material may have a thickness of from 50 to 300 pm, preferably from 100 to 250 pm, and more preferably from 150 to 200 pm.
- the coating material may have a tensile strength such that the load required to rupture an extruded coating of 100 pm thickness is at least 100 g, preferably at least 150 g, and more preferably at least 200 g.
- the extruded coating may have a tensile strength such that the load required to rupture an extruded coating of 100 pm thickness is up to 400 g, preferably up to 350 g, and more preferably up to 300 g.
- the extruded coating may have a tensile strength such that the load required to rupture an extruded coating of 100 pm thickness is from 100 to 400 g, preferably from 150 to 350 g, and more preferably from 200 to 300 g.
- Tensile strength is measured using a Brookfield CT3 texture analyser which is operated with a TA18 sphere (12.7 mm in diameter) and a fixture TA-RT-KIT.
- the system settings are: test type set as rupture, a test target correction of 50 g, a trigger load of 5 g and a test speed of 1 mm/s.
- the coating material is preferably applied to the filling composition in the form of an aqueous coating material.
- the coating material preferably comprises a polysaccharide.
- the polysaccharide may be a neutral polysaccharide, such as cellulose, or an anionic polysaccharide. Anionic polysaccharides are particularly preferred for use in the coating material.
- anionic polysaccharides are understood to contain functional groups which exist in an anionic form at a pH of 7.
- the anionic polysaccharide used in the aqueous coating material comprises uronic acid monomers.
- the anionic polysaccharide comprises uronic acid monomers selected from guluronic acid and mannuronic acid. More preferably, the anionic polysaccharide is alginate, i.e. a polymer comprising guluronic acid and mannuronic acid monomers.
- the alginate is preferably a high-guluronic acid alginate.
- the ratio of guluronic acid monomers to mannuronic acid monomers in the alginate may be greater than 1 :1 , preferably greater than 1.5:1 , and more preferably greater than 2:1.
- the alginate preferably comprises homopolymeric blocks of guluronic acid monomers.
- the anionic polysaccharide may also be a pectin ( e.g . a low methoxyl pectin) or, more preferably, a combination of an alginate and a pectin.
- Anionic polysaccharides may be included in the aqueous coating material in an amount of at least 2 %, preferably at least 2.5 %, and more preferably at least 2.8 % by weight of the coating material.
- Anionic polysaccharides may be included in a total amount of up to 8 %, preferably up to 6 %, and more preferably up to 4.5 % by weight of the coating material.
- the coating material may comprise anionic polysaccharides in a total amount of from 2 to 8 %, preferably from 2.5 to 6 %, and more preferably from 2.8 to 4.5 % by weight of the coating material.
- Preferred coating materials for use with the filling composition of the present invention also contain a plasticiser and an interrupting agent.
- Plasticisers are components which soften a coating material.
- the plasticiser used in the aqueous coating material of the present invention is preferably a polyol, such as a C 1-10 polyol, preferably a C 2-8 polyol, and more preferably a C 3-6 polyol.
- Suitable polyols include glycerol (propane-1 , 2, 3-triol), propylene glycol (also known as propane-1 ,2-diol) or sorbitol ((2S,3R,4R,5R)-hexane-1 ,2,3,4,5,6-hexol).
- Glycerol is particularly suitable for use in the casing materials of the present invention.
- Plasticisers may be included in the aqueous coating material in an amount of at least 8 % by weight, preferably at least 12 % by weight, and more preferably at least 18 % by weight of the coating material. Plasticisers may be included in a total amount of up to 42 %, preferably up to 38 %, and more preferably up to 32 % by weight of the coating material. Thus, the coating material may comprise plasticisers in a total amount of from 8 to 42 %, preferably from 12 to 38 %, and more preferably from 18 to 32 % by weight of the coating material.
- Interrupting agents disrupt the spatial orientation of the anionic polysaccharide chains in the coating material.
- Suitable interrupting agents for use in the coating materials include microcrystalline polysaccharides, such as microcrystalline cellulose, and starches, such as tapioca starch, potato-derived starches and corn starch. Microcrystalline cellulose and tapioca starch are preferably used, with microcrystalline cellulose particularly effective.
- Interrupting agents may be included in the aqueous coating material in an amount of at least 0.5 %, preferably at least 1 %, and more preferably at least 1.5 % by weight of the coating material.
- Interrupting agents may be included in a total amount of up to 8 % by weight, preferably up to 7 % by weight, and more preferably up to 6 % by weight of the coating material.
- the coating material may comprise interrupting agent in a total amount of from 0.5 to 8 %, preferably from 1 to 7 %, and more preferably from 1.5 to 6 % by weight of the coating material.
- Microcrystalline polysaccharides will preferably be used at a lower level than starches, e.g. in a totally amount of up to 2.5 % by weight, with starches preferably used in an amount of at least 4 % by weight of the coating material.
- the pH of the aqueous coating material used in the present invention is in the range of from 3.4 to 4.0.
- the pH may be in the range of from 3.5 to 3.9, and preferably in the range of from 3.6 to 3.8.
- the anionic polysaccharides exist in the coating material in a partially precipitated state, thereby providing desirable levels of viscosity for extrusion of the coating compositions.
- the pH level may be measured using standard methods, for instance by introducing a pH probe which is attached to a pH meter into the aqueous coating material. As is conventional in the art, pH measurements will be taken at 25 °C.
- the target pH level may be achieved by using an acid to lower the pH.
- Suitable acids include organic acids, in particular food grade acids such as citric acid, lactic acid, acetic acid, ascorbic acid and glucono-5-lactone.
- Citric acid is particularly suitable for controlling the pH level of the aqueous coating material. The acid will be used in an amount suitable to achieve the target pH level.
- the coating material may comprise an acidic buffer.
- the acidic buffer will generally consist of an acid and a metal salt of the same acid, such as a group 1 or group 2 metal salt.
- the buffer is selected from citric acid and sodium citrate; lactic acid and sodium lactate; acetic acid and sodium acetate; and ascorbic acid and sodium ascorbate.
- the acidic buffer may be used in the aqueous coating material an amount of at least 0.1 % by weight, preferably at least 0.5 % by weight, and more preferably at least 1 % by weight of the coating material.
- the acidic buffer may be used in a total amount of up to 10 % by weight, preferably up to 5 % by weight, and more preferably up to 3 % by weight of the coating material.
- the acidic buffer may be used in a total amount of 0.1 to 10 % by weight, preferably from 0.5 to 5 % by weight, and more preferably from 1 to 3 % by weight of the coating material.
- one or more further ingredients may be included in the coating material to help achieve these properties.
- one or more further ingredients include smoke derivatives, hydrocolloids and insoluble fibres. Hydrocolloids are particularly suitable for use in the casing compositions of the present invention.
- Suitable smoke derivatives include liquid smoke.
- the use of smoke derivatives in the coating material is desirable because of the flavour that they impart on to the coating.
- Smoke derivatives may also catalyse hydrolysis of the alginate chains so that texture of the casing is shortened.
- Smoke derivatives may also be used to increase the viscosity of the coating material.
- Smoke derivatives may be included in the aqueous coating material in an amount of at least 1 % by weight, preferably at least 2 % by weight, and more preferably at least 3 % by weight of the coating material.
- Smoke derivatives may be included in an amount of up to 10 % by weight, preferably up to 8 % by weight, and more preferably up to 5 % by weight of the coating material.
- the coating material may comprise smoke derivatives in an amount of from 1 to 10 % by weight, preferably from 2 to 8 % by weight, and more preferably from 3 to 5 % by weight of the coating material.
- the level of smoke derivatives is preferably limited since they may lead to an undesirable increase in viscosity in the coating material.
- the amount of smoke derivatives included in the aqueous coating material may be limited to less than 3.5 % by weight, preferably less than 1 % by weight, and more preferably less than 0.5 % by weight. In some embodiments, smoke derivatives may even be absent from the coating material.
- Suitable hydrocolloids include hydrocolloidal vegetable gums, and preferably guar gum.
- Other suitable hydrocolloidal vegetable gums include tara gum and locust bean gum. Hydrocolloids may be useful for increasing the viscosity of the coating material.
- Hydrocolloids may be included in the aqueous coating material in an amount of at least 0.1 % by weight, preferably at least 0.25 % by weight, and more preferably at least 0.4 % by weight of the coating material. Hydrocolloids may be included in an amount of up to 1 % by weight, preferably up to 0.75 % by weight, and more preferably up to 0.6 % by weight of the coating material.
- the coating material may comprise hydrocolloids in an amount of from 0.1 to 1 % by weight, preferably from 0.25 to 0.75 % by weight, and more preferably from 0.4 to 0.6 % by weight of the coating material.
- Suitable insoluble fibres include cellulose fibres other than microcrystalline cellulose, citrus fibres and collagen. Insoluble fibres in the coating material may be useful for increasing the viscosity of the coating material.
- Insoluble fibres may be included in the aqueous coating material in an amount of at least 0.5 % by weight, and preferably at least 1 % by weight of the coating material though, in preferred embodiments, insoluble fibres will not be used as preferred viscosity levels are already achieved in the coating material. Insoluble fibres may be included in an amount of up to 10 % by weight, preferably up to 5 % by weight, and more preferably up to 3 % by weight of the coating material. Thus, the coating material may comprise insoluble fibres in an amount of from 0 to 10 % by weight, preferably from 0.5 to 5 % by weight, and more preferably from 1 to 3 % by weight of the coating material.
- chelating agents include phosphates such as sodium hexametaphosphate. Colourings and flavourings, e.g. spices, may also be included in the coating material.
- the coating material is applied to the filling composition in the form of an aqueous composition.
- Water may be used in the aqueous coating material in an amount of at least 50 %, preferably at least 60 %, and more preferably at least 70 % by weight of the coating material.
- the aqueous coating material may have a viscosity of at least 20 Pa-s, preferably at least 25 Pa-s, and more preferably at least 30 Pa-s at 5 °C.
- the coating material may have a viscosity of up to 80 Pa-s, such as up to 70 Pa-s and preferably up to 60 Pa-s at 5 °C.
- the aqueous coating material may have a viscosity of from 20 to 80 Pa-s, such as 25 to 70 Pa-s, preferably from 30 to 60 Pa-s at 5 °C. These viscosities are preferred for extrusion of the coating material.
- Viscosity is measured in Pa-s using a Brookfield R/S-CPS+ Rheometer (cone and plate) which is operated with an external temperature control system at 5 °C, with a C25-1 spindle utilizing a sample volume of 0.08 ml.
- the system settings are: CSR setting, with a shear time of 120 s but a measuring point at 60 s under linear point distribution with the shear rate parameter selected, with a start and end value set at 20 s 1 , and a distribution measuring points number of 60.
- the measuring temperature is set to 4 °C.
- the aqueous coating material used in the present invention may be prepared by a method in which the anionic polysaccharide (preferably in an anhydrous form), plasticiser and interrupting agent are combined in the presence of water, and the pH of the coating material is adjusted so that it is in the range of from 3.4 to 4.0.
- the water is combined with components of the composition that are in liquid form (e.g . plasticisers) and subsequently combined with the dry components of the composition (e.g. powdered anionic polysaccharide and interrupting agent).
- the method for preparing the coating material comprises the step of pre-mixing the dry components (e.g. anionic polysaccharide and interrupting agent) and pre-mixing the liquid components (e.g. water and plasticiser), and subsequently combining the dry and liquid components.
- the step of forming the coating material may comprise the step of mixing the water, anionic surfactant, plasticiser, interrupting agent and any additional ingredients.
- Methods of mixing are known in the art. High shear mixing is preferably used. Suitable devices for carrying out high shear mixing are readily available.
- the viscosity of the coating material may increase over time.
- the coating material may be prepared over a period of greater than 10 minutes, preferably greater than 30 minutes, and more preferably greater than 1 hour. Whilst an increase in viscosity may be observed in these periods, it is generally preferable for the viscosity of the coating material to reach a steady state.
- the coating material may be prepared over a period of greater than 3 hours, and preferably greater than 6 hours, such as 8 or 10 hours, and such as for a period of greater than 12 hours.
- the coating material will generally be prepared at a temperature of from 10 to 40 °C, preferably from 15 to 30 °C, and more preferably from 20 to 25 °C.
- the coating material is preferably prepared in batches. Once the coating material has been prepared, it is preferably homogenised before it is used e.g. in an extrusion process. This is because, during the preparation of the coating material, pockets of insoluble anionic polysaccharide (in which many of the anionic moieties on the polysaccharide chain have been protonated) and soluble anionic polysaccharide (in which few of the anionic moieties on the polysaccharide chains have been protonated) may form. Homogenisation distributes protonated anionic polysaccharide in the form of insoluble particles throughout the coating material. The viscosity of the coating material may reduce as a result of homogenisation.
- Homogenisation may be carried out by mixing the coating material, e.g. using a mechanical mixer, a bowl cutter, vacuum blending, or ultrasonification. Slow blending, e.g. for a period of at least 8 hours, may also be used. Other mixing methods will be known to the person of skill in the art and may also be used.
- vacuum blending it used, the homogenisation process may be carried out for a period of at least 10 minutes, preferably at least 20 minutes, and more preferably at least 30 minutes.
- Vacuum blending may be carried out at a temperature of from 1 to 8 °C, preferably from 2 to 6 °C, for instance at about 4 °C. In order to remove air, the vacuum setting is preferably set high, e.g. at its maximum.
- the coated food product of the present invention may be obtained by a method in which the coating material is applied to the filling composition of the present invention.
- the coating material may be applied to the filling composition in an amount of at least 0.5 % by weight, preferably at least 1 % by weight, and more preferably at least 2.5 % by weight of the filling composition.
- the coating material may be applied to the filling composition in an amount of up to 20 % by weight, preferably up to 10 % by weight, and more preferably up to 5 % by weight of the filling composition.
- the coating material may be applied to the filling composition in an amount of from 0.5 to 20 % by weight, preferably from 1 to 10 % by weight, and more preferably from 2.5 to 5 % by weight of the filling composition.
- the coating material may be applied to the filling composition using methods that are known to the skilled person.
- the coating material is extruded and applied to the filling composition.
- the filling composition is preferably co-extruded with the coating material, though it will be appreciated that the coating material may be first extruded and subsequently applied to a filling composition.
- the coating material may be extruded through a circular die which encircles the co-extruded filling composition. This is particularly preferred when the food product is a sausage, since the coating material may be extruded on to the outside surface of the sausage filling.
- Extrusion may take place at a linear speed of at least 0.05 m/s, preferably at least 0.1 m/s, and more preferably at least 0.5 m/s. Extrusion may take place at a linear speed of up to 5 m/s, preferably up to 4.5 m/s, and more preferably up to 3.8 m/s. This, extrusion may take place at a linear speed of from 0.05 to 5 m/s, preferably from 0.1 to 4.5 m/s, and more preferably from 0.5 to 3.6 m/s.
- An advantage of the present invention is that the coating material may be extruded at relatively high speeds without compromising the integrity of the coating. Thus, in some embodiments, the coating material is extruded at a linear speed of greater than 1 m/s.
- the coating material may be strengthened by contacting the coated food product with group 2 metal ions.
- group 2 metal ions may act as ionic cross-linkers between the chains of the anionic polysaccharide.
- the group 2 metal ions are believed to interact with negatively charged groups that are present in the anionic polysaccharide.
- Group 2 metal ions are particularly effective at strengthening forms of alginate which comprises homopolymeric blocks of guluronic acid monomers.
- the coating material may be strengthened by contacting the coated food product with a solution containing group 2 metal ions, for instance by immersing the coated food product in the solution or by spraying the solution onto the coated food product.
- the group 2 metal ions are preferably selected from calcium ions, barium ions and magnesium ions. Calcium ions are generally preferred due their common use in food products.
- Suitable solutions for strengthening the casing include calcium chloride solutions. Suitable solutions may comprise group 2 metal salts in an amount of at least 5 % by weight, and preferably at least 10 % by weight of the solution.
- the method for preparing a coated food product comprises cooking the coated food product, preferably after it has been strengthened using group 2 metal ions.
- the coated food product may be steamed, boiled, fried, or smoked.
- the food product is cooked at a temperature of greater than 50 °C, and more preferably greater than 60 °C.
- the food product may be partially cooked, or fully cooked.
- the coated food product, optionally once cooked, may be further processed by at least one of drying, chilling ( e.g . at a temperature of between 1 and 10 °C), and freezing ( e.g . at a temperature of less than -5 °C).
- the coated food product may be packaged.
- the coated food product will be packaged as a single article. Generally, however, at least two, preferably at least four, and more preferably at least six coated food products will be included in a package.
- a coated food product of the present invention may be in a dried, chilled, frozen and/or packaged form.
- kits which may conveniently be used for preparing the filling composition and the coated food products disclosed herein.
- the kit may comprise: protein extender, modified starch and fibre; and instructions for preparing a filling composition or coated food product of the present invention.
- the kit further comprises a polysaccharide, and preferably a plasticiser and an interrupting agent; and instructions for preparing a coating material.
- the kit may comprise one or more further ingredients of the filling composition or coating material as described herein.
- the components of the kit are provided in anhydrous form.
- the present invention is based in part on the discovery a combination of protein extender, modified starch and fibre may be used for improving the extrusion and/or cooking and/or texture properties of a filling composition comprising water, e.g. in an amount of at least 30 % by weight of the filling composition, and animal matter.
- the present invention also provides the use of a filling composition of the present invention in a coated food product.
- the coated food product of the present invention may be prepared using an apparatus which comprises: a tank in which the filling composition of the present invention is held; and a coating device in which the filling composition is coated with a coating material, such as a coating material described herein.
- the tank may have a volume of greater than 1 L, preferably greater than 5 L, and more preferably greater than 10 L.
- a tank of this size enables batch-wise production of the filling composition.
- the filling composition of the present invention may be prepared in the tank.
- a water inlet may also be present on the tank to provide water for the filling composition.
- the apparatus may further comprise a mechanical mixer.
- the mechanical mixer may be used to mix the components of the filling composition.
- the mechanical mixer may be introduced into the tank to mix the filling composition.
- the tank may be coupled to a mechanical mixer and the filling composition passed from the tank to the mechanical mixer.
- the apparatus further comprises a coating device, such as an extruder.
- the coating device is used to coat the filling composition with the coating material preferably using a method disclosed herein.
- the apparatus may further comprise a strengthening station, in which the coating of the coated food product is strengthened by contacting the coated food product with group 2 metal ions preferably as described herein.
- Example 1 Screening of filling compositions An existing high moisture filling composition was used in a high-throughput extrusion process. The extrusion profile was poor, because the filling composition was too soft. Further deformation of the sausages was observed during cooking in a water bath. This was also believed to be due to the softness of the filling composition. The texture of the product on eating was also deemed too soft.
- filling compositions were prepared on a small scale.
- the filling compositions were based on the commercially available filling but contained varying quantities and types of protein extender, additives, starch, fiber and spice pack as shown in Figure 1.
- the filling compositions were tested for their ability to be co-extruded with a cellulose casing.
- the filling compositions were also tested for their hardness (maximum force required to compress a food between the molars, indicating the brittleness of the food), cohesiveness (an indication of the strength of internal bonds making up the body of the food), springiness index (the recovery properties of a food with 1 representing a completely elastic material and 0 representing a completely viscous material) and chewiness (an indication of the energy required to chew a solid food to a state where it is swallowable).
- Each filling composition was tested 5 times and an average taken. The measurements were obtained on a CT3TM texture analyzer (BROOKFIELD AMETEK) using the following settings:
- the filling compositions were also assessed for their eating quality.
- compositions C1 to C3 formed a poor filling emulsion compared to the Original, and so were not put forward for extrusion.
- Composition EF1 was not extrudable, and composition EF2 was barely extrudable though the structure did improve on cooking.
- Compositions EF3 to EF6 successfully extruded, but EF3 lacked elasticity, EF4 was too pasty / grainy, and EF5 and EF6 were too doughy on eating.
- Compositions EF7 to EF12 both extruded well and had good eating properties.
- Composition EF12 gave a firm extrudable product with poorer eating than some of the other compositions.
- Compositions EF13 and EF14 were extremely mushy in texture.
- Composition EF15 gave similar properties to EF1 1 , but with a less good, mushier, texture.
- compositions comprising a modified starch, protein extender and fiber exhibited the best combination of properties for a filling composition for a coated food product, with EF11 exhibiting the most promising properties of the compositions screened.
- compositions were prepared and tested in the same manner as those of Example 1 , but with co-extrusion into two alginate-based casing materials: one containing a glycerol plasticiser and a microcrystalline cellulose interrupting agent, and one containing a glycerol plasticiser and a tapioca starch interrupting agent. Details of the compositions and results of the testing are shown in Figure 2.
- Composition EF16 exhibited excellent extrusion properties, but slightly poorer eating than EF11 .
- Composition EF16 in which ElastitexTM was used in place of PurityTM exhibited good extrusion properties but slightly poorer eating than EF16. Where N-Hance® was used in place of PurityTM, EF16 was far too firm and too dry, thereby suggesting that a modified starch is necessary for the optimum balance of extrusion and texture properties.
- Composition EF1 1 but with more fibre, exhibited very good extrusion and eating properties.
- Composition EF 11 but with more fibre and Almidon NationalTM 1317 in place of Firm-texTM, also exhibited very good structure for extrusion and eating properties.
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Abstract
La présente invention concerne des compositions de remplissage destinées à être utilisées dans un produit alimentaire enrobé, ainsi que des produits alimentaires enrobés comprenant la composition de remplissage. Les compositions de remplissage sont particulièrement appropriées pour être utilisées dans le remplissage par extrusion de produits alimentaires enrobés, tels que des saucisses, et comprennent : une matière animale, un allongeur de protéine, de l'amidon modifié, des fibres et de l'eau.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB1802276.4A GB2570933A (en) | 2018-02-12 | 2018-02-12 | Filling composition for coated food products |
GB1802276.4 | 2018-02-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2019154883A1 true WO2019154883A1 (fr) | 2019-08-15 |
Family
ID=61731335
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2019/052947 WO2019154883A1 (fr) | 2018-02-12 | 2019-02-06 | Composition de remplissage pour produits alimentaires enrobés |
Country Status (5)
Country | Link |
---|---|
AR (1) | AR114367A1 (fr) |
GB (1) | GB2570933A (fr) |
UY (1) | UY38087A (fr) |
WO (1) | WO2019154883A1 (fr) |
ZA (1) | ZA201900853B (fr) |
Citations (8)
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WO1994023588A1 (fr) * | 1993-04-14 | 1994-10-27 | Griffith Laboratories Worldwide, Inc. | Matrice de liaison alimentaire pour denrees alimentaires formees |
US5945152A (en) * | 1998-01-26 | 1999-08-31 | Purser; David E. | Method of preparing a fully-cooked semi-moist shelf stable meat product |
WO2006023518A1 (fr) * | 2004-08-16 | 2006-03-02 | Solae Llc | Produit carné restructuré et procédé pour préparer celui-ci |
EP1147709B1 (fr) * | 1997-09-25 | 2006-09-06 | Solae, Llc | Composition protéine-amidon et émulsion de viande contenant cette composition |
US9433221B2 (en) * | 2012-12-14 | 2016-09-06 | Albert Handtmann Maschinenfabrik Gmbh & Co. Kg | Method for producing a foodstuff by coextrusion |
CN106616434A (zh) * | 2016-11-10 | 2017-05-10 | 山东嘉华保健品股份有限公司 | 一种复配大豆浓缩蛋白 |
US20170273340A1 (en) * | 2014-08-22 | 2017-09-28 | Freddy Hirsch Group (Pty) Ltd | Casing for food products |
CN107334082A (zh) * | 2017-07-13 | 2017-11-10 | 诸城市东方食品有限公司 | 一种蜜辣腿排及其制作方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN104489559A (zh) * | 2014-12-10 | 2015-04-08 | 夏华 | 一种红枣营养藕粉的制作方法 |
CN105614734A (zh) * | 2016-01-20 | 2016-06-01 | 西南民族大学 | 一种富含果蔬渣膳食纤维肉脯及其制作方法 |
CN106071938A (zh) * | 2016-06-14 | 2016-11-09 | 吉林大学 | 一种果蔬复合即食肉丸的制作方法 |
CN107439988A (zh) * | 2017-07-10 | 2017-12-08 | 山东商业职业技术学院 | 一种富含膳食纤维的牛肉丸及其制作方法 |
CN107495159B (zh) * | 2017-09-20 | 2020-11-20 | 中南林业科技大学 | 一种超微化雷竹笋膳食纤维火腿肠及其制备方法 |
-
2018
- 2018-02-12 GB GB1802276.4A patent/GB2570933A/en not_active Withdrawn
-
2019
- 2019-02-06 WO PCT/EP2019/052947 patent/WO2019154883A1/fr active Application Filing
- 2019-02-11 ZA ZA2019/00853A patent/ZA201900853B/en unknown
- 2019-02-12 AR ARP190100342A patent/AR114367A1/es unknown
- 2019-02-12 UY UY38087A patent/UY38087A/es not_active Application Discontinuation
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WO1994023588A1 (fr) * | 1993-04-14 | 1994-10-27 | Griffith Laboratories Worldwide, Inc. | Matrice de liaison alimentaire pour denrees alimentaires formees |
EP1147709B1 (fr) * | 1997-09-25 | 2006-09-06 | Solae, Llc | Composition protéine-amidon et émulsion de viande contenant cette composition |
US5945152A (en) * | 1998-01-26 | 1999-08-31 | Purser; David E. | Method of preparing a fully-cooked semi-moist shelf stable meat product |
WO2006023518A1 (fr) * | 2004-08-16 | 2006-03-02 | Solae Llc | Produit carné restructuré et procédé pour préparer celui-ci |
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DATABASE GNPD [online] MINTEL; 1 November 2017 (2017-11-01), ANONYMOUS: "Turkey Sausage", XP055578816, Database accession no. 5195401 * |
Also Published As
Publication number | Publication date |
---|---|
UY38087A (es) | 2019-10-01 |
GB2570933A (en) | 2019-08-14 |
ZA201900853B (en) | 2022-05-25 |
AR114367A1 (es) | 2020-08-26 |
GB201802276D0 (en) | 2018-03-28 |
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