DE2333579A1 - FISH PRODUCT AND METHOD FOR MANUFACTURING IT - Google Patents

Description

PAT H N TA N WA LT E

DR ". ING. VAN DER WERTH '■ DR. FRANZ LEDERER

21 HAMBURG PO 8 MUNICH SUN

WlLtTOKFIK ST «. S3 ■ TEl. .04 111 77 OS 61 O O O O C * 7 rt «" ^ «- OeAHN-fT *. 93 · TIt (OStIt 473947

Munich, June 28, 1973 Q 466 - D / d

Unilever N.V., Burgemeester s'Jacobplein 1, Rotterdam, the Netherlands

Fish product and process for its manufacture

The invention "relates to proteinaceous products for use as food, in particular shaped, freeze-thaw-stable and thermostable alginate gel products that. a characterizing one Contain protein component.

Although it will be apparent from the following description that the invention is particularly applicable to the manufacture of products in which the characterizing protein component of If it comes from fish, it goes without saying that similar products can also be made by crustaceans or crustaceans. In the following, the term "fish protein component" is used to denote any protein material produced by Fish or crustaceans. In addition, the invention is applicable to the use of protein material that from other animal sources, e.g. animal muscle meat such as poultry muscle meat, Milk or eggs.

The invention has particular advantages in the use of protein material with low functionality, i.e., protein material, that has been substantially denatured due to treatments such as heating or protein concentration or Extraction process. The invention enables such im

305684/1097

PtUTItHt »A NK AO .. KAITUK» S / ΙββΙί POCTSCHfCKt HAMItta i LCOI * ER r BREATHES MCM

Reconstitute essential denatured protein into food, which are suitable for human consumption.

It has been found that it is possible to prepare freeze-thaw stable, thermostable gels containing a protein component That are well suited for use in frozen foods.

Thus, the invention relates to food in the form of a thermostable Gels containing a polymer of a protein component and a propylene glycol ester of alginic acid.

The invention also relates to .a method for the production of Foods that are characterized by ". Is that one with a pH above 7 a protein component and a propylene glycol ester of alginic acid are mixed, with a water-insoluble Protein-alginate polymer is created in the form of a thermally stable gel.

As already stated, the protein component of any, Edible proteinaceous material and, for reasons of economy, may most suitably be obtained from protein sources which would normally require cleaning before use and which would otherwise result from proteinaceous waste material for animal feed, agricultural fertilizers or for other industries.

In the frozen fish industry, for example, it has long been known that there is a significant and inevitable waste of fish protein, especially that on heads and The skeletons of fresh or frozen fish that have been filleted hang: .is. Much of the fish that is after removal the fillet pieces are left behind, is inedible per se, but can be used in the glue industry or for the production of animal feed or fertilizers or other goods of little commercial value. In the last few years there have been considerable 8 traps for the extraction or recovery and purification

309884/1097

of "Waste ⁿ fish protein has been undertaken to make it useful in the manufacture of foodstuffs for human consumption. For example, purified fish protein (also known as fish meal or fish protein concentrate) can now be obtained from fish waste by several different methods which are outlined in the overview by Julius Brodie, "Fish By-Products Technology", AVI Publishing Go, Inc. (1965) 209. The preparation of a superior quality fish protein concentrate which is a particularly suitable protein ingredient for use in the present invention is disclosed in GB-PA 52 153/71 (complete specification).

It will be understood that the protein component is not necessarily must be cleaned or refined if it is safe for consumption. For example, alternative sources for Fish protein components consist of coarsely or finely chopped fish muscles that are not subjected to any protein extraction technology have been. For example, it is possible to use finely chopped fish muscles with an average length of less than 2 mm own; it is also possible to use coarsely minced fish muscles with an average length of over 2 mm. In the latter If so, the protein component may comprise fish muscle fibers or fiber bundles of, for example, 2 to 15 mm in length and up to 2 mm Diameter included; this fibrous fabric can expediently be used to give the product of the invention both a natural, to give a fibrous texture, as well as to ensure the necessary fish character.

Suitable propylene glycol esters of alginic acid are soluble esters which are expediently prepared for food purposes by reacting an alginic acid can be made with 1,2-propylene oxide.

The propylene glycol alginic acid esters can still have free carboxyl groups contain. However, for economic reasons it is advantageous to use propylene glycol alginic acid esters in which At least 50 percent of the carboxyl groups in alginic acid are esterified are.

309884/1097

The foods produced according to the invention can also contain other ingredients, such as edible salts, flavorings or aromas, Colorants or texturing aids included.

The foods of the invention can be prepared by first using a mixture of the protein ingredients and the alginic acid ester, making sure that the pH of the mixture is greater than 7, and if necessary one sufficient amount of water is added to the Yermichen and allow the polymerization to proceed, provided that the amount of water added is not so great that the mixture becomes so fluid that the formation of discrete structures by extrusion becomes impossible. Ideally the mixture should be about 15 to 30 weight percent fish protein solids and 0.6 to 2.5 percent by weight of the alginic acid ester, the actual proportions being according to nature the components and the texture of the thermostable gel to be produced are selected.

According to a particularly preferred embodiment of the invention the mixture contains 17 to 25 percent by weight of dried, powdered fish protein concentrate, 0.6 to 2.0 percent by weight Propylene glycol esters of alginic acid, the remainder, apart from minor components such as salts, colorants, flavorings or Flavorings or texturing auxiliaries, consisting of water; the pH is adjusted to a value of 7.5 to 9.5 at the time of preparation of the mixture.

The mixture can be converted into a thermostable one without further treatment Allow gel to harden, or it can be used as a component of a food product by mixing it with others Ingredients, before or after curing, mixed. Alternatively for this purpose, the mixture can also be shaped into a thermally stable gel by extrusion prior to hardening.

Post-extrusion curing can be facilitated by treating the extruded mixture with an aqueous solution of a alkaline material, such as sodium carbonate, sodium hydroxide or

309884/1097

Mixtures thereof, the use of a sodium carbonate solution is preferred to be facilitated. The mixture can quickly be converted into a thermally stable gel of the desired shape which can take the form of threads, fibers, hollow fibers, tubes, rods or strips, for example. So can e.g. threads of up to 5 mm in diameter or strips of up to 5 "mm thickness can be produced. the thickness of the extruded, thermally stable gel food is 0.75 mm.

After curing it may be necessary to adjust the pH of the gel food to a more suitable value. Ideally, the final pH of the gel food should be around 5 to 8, although the use of a slightly higher pH is acceptable came. The pH of the gel food can be lowered by reacting with a dilute, aqueous solution of an acid such as Acetic acid or hydrochloric acid, washes and then foreign liquid, e.g. by centrifugation, is removed. In general, the Concentration of the acid in the aqueous solution 0.5 to 5 percent (weight / volume), but the concentration chosen can vary from the strength of the specific acid used and the degree of alkalinity of the gel food. Ideally, the gel food should contain an amount of moisture that comparable to that of fresh fish muscles, d'.h. about 80 weight percent in the case of fish white muscles. the however, gelled products can have a moisture content of 90 weight percent or more after extrusion. The moisture content is lowered somewhat by any acid washing used to change the pH as described above. Nonetheless, this acid washing may not be sufficient to reduce the moisture content to the desired level, or the washing with acid may not be necessary anyway because of the pH be. An alternative method of reducing the moisture content is to remove the gelled product after it has hardened to immerse in a dilute saline solution for a short time, generally not exceeding 5 minutes, and then Remove foreign liquid, e.g. by centrifugation.

309884/1097

A combination of these methods may be used if necessary will. In general, the saline solution should contain 0.5 "to 5 percent (weight / volume) salt.

A particular use of the invention in accordance with the preferred embodiment described above is manufacture of fish portions, such as fish fingers, fish steaks, "fish cake" or fish pie fillings that are for storage in frozen food State until they are sold or prepared for consumption will. It has been found that up to 15 percent or more cod muscles in these products by the invention Gel foods in fragmented form, e.g. 2.5 cm long, polymerized alginate ester fish protein fibers with 0.5 mm Diameter, or polymerized alginate ester fish protein flakes, which are cut from an extruded tape of thermostable gel 16 mm wide and 0.3 to 1.0 mm thick can without significant deviations in the appearance, texture and taste of these products. The fish protein products of the invention may thus find particular use as food extenders, or they may as analogs Foods are used "self-justly". They reduce the likelihood of syneresis in products containing them, even when thawed from your frozen state and they are therefore particularly suitable for use in many types of foods where water retention occurs Thawing and, where appropriate, when cooking is desirable.

The examples illustrate the invention.

example 1

This example describes the production of flakes from fish protein concentrate, which is suitable for incorporation in fish fingers. An aqueous mixture that, in percent by weight, is 22.5 percent

309884 / 10S7

decolorized fish protein concentrate (made from cod waste according to the method described in GB-PA 52 153/71 (complete specification) ■), 1 percent propylene glycol ester of Alginic acid (Mfr. Alginate Industries Ltd., "Manucol Ester E / RH2"), in which 75 "to 80 percent of the carboxyl groups of the alginic acid esterified) and contains 76.5 percent water is made with acetic acid added to raise the pH set about 8.

and_ The mixture is degassed in vacuo through an opening of 0.75 χ 7 mm extruded into a mixture of 0.5 molar sodium carbonate and 0.2 molar sodium hydroxide, the residence time being in the solution is no more than 5 seconds to obtain solid streaks. The strips are then through Wash with 1 percent (weight / volume) acetic acid adjusted to pH 6 and finally to remove residual Centrifuged surface moisture.

The strips are cut to 0.5 to 1.5 cm in length to simulate flaky fish muscles and without further treatment in an amount of 15 or 30 percent, based on wet weight, incorporated into a mixture of sliced, filleted cod and sodium tripolyphosphate.

The mixture is then shaped, frozen and made into fish fingers divided. The products cannot be distinguished organoleptically from commercially available fish fingers.

Example 2

This example describes the production of flakes from fish protein concentrate for incorporation into fish fingers are suitable.

An aqueous mixture which, in percent by weight, is 22.5% decolorized Fish protein concentrate (as used in example 1),

309884/1097

1 percent propylene glycol ester of alginic acid (as in Example 1 used) and contains 76.5 percent water is made with the addition of acetic acid to adjust the pH to about 8.

The mixture is degassed in vacuo and extruded through an opening of 0.75 χ 7 mm into a mixture of 0.5 molar sodium carbonate and 0.2 molar sodium hydroxide, ... in order to obtain solid strips, the residence time in the Solution is no more than 5 seconds. The strips are adjusted to a pH of about ₉ T O with dilute acetic acid (1 percent, by weight / volume).

Then the water content of the strips is reduced by immersion in a 2.65 percent (weight / volume) saline solution for 60 seconds; residual surface moisture is removed by centrifugation. The salinity of the produced in this way Stripe is about 1.5 percent by weight.

The strips are cut to 0.5 to 1.5 cm in length to simulate flaky table muscles and without further treatment in an amount of 15 or 30 percent, based on the wet weight, a mixture of sliced, filleted cod and sodium tripolyphosphate incorporated.

The mixture is then shaped »frozen and turned into fish fingers divided. The products cannot be distinguished organoleptically from commercially available fish fingers.

Example 3

This example describes the application of a block technique for subsequent chopping and use in products.

An aqueous mixture with a pH of 8.4 is prepared which, by weight, contained 25 percent fish protein, that has been decolorized with alkaline peroxide, 0.8 percent

309884/1097

Propylene glycol ester of alginic acid (as used in Example 1) and contains 74.2 percent water.

The mixture is poured into a mold and stored at 20 ° C. for 16 hours. After this time it has hardened into a solid block.

The block is shredded into flakes, which are then treated with 1 percent (Weight / volume) acetic acid adjusted to a pH of 6.0 and, as before, fish fingers are incorporated.

Example 4

This example describes the use of added caustic in the block technique described in Example 3.

An aqueous mixture with a pH of 8.95 is prepared, that, by weight, 22.5 percent alkaline, discolored fish protein concentrate, 0.8 percent propylene glycol ester of Alginic acid (as used in Example 1), 10.0 percent 10 η sodium hydroxide and contains 66.7 percent water.

The mixture is degassed in vacuo, placed in a mold and at 3 ^° C. for 16 hours
Block hardened.

Stored at 3 ^° C. for hours. After that time it becomes a solid

The block is shredded into flakes, which are then added with 1 percent (Weight / volume) acetic acid adjusted to pH 6.0 and incorporated into fish fingers as previously described.

The simulated fish flakes produced according to Examples 1 to 4 can be incorporated into "fish cake" (a type of fish that is swimming in fat ^: baked, breaded or previously cooked fish coated with mashed potatoes), for example in an amount of 20 percent by weight, whereby the "fish cake" has the following composition before cutting and breading:

309884/1097

25th 2333 579 - 10 - 20th crushed fish muscles 53 simulated fish flakes 2 cooked potatoes spices

Examples 5 "to

The following three mixtures are prepared and made into gelled foods according to the invention. All percentages relate to weight, unless otherwise stated.

Example 5

Fish protein concentrate '25 Propylene glycol ester of alginic acid * 2.5

Water 72 antifoam agent ⁵ '0.5

Example 6

JL

Sägemileh ⁴ ^ 86

Pisch Protein Concentrate '10

20 percent (weight / volume),

aqueous sodium hydroxide solution 2.5

Propylene glycol ester of alginic acid ³ '1 antifoam agent' 0.5

Example 7

Jl.

cooked brown shrimp or shrimp shower 84

Fish protein concentrate ' 9

20 percent (weight / volume),

aqueous sodium hydroxide solution 1,4

Water 4

Propylene glycol ester of alginic acid '1 * 4 Antifoam- ^ ·' 309884/1097 ° * ²

¹ ^ produced from cable waste according to the method described in GB-PA 52 153/71 (complete specification).

² ^ available commercially under the name "Alginade K" (Herst. Alginate Industries, Limited); about 30 percent of the carboxyl groups in alginic acid are esterified.

'' in stores under the name "Silicone MS Antifoam A" (Herst. Hopkins & Williams).

. ' Sawing or cutting waste from a conventional system for the production of fish fingers, which consists of very finely chopped up fish muscles and is essentially denatured by the heat caused by the sawing or cutting friction.

* ^ Commercially available under the name "Manucol Ester E / RH2 ^W (Herst. Alginate Industries, Limited); 75 to 80 percent of the carboxyl groups of the alginic acid are esterified.

Each mixture is extruded into a bath which is an aqueous solution of 0.5 molar sodium carbonate and 0.2 molar sodium hydroxide and held in the bath for a residence time of 5 seconds. After using the pH of the extruded material, adjusted to 6 by 1 percent (w / v) acetic acid foreign fluid is removed. The gelled products are then cooked using indirect steam heating.

In example 5, a softer and more paste-like gel results than in example 1. The gel of example 5 is hardly satisfactory as a textured food ingredient.

Example 6 produces a very satisfactory, solid, white gel.

Example 7 produces a colored but firm gel which is suitable for use in a textured food.

309884/1097

B e i s ρ i e-.l 8

This example describes the applicability of the invention to proteinaceous material obtained from a source other than fish originates.

The following mixture is made into a gel food using the procedure of Examples 5 "through 7. All Percentages relate to weight, unless stated otherwise.

JL

raw, finely chopped beef 90.5

Water 5

20 percent (weight / volume) aqueous Sodium hydroxide solution 3

Propylene glycol ester of alginic acid '1

ο)
Antifoam agent '0.5

'' in trade under the name "Manucol Ester E / RH2" (manuf. Alginate Industries, Limited); 75 to 80 percent of the carboxyl groups in alginic acid are esterified.

¹ commercially under the name "Silicone MS Antifoam A"

(Herst. Hopkins & Williams).

The extruded gel food is heated by indirect steam heating cooked. The gel food has a firm, chewable, fibrous texture.

Patent claims

309884/1097

Claims (15)

Claims Process for the production of a protein-containing food, characterized in that "at a pH above 7 a protein component and a propylene glycol ester of alginic acid are mixed, creating a water-insoluble." Protein-alginate polymer is formed in the form of a thermostable gel. 2. The method according to claim 1, characterized in that at least 50 percent of the carboxyl groups of the alginic acid in the propylene glycol ester are esterified. 3. The method according to claim 1 or 2, characterized in that the mixture of the protein component and the propylene glycol ester is extruded. 4. The method according to claim 3, characterized in that the curing of the gel by bringing the extruded into contact Mixture with an aqueous, alkaline solution is facilitated. · 5. The method according to any one of the preceding claims, characterized in that the pH of the gel after curing to a Value is set in the range from 5 to 8. 6. "The method according to claim 5, characterized in that the pH adjustment by washing the gel ίη a dilute, aqueous, acidic solution, followed by removal of foreign liquid, is achieved. 7. The method according to any one of the preceding claims, characterized in that the protein component is a substantially denatured material. 8. The method according to any one of the preceding claims, characterized in that the protein component is a fish protein component is. 309884/1097 9. The method according to any one of the preceding claims, characterized in that the protein component is a dry, powdered Fish protein concentrate is. 10. The method according to claim 9, characterized in that the mixture, based on weight, 17 to 25 percent of the fish protein concentrate and 0.6 to 2.0 percent of the propylene glycol ester, with the remainder, apart from minor components, consists of water. 11. The method according to claim 10, characterized in that the pH of the mixture during manufacture to a value in the range is set from 8.5 to 9.5. 12. Protein-containing food ingredient, characterized in that that it is in the form of a thermostable gel obtained by a method according to any one of the preceding claims. has been made. 13. Food product, characterized in that it contains a protein-containing food ingredient according to claim 12. 14. Food product according to claim 15, characterized in that that the proteinaceous food ingredient is derived from fish and is in fragmented form, and that that Food product additionally contains crushed fish muscles. 15. Food product according to claim 14, characterized in that that it's a fish finger. 309884/109?