阅读说明：本技术 制备热改性淀粉的方法 (Method for preparing thermally modified starch ) 是由 S·博克 C·奎蒂尔 V·维亚茨 于 2018-12-20 设计创作，主要内容包括：本发明涉及一种生产热改性淀粉的方法,该方法包括以下步骤：(i)制备含有按重量计在30％与40％之间、优选按重量计在35％与37％之间固体物质的淀粉乳,(ii)添加粉末状碱性剂,以便获得在0.7与2.5mS/cm之间的最终电导率,(iii)确保0.5与5小时之间的接触时间,(iv)过滤并干燥该淀粉乳,(v)以及加热该经干燥的淀粉以使其达到大于180℃的温度持续在8与50分钟之间、优选在10与40分钟之间、甚至更优选在12与35分钟之间的停留时间。(The invention relates to a method for producing thermally modified starch, comprising the following steps: (i) preparing a starch milk containing between 30 and 40% by weight, preferably between 35 and 37% by weight of solid matter, (ii) adding a powdered alkaline agent so as to obtain a final conductivity between 0.7 and 2.5mS/cm, (iii) ensuring a contact time between 0.5 and 5 hours, (iv) filtering and drying the starch milk, (v) and heating the dried starch to reach a temperature of more than 180 ℃ for a residence time between 8 and 50 minutes, preferably between 10 and 40 minutes, even more preferably between 12 and 35 minutes.)

1. A process for producing a thermally modified starch comprising the steps of:

(i) preparing a starch milk having a solids content of between 30% and 40% by weight, preferably between 35% and 37%,

(ii) adding a powdery alkaline agent in order to obtain a final conductivity between 0.7 and 2.5mS/cm, measured after drying and resuspending to 20% solids content,

(iii) a contact time between 0.5 and 5 hours is ensured,

(iv) the starch milk is filtered and dried and the starch milk,

(v) heating the dried starch so as to bring it to a temperature higher than 180 ℃ for a residence time of between 8 and 50 minutes, preferably between 10 and 40 minutes, even more preferentially between 12 and 35 minutes.

2. The method of claim 1, wherein the starch is derived from waxy corn.

3. The method of claim 1, wherein the starch is derived from a source selected from the group consisting of potato, tapioca, and pea.

4. The method of claim 1, wherein the alkaline agent is preferably selected from the group consisting of: sodium hydroxide, sodium carbonate, tetrasodium pyrophosphate, ammonium orthophosphate, disodium orthophosphate, trisodium phosphate, calcium carbonate, calcium hydroxide, potassium carbonate, and potassium hydroxide, alone or in combination, will be employed, and even more preferably sodium carbonate.

5. The process according to claim 4, characterized in that the temperature increase of the dry starch obtained in step (iv) is carried out in a device of the continuous turbine reactor type, the nominal temperature of which is set above 190 ℃, preferably between 195 ℃ and 240 ℃, and the Δ T, defined as the difference between the nominal temperature and the temperature of the product leaving the reactor, is between 15 ℃ and 25 ℃.

6. The method of claim 2,

-the final conductivity of the product, after drying and resuspension to 20% solids content, is between 1.75 and 2mS/cm,

the heating conditions were as follows:

-a nominal temperature of about 200 ℃,

a residence time of 20 minutes,

-a value of Δ T from 16 ℃ to 17 ℃.

7. The method of claim 2,

-the final conductivity of the product, after drying and resuspension to 20% solids content, is between 1.2 and 1.32mS/cm,

the heating conditions were as follows:

-a nominal temperature of about 210 ℃,

a residence time between 15 and 20 minutes,

-a value of Δ T from 21 ℃ to 23 ℃.

8. The method of claim 2,

-the final conductivity of the product after drying and resuspension to 20% solids content is between 1.4 and 1.6mS/cm,

the heating conditions were as follows:

-a nominal temperature of about 210 ℃,

a residence time between 25 and 30 minutes,

-a value of Δ T at 22 ℃.

9. The method of claim 3,

-the final conductivity of the product after drying and resuspension to 20% solids content is about 1.4mS/cm,

the heating conditions were as follows:

-a nominal temperature of about 210 ℃,

a residence time of 35 minutes,

-a value of Δ T at 22 ℃.

10. Use of a thermally modified starch produced by the method according to any of the preceding claims as a thickener or conditioner in food applications, notably in soups, sauces and mayonnaises, in desserts such as yoghurt, fruit preparations of yoghurt, stirred fermented milk, heat-sterilised yoghurt or dessert cream, beverages, ready meals and meat-based or fish-based products such as surimi.

11. Use of a thermally modified starch produced by the method of any one of claims 8 and 9 as a thickener or conditioner in sauce applications, and more particularly in "tomato paste" sauces.

12. Use of the heat-modified starch produced by the process as claimed in claim 7, 8 or 9 as a thickener or texturizer in confectionery products such as yoghurts and stirred fermented milks.

13. Use of a thermally modified starch produced by the process according to claim 9 as a thickener or conditioner in meatless meat-spaghetti-type sauce applications, and more particularly in tomato sauce.

14. Use of a thermally modified starch produced by the method of claim 8 as a thickener or texturizer in heat sterilised yoghurt applications and fruit preparations for yoghurt.

15. Use of a thermally modified starch produced by the process of claim 8 as a thickener or texturizer for the preparation of low fat mayonnaise at elevated temperatures.

Background

Biochemically synthesized starch is a source of carbohydrates, one of the most widespread organic substances in the plant kingdom, and it constitutes a nutritional pool for organisms.

Starch has long been used in the food industry not only as a nutritional ingredient, but also as a thickener, binder, stabilizer or gelling agent due to its technical properties.

For example, native starch is used in products that require cooking. In particular, corn starch is the basis for "tart meals".

Due to the high amylose content, the corn starch retrogresses and thus is strongly gelatinized. It allows the production of shaped patties after cooking and cooling.

It is also suitable for use in custodian sauce (custard cream) mixtures.

However, said starch cannot be included in pastries intended to be frozen, since upon thawing the syneresis phenomenon, reflected in the expulsion of water, destroys the texture of the cream.

Thus, starch in its native form has limited application due to syneresis, also due to:

its low shear stress resistance and heat treatment resistance,

poor processability thereof, and

its low solubility in common organic solvents.

Therefore, in order to meet the currently growing technical demands, the properties of starch must be optimized by various methods called "modification".

These major modifications, in turn, relate to adapting the starch to the technical constraints imposed by cooking and also freezing/thawing, canning or sterilization, and to making it compatible with modern nutraceuticals (microwave oven cooked food, ready-to-eat meals, "high temperature foods", etc.).

The modification of the starch then involves correcting one or more of the above-mentioned drawbacks, thereby improving its versatility and satisfying the consumer needs.

Starch modification techniques have been generally divided into four categories: physical, chemical, enzymatic and genetic, the ultimate goal being to produce various derivatives with optimized physicochemical properties.

Chemical and physical modifications are most often performed.

Chemical treatment involves the introduction of functional groups into the starch, which significantly alter its physicochemical properties. This modification of granular native starch does have a profound effect on gelatinization, binding and retrogradation behavior.

Typically, these modifications are achieved by chemical derivatization, such as esterification, etherification, crosslinking, or grafting.

However, chemical modifications are less desirable (also for environmental reasons) to consumers in food applications, even if some are considered safe.

Various physical modifications have therefore been proposed, for example:

-Heat Moisture Treatment (HMT) comprising treating the starch at a controlled moisture level (22% -27%) and at elevated temperature for 16 hours in order to modify the structure and physicochemical characteristics of the starch;

-annealing, which comprises treating the starch in excess water at a temperature below the gelatinization temperature so as to approach the glass transition temperature;

-high pressure treatment (HPP), by which amorphous regions of the starch granules are hydrated, which results in deformation of the crystalline parts of the granules and promotes accessibility of said crystalline regions to water;

glow discharge plasma treatment, which generates energetic electrons and other highly reactive species at ambient temperature. When applied to starch, these actives excite the chemical groups of the starch and cause significant crosslinking of the macromolecules;

-Osmotic Pressure Treatment (OPT) carried out in the presence of a solution with a high salt content. The starch was suspended in sodium sulfate to produce a homogeneous suspension.

The treated starch is changed from type B to type A, so that the gelatinization temperature is obviously improved;

treatment by "thermal inhibition". In general, heat inhibition means the dehydration of starch until an anhydrous or substantially anhydrous state is reached (i.e., < 1% moisture), followed by a heat treatment at greater than 100 ℃ for a period of time sufficient to "inhibit" the starch, in this example in order to impart its cross-linked starch properties. Furthermore, before the severe dehydration step is carried out, the starch must be subjected to at least neutral to preferentially alkaline pH conditions.

An alternative form of "heat suppression" treatment is proposed in the solvent phase, which involves heating the non-pregelatinized granular starch in an alcoholic medium at a temperature of 120 ℃ to 200 ℃ in the presence of a base and a salt for 5 minutes to 2 hours.

In any case, the thermal inhibition process then produces a starch paste with increased anti-visbreaking properties and a tack-free texture.

The technical field to which the present invention is applicable is that of carrying out the heat-inhibiting treatment of starch in the absence of an aqueous alcoholic solvent.

In this particular technical field, US 6221420 may be more particularly mentioned, which describes a thermally inhibited starch obtained by dehydration followed by thermal treatment.

The method mainly comprises the following steps:

-dehydrating starch at a temperature between 100 ℃ and 125 ℃ to a water content of less than 1%, and then

-heat-treating the dry starch thus obtained in a fluidized reaction bed at about 140 ℃ for a period of about 20 hours.

Preferably, before the starch dehydration step, it is recommended to carry out an alkalization step of the starch, bringing the pH of the starch suspension to a value between 7 and 10, preferably between 8 and 10.

At this stage, before the actual dehydration step preceding the inhibition step, then the water content of the starch (as shown) is between 8% and 10%.

US 2001/0017133 describes a similar process in which the starch is also dehydrated at a temperature below 125 ℃ for a period of up to 20 hours, preferably between 3 hours 30 minutes and 4 hours 30 minutes, before the start of the inhibition process (at a temperature above 100 ℃, preferably between 120 ℃ and 180 ℃, more preferably between 140 ℃ and 160 ℃).

Prior to the dewatering step, a conventional alkalization step produces a starch suspension having a pH between 7.5 and 11.2, preferably between 8 and 9.5, and a water content between 2% and 15%.

A variant is proposed in patent application WO 2014/042537, which involves heating the alkaline starch to a temperature between 140 ℃ and 190 ℃, taking care to ensure that the inhibition process starts and proceeds in the presence of a sufficient amount of water (i.e. more than 1% water).

In other words, the process recommends the thermal inhibition of the pre-alkalized starch without a dewatering step.

Thus, the starch product or starch is brought to a pH between 9.1 and 11.2, preferably to a value of about 10, and the moisture is adjusted to between 2% and 22%, preferably between 5% and 10%.

The powder or the starch is then directly heat-inhibited for a period of 30 minutes at a temperature between 140 ℃ and 190 ℃, preferably between 140 ℃ and 180 ℃.

From all the foregoing observations, the thermal inhibition method for stabilizing the viscosity of starch comprises a process that requires:

using long treatment times, i.e. up to 20 hours, and

according to the methods proposed in the prior art, the water content of the starch to be treated is controlled to a value, whether lower than 1%, or on the other hand between 2% and 22%.

Thus, there remains a need for a novel method of inhibiting starch that enables further reduction of reaction time without having to control the water content of the starch to be "heat inhibited".

Disclosure of Invention

The present invention therefore relates to a process for producing thermally modified starch from starch milk, comprising the following steps:

(i) preparing a starch milk having a solids content of between 30% and 40% by weight, preferably between 35% and 37%,

(ii) adding a powdered alkaline agent in order to obtain a final conductivity between 0.7 and 2.5mS/cm,

(iii) a contact time between 0.5 and 5 hours is ensured,

(iv) the starch milk is filtered and dried and the starch milk,

(v) heating the dried starch so as to bring it to a temperature higher than 180 ℃ for a residence time of between 8 and 50 minutes, preferably between 10 and 40 minutes, even more preferentially between 12 and 35 minutes.

The starch to be used in the process of the invention may be of any origin, such as corn, waxy corn, high amylose corn, wheat, waxy wheat, pea, potato, waxy potato, tapioca, waxy tapioca, rice, konjac, and the like.

Preferably, corn starch, more particularly waxy corn starch (with a high content of amylopectin), potato starch, tapioca starch and pea starch will be chosen, as will be explained below.

The alkaline agent is preferably selected from the group consisting of: sodium hydroxide, sodium carbonate, tetrasodium pyrophosphate, ammonium orthophosphate, disodium orthophosphate, trisodium phosphate, calcium carbonate, calcium hydroxide, potassium carbonate and potassium hydroxide, taken alone or in combination, will be taken alone or in combination, even more preferably sodium carbonate.

The process according to the invention first requires the preparation of a starch milk with a solid content of between 30 and 40% by weight, preferably between 35 and 37%. As will be explained below, the solids content is set at 36.5% by weight.

Next, the next step consists in controlling the alkaline impregnation of the starch by adding an alkaline agent in powder form to obtain a final conductivity between 0.7 and 2.5mS/cm on the powder resuspended to 20% solids content.

Contact times of between 0.5 and 5 hours are then ensured.

In particular, the applicant company has found that:

the direct addition of an alkaline agent (more particularly sodium carbonate) to the milk phase enables the desired high pH (between 10.2 and 10.8, preferably between 10.5 and 10.65) to be achieved more efficiently than by spraying sodium carbonate onto starch as a dry phase, in a manner that allows better migration of carbonate into the starch particles when compared to impregnation as a powder.

Furthermore, since the impregnation in the powder phase requires the adjustment of the moisture of the starch to a high value, part of the energy dedicated to the product treatment is lost to ensure the evaporation of the residual water.

Controlling the level of impregnation of the starch by conductivity measurements enables the desired accuracy of the high pH value to be achieved.

The final step consists in heating the dry starch thus obtained so as to bring it to a temperature higher than 180 ℃ for a residence time of between 8 and 50 minutes, preferably between 10 and 40 minutes, even more preferentially between 12 and 35 minutes.

The applicant company has noted that the duration of the residence time can be adjusted according to the nature of the starch chosen.

Thus, as will be noted hereinafter, the treatment of waxy corn starch requires a residence time of from 15 to 20 minutes, or up to 30 or even 35 minutes, whereas the treatment of pea starch takes only 10 to 25 minutes.

As will be explained below, this treatment will advantageously be carried out in a thermal treatment device combining heat exchange by conduction and by convection, which is of the turbo-dryer type, for example at least one VOMM continuous turbo-dryer, which therefore enables very short reaction times of the order of a few minutes, i.e. less than 5 minutes per thermal treatment phase, to be achieved depending on the dimensions of the VOMM machine.

The nominal temperature is then set at a value greater than 190 ℃, preferably between 195 ℃ and 240 ℃, and the Δ Τ, defined as the temperature difference between the nominal temperature and the temperature at which the product leaves the reactor, is between 15 ℃ and 25 ℃.

The thermally modified starches according to the invention will advantageously be used, according to their respective characteristics, as texturizing and thickening agents in food applications, notably in soups, sauces, beverages and ready meals, and in desserts such as yoghurt and stirred fermented milk and "hot sterilised" yoghurt.

Due to their structure-modifying and gelling properties, they will also find many applications in a wide variety of fields:

soups and sauces (pasteurized and sterilized),

-a pasta sauce containing gravy,

desserts such as yoghurt, stirred fermented milks, "heat-sterilised" yoghurt and dessert creams,

-hot oil, vinegar juice and mayonnaise,

a filling for fruit patties, a fruit, or a meat or meat-stabilizing filling, which is sweet or salty, a meal (pre-cooked meal with short shelf life),

-pudding (dry mix to be cooked),

baby food cans/baby preparations (baby food jars/infant preparations),

-a beverage, the beverage comprising a liquid,

ready-to-eat meals, meat-based or fish-based products, such as surimi,

-animal feed.

The present invention will be more clearly understood by reference to the following examples, which are intended to be illustrative and not limiting.

Materials and methods

Measuring conductivity

The method used herein is adapted from European Pharmacopea-official edition-Conductivity (section 2.2.38).

Materials:

knick 703 electronic conductivity meter, also equipped with its measuring cell, was examined according to the procedure described in the relevant instruction manual.

The procedure is as follows:

a solution containing 20g of sample and 80g of distilled water was prepared having a resistivity of greater than 500000 ohms.

Measurements were made at 20 ℃ using a conductivity meter, with reference to the procedure shown in the machine's operating manual.

Values are expressed in microsiemens per centimeter (. mu.S/cm).

Measurement of the viscosity of starch suspensions using a Rapid Viscoanalyser (RVA)

This measurement is carried out at an acidic pH (between 2.5 and 3.5) under the given concentration conditions and according to a suitable temperature/time analysis profile.

Two buffer solutions were prepared:

buffer solution A

The following were added to a1 liter beaker containing 500ml demineralized water:

o 91.0g citric acid monohydrate (> 99.5% purity) and homogenized,

o 33.0g sodium chloride (purity > 99.5%) and homogenized until completely dissolved,

o 300.0g of 1N sodium hydroxide.

The contents were transferred to a graduated cylinder of 1L and replenished to 1L with demineralized water.

Buffer B

100g of buffer A were mixed with 334.0g of demineralized water.

The product to be analyzed was prepared as follows:

a mass of 1.37g of the dry product to be analyzed thus obtained was introduced directly into the viscometer bowl and a solution of buffer B was introduced until a mass equal to 28.00 ± 0.01g was obtained. The mixture was homogenized with a stirring blade of a rapid visco-analyzer (RVA-New Port Scientific).

Time/temperature and velocity analysis profiles in the RVA were then generated as follows:

and (4) finishing the test: 00:20:05(hh: mm: ss)

Initial temperature: 50 ℃ plus or minus 0.5 DEG C

Data acquisition interval: 2 seconds

Sensitivity: is low in

Measurements are given in RVU (units used to represent viscosity obtained on an RVA), assuming 1RVU unit-12 centipoise (cP).

Here, it is to be noted that 1cP is 1 mpa.s.

Thus, the results will be presented in mpa.s.

These measurements will be the value of the viscosity taken "at peak", i.e. the maximum viscosity value between 4 and 6 minutes, and the value of the viscosity taken "at drop", i.e. the difference between the viscosity at peak and the viscosity measured at 17 minutes.

Example 1: preparation of thermally modified starch "A"

1) The alkalization of waxy corn starch was carried out according to the following steps:

-preparing a starch suspension having a Solids Content (SC) of 36.5%;

-adding powdered sodium carbonate to obtain a final conductivity between 1.75 and 2mS/cm on the powder resuspended to 20% SC;

-ensuring a contact time of 5 hours;

-filtering and drying to between 10% and 14% starch equilibrium moisture.

2) Thermal treatment

The product thus obtained is subjected to a thermal treatment in successive VOMM continuous turbo-reactors, with a nominal temperature set at 200 ℃, and configured so as to subject the product to a residence time of 20 minutes, and so that the temperature difference between the nominal temperature and the temperature at which the product exits the reactor (called Δ Τ) is of a value of about 16 ℃ to 17 ℃.

Process parameters

RVA viscosity measurements were made and are presented in the table below.

Results

Example 2: preparation of thermally modified starch "B"

1) The alkalization of waxy corn starch was carried out according to the following steps:

-preparing a starch suspension having a Solids Content (SC) of 36.5%;

-adding powdered sodium carbonate to obtain a final conductivity between 1.2 and 1.32mS/cm on the powder resuspended to 20% SC;

-ensuring a contact time of 1 hour;

-filtering and drying to between 10% and 14% starch equilibrium moisture.

2) Thermal treatment

The product thus obtained is subjected to a thermal treatment in successive VOMM continuous turbo-reactors, the nominal temperature of which is set at 210 ℃, and configured so as to subject the product to a residence time of between 15 and 20 minutes, and so that the temperature difference between the nominal temperature and the temperature at which the product exits the reactor (called Δ Τ) is of a value of about 21 ℃ to 23 ℃.

Process parameters

RVA viscosity measurements were made and are presented in the table below.

Results

Testing	RVA Peak (mPa.s)	RVA decrease (mPa.s)
			Waxy corn base	1020	914
B-1	606	-2
			B-2	682	69

Example 3: preparation of thermally modified starch "C"

3) The alkalization of waxy corn starch was carried out according to the following steps:

-preparing a starch suspension having a Solids Content (SC) of 36.5%;

-adding powdered sodium carbonate to obtain a final conductivity of 1.4mS/cm or 1.6mS/cm on the powder resuspended to 20% SC;

-ensuring a contact time of 1 hour;

-filtering and drying to between 10% and 14% starch equilibrium moisture.

4) Thermal treatment

The product thus obtained is subjected to a thermal treatment in successive VOMM continuous turbo-reactors, the nominal temperature of which is set at 210 ℃, and configured so as to subject the product to a residence time of between 25 and 30 minutes, and so that the temperature difference between the nominal temperature and the temperature at which the product exits the reactor (called Δ Τ) is of a value of about 22 ℃.

Process parameters

RVA viscosity measurements were made and are presented in the table below.

Results

Testing	RVA Peak (mPa.s)	RVA decrease (mPa.s)
			Waxy corn base	1020	914
C-1	409	-116
			C-2	358	-130
C-3	282	-94

Example 4: preparation of thermally modified starch "D"

The alkalization of waxy corn starch was carried out according to the following steps:

-preparing a starch suspension having a Solids Content (SC) of 36.5%;

-adding powdered sodium carbonate to obtain a final conductivity of 1.4mS/cm on the powder resuspended to 20% SC;

-ensuring a contact time of 1 hour;

-filtering and drying to between 10% and 14% starch equilibrium moisture.

5) Thermal treatment

The product thus obtained is subjected to a thermal treatment in successive VOMM continuous turbine reactors, with a nominal temperature set at 210 ℃, and configured so as to subject the product to a residence time of 35 minutes, and so that the temperature difference between the nominal temperature and the temperature at which the product exits the reactor (called Δ Τ) is of a value of about 22 ℃.

Process parameters

RVA viscosity measurements were made and are presented in the table below.

Results

Testing	RVA Peak (mPa.s)	RVA decrease (mPa.s)
			Waxy corn base	1020	914
D	274	-182

In summary, for these first four examples:

each family of starches thermally modified according to the invention has an improved stability during the use process with respect to native starches: less viscosity increase and less retrogradation was observed during the use of these starches.

In this last point, it was in fact observed that the more the RVA drops towards 0 or becomes negative, the more the product will be functionalized and the less it will exhibit retrogradation.

Final conclusions regarding the results of these first four examples

Family "D" of thermally modified starches refers to products having the greatest resistance to shear, acidity to the medium, and heat treatment.

Family "C" thermally modified starches are slightly less tolerant than family "D" thermally modified starches, family "B" thermally modified starches are slightly less tolerant than family "C" thermally modified starches, and family "a" thermally modified starches are less tolerant than family "B" thermally modified starches.

The choice of the use of these starches will therefore be made according to the intended application and therefore the shear, acidity and temperature conditions used, as will be demonstrated in the working examples below.

Example 5: comparative study

The products according to the invention were analyzed in comparison with commercial products of the same kind according to the following protocol:

-resuspending the starch at 36.5% solids content;

-neutralization with 20% hydrochloric acid to pH 5.5 ± 1;

-filtration, washing to obtain a conductivity of less than 500 μ S, drying to a conventional moisture content of the starch of between 10% and 14%.

About 15-20 minutes to obtain a reaction with2600 an equivalent compound

About 20-30 minutes to obtain a reaction withPlus-equivalent compounds

About 25-35 minutes to obtain a reaction with2300 equivalent compound

→ less functionalized products

Depending on other process parameters such as Δ T and dosage of carbonate.

Example 6: use of thermally modified starch "D" in tomato sauce-tomato paste

The analysis was based on the following control formula:

composition (I)	Amount (%)
		Tomato premix at 14.9 ° brix
Water (W)	23.0
		28% tomato concentrate	26.0
Starch premix
		Water (W)	5.0
Testing of starch	3.2
		Salt (salt)	2.0
Vinegar premix
		8-degree vinegar	8.8
Syrup premix, at 53.1 ° brix
		Water (W)	17.0
Sucrose	15.0
Total of	100

The process for preparing tomato paste tomato sauce is as follows:

for a 1.5kg batch:

1. cooking steps on a 2L Hotmix Pro Combi cooker:

nominal value: 100 deg.C, 30 minutes, speed 1

a. Mixing the premix with tomato at a speed of 1-120rpm-1 minute

b. Adding starch premix and salt

c. Cooking at 100 deg.C for 30 min at speed 1

Nominal value: 100 ℃ and speed 2

d. The vinegar premix and sucrose syrup were added at speed 2 at 100 ℃ until a temperature of 92 ℃ was reached

2. packaging/Conditioning

Fill 375ml glass bottles at a temperature of 60 ℃ to 65 ℃.

3. Pasteurization

Autoclaving at 85 ℃ for 8 minutes (apparatus: Steriflow rotation double Process)900mm-1 basket-reference NS911R MP F L W STEAM,2017,www.steriflow.com/en；rotating: no (static) -Heat treatment with Water Cascade by pasteurization)

Finally, the formulation is characterized in that:

-total water content: 43 percent

-pH：3.66

-brix: 29.5

The various starches tested were as follows:

thermally modified starch "D" according to the invention (prepared according to example 4)

Sold by the applicant companyCH2020 (acetylated adipate cross-linked waxy corn starch)

Sold by the company Ingredion (Ingredion)2300

-by Tylen (Tate)&L yle) sold by the company

Various tomato sauces were evaluated by means of the following measurements:

1.cooking level of starch

The cooking level was determined by light microscopy (L eica microscope- × 20 lens and × 150 magnification.) the sample was dispersed in demineralized water and then stained with L ugol for the purpose of revealing the starch granules.

Optical microscopy gave a variety of information:

→ check for the presence and appearance of starch particles. They may be "uncooked"; "slightly cooked"; "medium cooked"; "well cooked"; "fragmented"; or "dissolved (absent)" is present.

→ observation under polarized light shows or otherwise shows birefringence crossing of uncooked starch particles (which enables monitoring of the effective cooking or other aspects of the starch).

2.Sensory characterization

Sensory characterization was subjective and was assessed visually and textually (by spoon and/or in the mouth) by a trained panel of 5 persons. They enable the quality of the products manufactured to be evaluated first here and are produced here only for illustrative purposes.

3.Viscosity of the oil

The measurements were performed on a Brookfield DV1 rotary rheometer.

In general, the rheology of food products is characterized by non-newtonian behavior: the viscosity varies with the level of shear applied.

A brookfield viscometer is used here at three rotational speeds to confirm (or otherwise confirm) this behavior.

The use conditions are as follows:

-a main shaft: #63

-rotational speed: 5; 10; 20rpm

-total range: 24000; 12000; 6000mPa.s

-rotation time: 30 seconds

-sample temperature: 25 ℃ (Environment)

Amount of container/glass jar/200 m L

Repeatability: average of three measurements. Precision: 5 percent of

4.Rheology of

4.a.Flow measurement

Equipment: anton Paar (Anton Paar), MCR301 rheometer

Characterization of the behavior of non-Newtonian fluids. The instrument applies a specific stress field or strain on the fluid and monitors the resulting strain or stress.

The results are expressed as a log scale plot of viscosity (pa.s) as a function of shear rate (γ).

The results of note are the viscosities at γ ═ 10s "1 (equivalent shear of texture measured by spoon) and γ ═ 40 s" 1 (equivalent shear of texture measured in the mouth).

Yield point represents the minimum stress to be applied to place a product or material in motion.

It was calculated using the Herschel Bulkley model using a stress versus shear curve (derived from the flow curve).

Geometry: concentric cylinder

And (3) analysis: oscillation

Temperature: 20 deg.C (+1 minute temperature stabilization)

Time: 10 minutes

Oscillating stress: 0.1 to 1000Pa

Repeatability: average of three measurements

Precision: 5 percent of

4.b.Viscoelastic behaviour G '/G'

Equipment: TA Instruments, DHR-2 rheometer

Characterization of the behavior of non-Newtonian fluids. The instrument applies a specific stress field or strain on the fluid and monitors the resulting strain or stress.

These results are shown in the table as the elastic modulus (G ') characterizing the solid part and the viscous modulus (G') characterizing the liquid part.

A general explanation for food product analysis is "liquid type behavior" if (G '< G ") and" solid type behavior "if (G' > G").

Geometry: concentric cylinder

And (3) analysis: oscillation

Temperature: 20 deg.C (+1 minute temperature stabilization)

Stress frequency: 1Hz

Oscillating stress: 0.02 to 880Pa

Repeatability: average of three measurements

Precision: 5 percent of

Results and discussion:

1. cooking action

The microscope allows a qualitative analysis of the cooking level of the starch granules.

Typically, no significant difference was observed between the cook level upon exiting Hotmix and after passing through the autoclave. Thus, the autoclave pasteurization step is considered a "sanitization" step, rather than an additional cooking step.

Two kinds of starchAnd2300, microscopic observation showed well cooked starch granules.

Microscopic observation of CH2020 showed well cooked starch granules and a certain amount of crumblingAnd (3) crumbs.

Microscopic observation of the thermally modified starch "D" according to the invention showed well cooked starch granules and a small amount of original granules.

This product was observed to be less crumbled and slightly cooked worse than the other products. It is the most resistant of the tested products.

2. Sensory characterization

The samples were evaluated with a spoon and sorted from most viscous (most viscous) to most fluid (least viscous).

There is no significant difference, indicating that the thermally modified starch according to the invention is a replacement for the conventionally proposed products for imparting the native starch properties of chemically modified starches.

3. Viscosity measurement

The graph of fig. 1 shows the brookfield viscosity profiles of the four products tested at three rotational speeds (5, 10 and 20 rpm).

The overall shear thinning behavior was confirmed: the higher the shear, the lower the viscosity of the product. For some samples, the viscosity reached the limit of measurement (full scale) at speeds of 10 and 20 rpm.

The product classifications in the following table (from most viscous to most fluid) were made using tests measured at 5 rpm.

The thermally modified starch "D" according to the invention represents the most fluid product, taking into account the entire viscosity range (from 11260 to 21770 mPa-1) obtained with the various thermally inhibited starch tests, and2300 denotes the most viscous product.

4. Rheological measurements

Flow of 4.a

Yield point represents the minimum stress to be applied to place a product or material in motion.

It was calculated using the Herschel Bulkley model using a stress versus shear curve (derived from the flow curve) -see figure 2.

The yield point calculated from the tomato paste test is shown in the table below, ranging from most viscous to most fluid.

Behavior of the thermally modified starch "D" according to the invention2300 behaves equivalently.

On the flow result chart for determining the yield point, 10s were selected for consideration^-1Viscosity at shear rate (shear denotes shear applied by a spoon).

The results are presented in the chart of fig. 3 reproduced in the table below.

The thermally modified starch "D" has a moderate viscosity value.

Viscoelastic behaviour G '/G'

For all tomato paste tests, G' predominates, which demonstrates that tomato paste has "solid type behavior".

However, they show different viscoelastic behavior.

The results were consistent with the foregoing results.

And (4) conclusion:

in tomato sauce applications, the thermally modified starch "D" according to the invention has a thermal inhibition comparable to chemically modified waxy starchStarch of2300 equivalent behavior.

Example 7: use of thermally modified starches "B", "C" and "D" in stirred fermented yogurts or milks

Conventional stirred yoghurt (or fermented milk) formulations contain a more creamy texture of starch.

Measurement of fermentation broth 20U/100L

The designation "yoghurt" or "fermented milk" does not allow the incorporation of starch in some countries, and in this case, such products will be referred to as fermented special dairy products.

The products tested were (according to the names of the preceding examples):

results and discussion:

1. fermentation characteristics:

some differences were observed between the fermentation times. They are more relevant to the reproducibility of the tests under laboratory conditions than the starch itself.

2. Cooking behavior:

in various steps of the process, the cooking state of the starch was monitored with an optical microscope (as in example 6):

-prior to homogenization at 60 ℃ (visualization of any original particles under polarized light)

After homogenization and pasteurization

After fermentation and refining (finished product)

For better visualization of the starch L ugol dye was used, which dyes the particles blue in the presence of amylose and brown in the presence of amylopectin only.

The cooked state of the starch did not show any significant difference before homogenization (60 c) (polarized light).

Some of the starch already started swelling at 60 ℃ before homogenization. This is explained by the difference in swelling temperature inherent to each starch.

After pasteurization, the cooking state depends on the starch used. It should be noted that the batch corresponding to the thermally modified starch "D" according to the invention confirms the results explained in example 6. The presence of a large number of primary particles indicates that these products are better resistant to heat treatment.

It should be noted that no particle debris was observed in any of the photographs. This means that all particles of the various batches are not damaged by heat treatment or shear.

3. Rheological measurements

The viscosity was measured after 1 day, 7 days, 15 days and 21 days.

Values are given within ± 5% uncertainty.

Hysteresis loop area (Pa)

It was observed that after 1 day, the test for lowest viscosity was based on2300 andand (3) testing of CJ 5025.

However, the viscosity difference remains small and is not constant upon storage.

4. Sensory characterization

This group consisted of 29 of the staff of the Roquette company (Roquette). During tasting the product, 11 and then 13 participated in two different stages.

This group was eligible for tasting the formulated product. The panel was trained to check its performance in the following ways:

the ability to discriminate between products

Consistency, correct use of descriptors

Repeatability, ability to check the submitted product twice

Tasting conditions were:

sensory analysis was performed in a dedicated laboratory with separate chambers, a calm, odorless environment (to help focus), and white light illumination.

The tasting was performed blindly with a three digit code and the products were presented in a random order to avoid persistence effects.

Furthermore, the tasting of the test was carried out in two series to avoid saturation during this phase:

-series 1:2300. thermally modified starch D, thermally modified starch C-1, and thermally modified starch C-2 "

-series 2:2300. thermally modified starch' B-2CJ5025

The method comprises the following steps: flash characteristic curve (JM Siefermann, 2000)

Results analysis was performed by multifactorial analysis (j. pagnes, 1994) and shows that:

for series 1:

three descriptions "shiny", "creamy taste" and "astringent" are not distinguishable on this series of products.

Yoghurts formulated with heat modified starches "C-1" and "C-2" were similar in that they were more creamy, sweeter, fatter, and grainier than the other products. However, the thermally modified starch "C-1" gives a product that is more soft, less acidic and less viscous than the thermally modified starch "C-2".

The thermally modified starch "D" is not as acidic as the thermally modified starch "C-1".

For series 2:

the five descriptions "shiny", "sweet", "gummy", "milky taste" and "astringent" are not discernable in this series.

However, the group members determined the following differences:

o thermally modified starch "B" is very viscous, granular, acidic, has a creamy feel and a spreadable texture,

o2300 have similar organoleptic profiles, but are less acidic and less grainy,

oCJ5025 is the least granular, least viscous and least fat product.

This result can be consistent with microscopic observations of the particles:CJ5025 particles are not very swollen and thus provide a lower viscosity than other particles.

The conclusion of this study was that all tested starches appeared to survive the process used herein, as no starch fragments were observed.

For some of them, the starch according to the invention has characteristics similar to those of the already existing products: thus, the thermally modified starch "D" only differs in that the acidity of the yoghurt is slightly higher.

Similarly, thermally modified starch "C-1" produces a product similar to existing products.

The thermally modified starch "C-2" even enables to reach milk fat levels perceived as excellent. Thus, it can be used at lower doses for the same result.

Example 8: use of thermally modified starch "D" in tomato sauce-fleshless Italian meat paste (Bologese)

The basic formulation used was as follows:

the various starches tested were as follows:

thermally modified starch "D" according to the invention (prepared according to example 4)

Sold by the applicant companyCH2020 (acetylated adipate cross-linked waxy corn starch)

Sold by the company Yiruian2300

The formula procedure is as follows:

1. preparing a premix:

a. tomato pulp and onion

b. Water and other liquid components

c. Powder of

2. A fluid sauce of premix (tomato pulp and onion) was prepared using a Hotmix mixer (speed 6 for 1 minute). The premix must be free of particles in order not to interfere during rheological analysis of the product.

3. Add premix (Water and other liquid ingredients)

4. Standing at speed 3 for 1 minute

5. Add powder premix (at speed 3 for 1 min)

6. Pre-cooking (speed 3/10 min/80 ℃ C.)

7. Optional treatments are as follows:

and (3) heat treatment equipment:

o an autoclave, and (c) an autoclave,

o-spin two-process Steriflow900mm-1 basket-1 door

The internal control system of the Steriflow machine (MPI Expert, Inc.) is used to manage the process cycle.

With the aid of a temperature probe placed in the center of the product (coldest spot), the machine records useful data during the cycle for research purposes:

■ Start temperature Start ℃: Start to check the correct reproducibility of the sample production process

■ Max temperature Max T c to check the highest temperature reached in the center of the product,

■MAX F₀(minutes): this value gives information about the strength of the heat treatment. It represents the exposure time of the product to a treatment that results in the same reduction in the number of microorganisms achieved at a reference temperature, i.e. 121.1 ℃, which is the destruction temperature of Clostridium botulinum. The term "pasteurisation value or PV" is used in the case of pasteurisation, or the term "sterilisation value or SV" is used in the case of sterilisation.

For example, a sterilization value of 3 minutes means that the experiment carried out corresponds to an experiment carried out at a constant temperature equal to the reference temperature (121.1 ℃) for 3 minutes.

F₀＝ΔT*10(T-121/Z)

“MAX F₀"is the sum of all values over the entire cycle, calculated from the Z value and the reference temperature (T)

Colorimetry measurement apparatus:

equipment: konica Minolta, CM-5 Spectrophotometer

Color analysis method L aBb colorimetric space/Delta E CIE2000

Sample preparation: 6g of powder wrapped in Petri dishes (Conicamideak reference 1870-

A measurement area:30mm of which35mm aiming mask

Measurement type: a reflectivity; the method comprises the following steps: petri dish

The observer: 10 °/light source: d65

Repeatability: 0.004

The luminance L indicates the darkest black color at L ═ 0 and the brightest white color at L ═ 100.

Color channels a and b represent the true values of neutral gray when a is 0 and b is 0.

The color difference AE (Δ E) between the color of the selected sample L1 a1b1 and the reference color L2 a2b2 was calculated.

By means of an online calculator www.brucelindbloom.com

The results are calculated (part "calculate"/"color difference calculator"), wherein the "CIE 2000" results are used.

The smaller the Δ Ε value, the more similar the color of the two products.

If Δ E >1.5, the color difference is considered perceptible to the human eye.

Sensory characterization:

sensory characterization is subjective assessment and review (by spoon and/or in the mouth) in terms of visual aspects and texture.

→ syneresis measurement

Depending on the resistance of the starch to the process (freezing and/or heat treatment), a certain amount of syneresis (water release) may occur.

The product was sieved (fine mesh) for 6 minutes, the amount of phases was weighed, and the results are given as percentages.

After sieving and weighing of the syneresis, the two phases of the sample (syneresis water and remaining sauce) are returned to the tank.

Sensory properties were evaluated mainly on the remaining sauce phase (the sauce may be more concentrated or more viscous).

Cooking level of starch

As in example 5 above, the cooking level was determined by microscopy.

Rheological measurements

Characterization of non-Newtonian fluid behavior: the instrument applies a specific stress field or strain on the fluid and monitors the resulting strain or stress.

Geometry: CC27 concentric cylinder

Analysis conditions were as follows: all samples were analyzed for rheology after stabilization at 20 ℃ 1 day after the production day.

Reproducibility of all analyses: average of three measurements

Precision: 5 percent of

→Viscosity as a function of stress-flow measurement

The results are represented by a logarithmic scale curve which gives the viscosity (pa.s) as a function of shear rate (γ).

The results of note are at the following viscosities:

·γ＝5s^-1(shear denotes shear of static product)

·γ＝10s^-1To 40s^-1(shear means shear applied in the mouth during chewing)

·γ＝100s^-1(shear means shear applied by spoon)

·γ＝350s^-1(shear means industrial process-i.e. shear applied in a pump)

→ yield point

Yield point represents the minimum stress to be applied to place a product or material in motion. The lower the result, the less effort is required to put it in motion.

It was calculated using the Herschel Bulkley model using a stress versus shear curve (derived from the flow curve).

→ characterization of viscoelasticity

The results of the viscoelastic behaviour (G '/G ") are expressed in the table in terms of the elastic modulus (G') characterizing the solid fraction and the viscous modulus (G") characterizing the liquid fraction.

A general explanation for food product analysis is "liquid type behavior" if (G '< G ") and" solid type behavior "if (G' > G").

The results are as follows:

_o1. heat treatment data (pasteurisation/sterilisation) -measurement of Start T ℃/Max T ℃/Max F

These results reflect:

good reproducibility of the treatment method. The starting temperature for all tests was about 57 ℃ to 61 ℃.

Sufficient duration of the step phase (for pasteurization and sterilization). The maximum temperature is close to the set temperature.

Furthermore, the thermally modified starch "D" according to the invention has a behaviour comparable to conventional thermally inhibited starches.

2. Colorimetric analysis

The color difference AE (Δ E) between the color of the selected sample L1 a1b1 and the reference color L2 a2b2 was calculated.

To obtain the most comprehensive comparison, it is calculated at four different viewing angles:

Δ E: (repro CH 20): two batchesRepetitive study of CH2020

Modified by referenceΔ E for comparative studies between the CH2020 prototype and the thermally modified starch "D".

·2300 Δ E of the comparative study with thermally modified starch "D".

Modified by referenceCH2020 and2300 Δ E of the comparative study.

The results are shown in fig. 4.

It should be noted that the smaller the Δ Ε value, the more similar the color of the two products. If Δ E >1.5, the color difference is considered perceptible to the human eye.

Only byThe Δ E results of repeated studies of CH2020(Δ E (repro CH20)) were less than 1.5.

All other Δ E results are very different:

between batchesThe color of CH2020 is significantly similar.

Color of thermally modified starch "D" andthe color of CH2020 is significantly different.

Color of thermally modified starch "D" and2300 are significantly different in color, but are comparatively different fromThe color of CH2020 is less pronounced than it is.

Color of CH2020 and2300 color was significantly different, but less pronounced relative to the thermally modified starch "D", where the lightness between the C L EARAM CH2020 prototype and the thermally modified starch "D" was lower and the color saturation was lower.

3. Sensory evaluation

It is reminded that these products were subjected to three different treatment options and observed at 20 ℃ on day + 1.

The pasteurized sample is taken as a reference, since it is considered to be closest to the intended target of this type of matrix in terms of visual aspect and texture.

All frozen and thawed samples exhibited syneresis and also had a grainy, micro-gelled texture, etc.

In comparison to the other two products, thermally modified starch "D" has:

less syneresis

More spreadable, less tacky texture during freeze/thaw

All sterilized products had a more fluid texture and a non-uniform, darker red color (associated with a more pronounced Maillard reaction).

4. Rheology study

The histograms presented in the following figures show the mean of the results of each test for the following three parameters: viscosity, yield point and viscoelasticity as a function of stress.

FIG. 5: viscosity change with stress

The results show good reproducibility of the results for three replicates of each sample.

The histogram is a complete and simplified view (average of three replicates). Each bar represents a noteworthy viscosity result (5; 10; 100; 350 s-1).

For both heat treatments, all samples had shear thinning behavior (viscosity decreased with increasing shear rate).

The sterilized sample (S) is more fluid than its pasteurized sample (P). Regardless of the starch, heat treatment has an effect on the rheological behavior.

For the pasteurized and sterilized samples,2300 presents a comparative referencePoor results of CH 2020.

The thermally modified starch "D" has a lower viscosity than under sterilization conditions in which the thermally modified starch "D" appears to be slightly more viscous2300 viscosity.

Component classes show that under pasteurization conditions, thermally modified starch "D" and2300 have similar performance qualities.

FIG. 6: yield point

For the results of the preceding analysis (viscosity as a function of stress), there are similar characteristic curves in the product classification:

the sterilized sample (S) had a yield point slightly lower than that of the pasteurized sample (P). Heat treatment has an effect on rheological behavior: the resistance of the starch to such high heat treatments is reduced.

For pasteurized samples, the method is described inCH2020 reference between the prototype and the thermally modified starch "D",2300 exhibits moderate results.

Thermally modified starch "D" appears to be the most effective and closest to the reference product: (CH2020 and2300)。

FIG. 7: viscoelastic characterization

For each test, G' predominates over G ", demonstrating that the product has" solid type behavior ".

The histogram only focuses on the value G'.

As for the flow analysis results, there are similar characteristic curves in the product classification:

the sterilized sample (S) has a lower cohesion than its pasteurized sample (P). Heat treatment affects the rheological behaviour by damaging the starch. Overall, all heat-treated starches are less resistant to sterilization treatments.

In the case of the pasteurized sample,2300 shown in close proximityCohesion of CH2020 cohesion.

The heat treated starch "D" appeared to be cohesive.

In the case of the sterilized samples, the samples were,2300 shows cohesion closer to that of the heat-treated starch "D".

Final conclusion of the rheological analysis：

The sterilization process conditions defined for this study appear to be discriminatory parameters.

This processing option enables further discrimination between and among each otherCH2020 and2300 part by weight of native starch.

Heat-treated starch "D" is classified as a thermally modified reference product class, like2300。

Example 9: use of thermally modified starch 'C' in heat-sterilized yoghurt

The heat-modified starch obtained by means of the method according to the invention is tested in heat-sterilized yoghurt, also referred to as ambient yoghurt or extended shelf life yoghurt.

These yoghurts are subjected to a heat treatment after fermentation, which makes it possible to preserve them at room temperature for several months.

The various starches tested were as follows:

-thermally modified starch "C" (prepared according to example 3) according to the invention;

sold by the applicant companyCJ5025 (acetylated distarch phosphate), modified starch conventionally used in room temperature stable drinking yoghurt applications-see https:// www.roquette.com/food-and-nutrition/day/texturising-solutions/;

sold by the company Yiruian2300。

The formula is as follows:

starch was tested in strawberry flavored drinking yogurt with fruit concentrate.

The preparation method comprises the following steps:

hydration of the ingredients in milk (milk powder, sugar, pectin and starch) at 50 ℃ for 30 minutes

Cream was added and mixed with a Silverson mixer (3500rpm) for 5 minutes.

Homogenization: depending on the starch used, 100 bar at 65 ℃ or 60 ℃

Pasteurization in a plate exchanger at 30L/h at 95 ℃ for 7 minutes

Adding lactic acid fermentation broth (20U/200L) to the mixture at 42 deg.C

Fermentation at 42 ℃ until a pH of 4.5 is reached

Addition of strawberry jam concentrate

Heat sterilization, preheating to 60 ℃ and heat sterilization at 85 ℃ for 30 seconds in a plate exchanger at 30L/h

Cooling to 50 deg.C

Packaged and stored at room temperature

The characteristics of the process and fermentation:

starch has no effect on fermentation time. The three products reached the desired pH in equal time.

In the visual aspect:

the product had a slight off-white color before the addition of the strawberry jam.

Cooking state of starch:

in each step of the process, the cooking state of the starch is monitored by optical microscopy

After homogenization and first heat treatment (pasteurization)

After the second heat treatment (heat sterilization)

The article was colored with L ugol to improve visualization of the starch.

After pasteurization, the starch granules swell satisfactorily overall. Modified starch (with minimal swellingCJ 5025). No debris was observed.

After the second heat treatment

Satisfactory swollen particles were observed in these three products. No starch pieces were visible. The starch withstands the heat treatment satisfactorily.

On average, the average of the average,the swelling of 2300 particles appears to be slightly lower than that of the thermally modified starch "C".

Rheological measurements

The viscosity was measured after day 1, day 7, day 15 and day 30.

Values are given within ± 5% uncertainty.

FIG. 8 is presented at 40s^-1Viscosity chart of (b).

Two tests with starch without chemical modification had similar viscosities.

On the other hand, byThe test of CJ5025 is less sticky at all storage times.

The change in viscosity showed that the starch in the yoghurt did not retrogradation, since an increase in viscosity was then observed upon storage.

Water holding capacity

The water holding capacity of the yoghurt was analysed by carrying out the following test adapted from Harte and Barbosa-Canovas:

-centrifuging a mass W1 of yoghurt at 4000g and 10 ℃ for 30 minutes.

-weighing the whey separated after centrifugation: w2

-water holding capacity: WHC (%) - (1-W2/W1) x 100

It was found that the water holding capacity of the starch according to the invention is close to that obtained with modified starches.

Furthermore, it was stable upon storage, confirming the absence of syneresis. However, competitive starches retain slightly less water.

Tasting yogurt

These three products were evaluated by a professional dairy taster. The comments collected are as follows:

-CJ 5025: astringent, coated, slightly acidic-2300: is sour, astringent, moderately viscous in the mouth

-thermally modified starch "C": is slightly sour, slightly astringent, mild, and viscous in the mouth.

This taste makes it possible to confirm that the starch used does not introduce any off-flavours into the yoghurt.

On the other hand, they are distinguishable in terms of perceived acidity,2300 provide the largestAnd (4) acidity.

The thermally modified starch "C" makes it possible to obtain yoghurts with a more excellent taste quality.

In summary, the thermally modified starch according to the invention thus has at least comparable properties to the modified or unmodified starch conventionally used in this application and has been demonstrated to be comparable2300 are more organoleptically acceptable.

Example 10: use of thermally modified starch "C" in low fat mayonnaise according to thermal processing

The thermally modified starches obtained with the process according to the invention were tested in mayonnaises prepared by thermal processing, which have a low fat content (25-35% fat).

The various starches tested were as follows:

-thermally modified starch "C" (prepared according to example 3) according to the invention;

sold by the applicant companyCH2020 (acetylated adipate cross-linked waxy corn starch);

sold by the company Yiruian2300。

The formula is as follows:

the preparation method comprises the following steps:

suitable for amounts from 800g to 2kg, where a batch of 1kg of low fat mayonnaise was prepared.

A 2L Hotmix Pro Creative mixer was used (speed 1E 480 rpm; speed 3: 800 rpm; speed 4: 1800 rpm; speed 5: 3000 rpm; speed 6: 4000 rpm).

Phase A: the starch milk was cooked in the bowl of the Hotmix machine (speed 1E, 90 ℃, 10 minutes). Standing and cooling to 50 ℃.

Phase B: liquid ingredients (starch paste and mustard) were prepared in the bowl of the Hotmix machine. The powder was prepared in a separate container.

This powder mixture was thoroughly dispersed and homogenized.

Phases C and D were prepared in separate vessels.

Hydration of phase B

The powder mixture was added to the Hotmix bowl where the starch milk was kept at 50 ℃ and mixed for 1 minute at speed 3.

Emulsification + hydration of hydrocolloids

Add phase C through the top of the vessel and then add phase D in portions.

The speed was changed from 4 to 6 depending on the consistency of the product, without exceeding a mixing time of 3 minutes.

And (3) completing emulsification:

mixing was continued at speed 6 for 1 minute.

Analytical method

Sensory characterization

Sensory characterization is subjective assessment and review (by spoon and/or in the mouth) in terms of visual aspects and texture.

Colorimetric method

Equipment: cM-5 spectrophotometer, Cornica Mentada

Color analysis methods L aBb and L cHdegree colorimetric spaces/Δ E CIE2000

Sample preparation: 20g in a disposable Petri dish (VWR, "round PS Petri dish without flanges", plastic, diameter 55mm)

A measurement area:30mm of which35mm aiming mask

Measurement type: a reflectivity; not including a Specular Component (SCE)

The observer: 10 °/light source: d65

Repeatability: 0.004

The luminance L indicates the darkest black color at L ═ 0 and the brightest white color at L ═ 100.

Color channels a and b represent the coordinates of the color. The values a-0 and b-0 represent true neutral gray.

C denotes chroma. The difference ac between the two samples is considered to show a lighter (+) or darker (-) color.

(can be stated as pigment quantity)

h ° denotes the hue angle (in degrees), which is exactly the color.

The colorimetric space difference (L cc h °) is easier to read and interpret than the colorimetric space (L a b).

Calculating the selected sample color L₁a₁b₁And a reference color L₂a₂b₂(or L)₁C₁h₁And L₂C₂h₂) A color difference Δ E (Δ E) therebetween.

Using a catalyst from Konica corporation (Konica)The Color software calculates the result using the "CIE 2000" formula (closest to the perception of the human eye).

The smaller the Δ Ε value, the more similar the color of the two products.

If AE >1.5, the chromatic aberration is considered perceptible to the human eye.

The analysis was performed on mayonnaise at 15 ℃.

Cooking level-light microscope for starch

L eica

The sample was dispersed in demineralized water and then stained with L ugol to reveal the starch granules iodine reacted with amylose and formed a complex of helical structure giving blue/purple if the starch was rich in amylose otherwise the colour of the starch granules remained brown/yellow.

Optical microscopy gave a variety of information:

→ shows the size and dispersion of oil bubbles. The smaller and more uniform the emulsification, the more effective the emulsification.

→ check for the presence and appearance of starch particles. They may be uncooked; slightly cooked; medium cooked; well cooked; as debris; or dissolved (absent) presence.

→ observation under polarized light shows or otherwise shows birefringence crossing of uncooked starch particles (which enables monitoring of the effective cooking or other aspects of the starch).

White light- × 20 lens-power × 150

Rheology of

Characterization of the behavior of non-Newtonian fluids. The instrument applies a specific stress or strain on the fluid and monitors the resulting strain or stress.

Analysis conditions were as follows: all samples were analyzed for rheology 1 day after the production day.

Reproducibility of all analyses: average of three measurements

Precision: 5 percent of

Flow of

The flow results are expressed as a logarithmic scale curve of viscosity (pa.s) as a function of shear rate (γ).

Noteworthy viscosity results may be noted at the following shear rates:

·γ＝5s^-1(equivalent texture shear for static product measurement)

·γ＝10s^-1To 40s^-1(chewing-equivalent texture shear measured during mouthfeel)

·γ＝100s^-1(stirring-equivalent texture shearing measured during sensory Properties by spoon)

·γ＝350s^-1(Industrial Process-i.e., equivalent texture shear measured during Pump)

Instrumentation and analytical methods:

yield point

Yield point represents the minimum stress to be applied to place a product or material in motion. The lower the result, the less effort is required to put it in motion.

It was calculated using the Herschel Bulkley model using a stress versus shear curve (derived from the flow curve).

Instrumentation and analytical methods:

oscillation

The results of the viscoelastic behaviour (G '/G ") are expressed in the table in terms of the elastic modulus (G') characterizing the solid fraction and the viscous modulus (G") characterizing the liquid fraction. A general explanation for food product analysis is "liquid type behavior" if (G '< G ") and" solid type behavior "if (G' > G").

Instrumentation and analytical methods:

results

Sensory evaluation (h +12 hours)

Comment on:

after use: due to the temperature starting from 50 ℃ and the shearing process, the product is hot and rather fluid, more particularly for the heat inhibited starch and the heat modified starch "C" according to the invention.

After 12 hours of maturation at +5 ℃: the product is equivalent except that the heat inhibited starch and the heat modified starch "C" according to the invention have a darker color. Furthermore, the mayonnaise prepared from the thermally modified starch "C" appeared to be somewhat more fluid for texture by spoon.

The heat-inhibited starch and the heat-modified starch "C" according to the present invention showed almost no difference with respect to texture in the mouth, andthe CH2020 control had a slightly sticky and more tacky texture.

The heat inhibited and heat modified starches "C" according to the invention have no aftertaste.

Modified starchCH2020 is less damaged during this process. Furthermore, the heat inhibited starch and the heat modified starch "C" according to the invention have reduced viscosity properties for equivalent dosages.

Colorimetric method

As measured value

Relative toMeasured difference of CH2020

Comment on:

and use as a standardTest comparison of CH 2020:

Δ L two test ratios of thermally inhibited starch and thermally modified starch "C" according to the inventionCH2020 is deeper.

ΔC*：2300 shown in close proximityCH2020, while the thermally modified starch "C" according to the invention shows a higher amount of colour.

Δ h —: the heat inhibited starch and the heat modified starch "C" according to the present invention show different color tones, but the heat modified starch "C" according to the present invention is more apparent.

ΔE：2300 shows a Δ Ε of less than 1.5, which is theoretically indicative ofThe chromatic aberration of CH2020 is not significant.

The thermally modified starch "C" according to the invention shows a Δ E of greater than 1.5, which means that the colour of the sample is considered to be equal toThe color of CH2020 is significantly different.

Cooking level-light microscope for starch

Regardless of the starch used, no granular starch is present in the formulation anymore, which may be due to the cooking process and the high shear level.

Rheology of

Flow measurement

All samples had shear thinning behavior (viscosity decreased with increasing shear rate).

At 40s^-1(indicating the mouthfeel) under the condition of no toxic and side effects,CH2020 and2300 are similar in viscosity. Thermally modified starch "C" is very slightly inferior.

The viscosity loss with respect to shear rate is equivalent for these three samples. Rheological analysis confirmed the sensory results, with minor differences between the textures of the samples in the mouth.

Yield point

According to the Herschel Bulkley model and measurement conditions, the samples showed no stress. The sample was also easy to pour out.

Oscillation measurement

For each analytical test, G' predominates over G ", which demonstrates that the product has" solid type behavior ".

The consistency (i.e., G' level) of CH2020 and thermally modified starch "C" are similar.

2300 is slightly less elastic than the other more tolerant samples.

This analysis also confirmed the sensory results.

And (4) conclusion:

all starches show the same weakness when subjected to high stresses of mayonnaise processed at elevated temperatures.

All particles were destroyed.

Although the treated product had a fluid texture, all starch retrogressed during ripening and imparted an acceptable texture to the final sauce.

Notice the use ofThe texture of the control test of CH2020 is slightly viscous, but not very noticeable.

A significant dark color of mayonnaise with heat modified starch "C" was noted.

Example 11: use of thermally modified starch 'C' in yoghurt fruit preparations

Often, fruit preparations of yoghurt contain starch in order to optimise their viscosity and to keep them stable throughout the shelf life of the product. They are mixed with the white substance of the yoghurt in proportions which can vary generally between 10% and 20%.

The various starches tested were as follows:

-thermally modified starch "C" (prepared according to example 3) according to the invention;

sold by the company Yiruian2300 andPrima 600

sold by the applicant companyCR0820, chemically modified starch (hydroxypropyl phosphate)

The formula is as follows:

starch was tested in strawberry fruit preparations.

% of	Formulation of
			％
Strawberry jam	45.0
		Water (W)	31.0
Sucrose	20.0
		Testing of starch	4.0
	100.0

The preparation method comprises the following steps:

mixing water and strawberry jam in a household food mixer.

Mixing at 800rpm for 2 minutes,

addition of sugar and starch

Mixing at 800rpm for 2 minutes,

heating to 90 ℃/95 ℃ in a food mixer

Hold at 90 ℃/95 ℃ for 10 minutes, mix at 1800rpm

Packaging, cooling and storage at 4 ℃.

And (3) testing:

pH of the test:

testing	1	2	3	4
					pH	3.55	3.45	3.45	3.50

All tests had a very acidic pH, which may have an effect on the degradation of starch during cooking.

Cooking state of starch:

after cooking, the starch cooking status of the fruit preparation was monitored by optical microscopy.

The article was colored with L ugol to improve visualization of the starch.

-thermally modified starch "C":

well-cooked (swollen) particles and fragments of particles were observed. Thus, a portion of the particles are destroyed by the manufacturing process.

-2300: a certain number of intact, well-cooked particles were also found, but they appeared to be smaller in number. In addition, many fragments were observed.

-Prima 600: leaving only some visible particles. Thus, it appears that most of the particles are destroyed during cooking.

-CR 0820: in this case, almost no intact particles are retained.

Thus, the thermally modified starch according to the invention is one of the tested products that is most able to retain its granular structure, which means that it is able to withstand the thermal and acid conditions of the medium.

Texture measurement

Bostwick flow after 12 days (20 ℃, 90g product)

It is found to be other than by using more fluidThe flow behavior between starches was relatively similar outside the tests for CR0820 modified starch.

Viscosity of the oil

The viscosity was measured after 1 day, 15 days and 30 days.

Values are given within ± 5% uncertainty.

The viscosity of the fruit preparation containing C L EARAM CR0820 is seen to be higher in the graph of FIG. 9 it tends to stabilize, or even drop slightly.

Thermally modified starch "C" gives close to utility2300 and slightly increases over time.

Finally, the process is carried out in a batch,prima 600 is the lowest viscosity product. It is stable on storage.

Sensory analysis

Four products were evaluated by a trained group of 13 people. The method used is a flash characteristic curve method: the team member itself selects the criteria that appear to be most discriminating between samples and then classifies them according to the selected criteria.

The conclusion of the sensory analysis is as follows:

the thermally modified starch "C" gave a less viscous (in the mouth and with a spoon), less sticky, and more gummy fruit preparation than the modified starch C L EARAM CR 0820.

Relative to starchPrima 600 and2300：

o2300 produce a fruit preparation which is sticky and spreadable in the mouth, but tacky and has an aftertaste.

oPrima 600 provides little texture (mouth and spoon), but it gives good gloss and retains sweetness.

The starch according to the invention has a soft-sweet feel, is slightly tacky and slightly sweet.

Thus, sensory analysis confirmed the results of the rheological measurements, in which the texture of the modified starch was thicker.

In conclusion, it can be seen in all these results that the properties of the thermally modified starch according to the invention are close to those of the thermally modified starch2300.

Higher shear resistance under acidic conditionsCR0820 (starch commonly used in fruit preparations) shear tolerance. On the other hand, the viscosity obtained is slightly lower.

Example 12: preparation of thermally modified starch from potato starch

1) The alkalization of the potato starch is carried out according to the following steps:

-preparation of a potato starch suspension with a Solids Content (SC) of 36.5%

-addition of powdered sodium carbonate to obtain a final conductivity between 0.7 and 1.1mS on the powder resuspended to 20% SC

Ensure a contact time of 1 hour

-filtering and drying to between 12% and 18% starch equilibrium moisture

2) Thermal treatment

The product thus obtained is subjected to a thermal treatment in successive VOMM continuous turbo-reactors, the nominal temperature of which is set at 210 ℃, and configured so as to subject the product to a residence time of about 30-35 minutes, and so that the temperature difference between the nominal temperature and the temperature at which the product exits the reactor (called Δ Τ) is of a value of about 19-22 ℃.

Process parameters

RVA viscosity measurements were made and are presented in the table below.

As a result:

comparative study

The analysis was performed by comparing the product according to the invention with commercial products of the same category. The products derived from the invention were treated according to the following protocol:

resuspension of starch at 36.5% SC

Neutralization with 20% hydrochloric acid to pH 5.5. + -. 1

-filtration, washing to obtain a conductivity of less than 500 μ S, drying to a conventional moisture content of starch of between 14% and 18%

Each of the examples E-1, E-2 and E-3 of thermally modified potato starch according to the invention has an improved stability during use relative to native starch: less viscosity increase and less retrogradation was observed during the use of these starches. This is seen by measuring the droplets with an RVA viscometer: the more negative the droplets, the more resistant the starch is to shear, acidity of the medium and heat treatment.

Each of the examples E-1, E-2 and E-3 of the thermally modified potato starch according to the invention can be compared with other heat-inhibiting products of the prior art based on potato starch, such as NOVATION 1900 or Beco Gel P4500. The most resistant products are those derived from the present invention as a result of the RVA viscometer.

Similarly, each example of a thermally modified potato starch according to the invention, E-1, E-2 and E-3, can be compared to examples on waxy maize and notably family D: examples of potato starch E-1, E-2 and E-3 have a higher peak viscosity for the same measured solids content and are more resistant to the process. The choice of the use of these starches will therefore be made according to the intended application and therefore according to the shear, acidity and temperature conditions used.

Example 13: preparation of thermally modified tapioca starch

1) The alkalization of the tapioca starch is carried out according to the following steps:

-preparing a tapioca starch suspension having a Solids Content (SC) of 36.5%

-addition of powdered sodium carbonate to obtain a final conductivity between 0.7 and 1.1mS on the powder resuspended to 20% SC

Ensure a contact time of 1 hour

-filtering and drying to between 10% and 15% starch equilibrium moisture

2) Thermal treatment

The product thus obtained is subjected to a thermal treatment in successive VOMM continuous turbo-reactors, the nominal temperature of which is set at 210 ℃, and configured so as to subject the product to a residence time of about 20 to 35 minutes, and so that the temperature difference between the nominal temperature and the temperature at which the product exits the reactor (called Δ T) is of a value of about 22 ℃ to 27 ℃.

Process parameters

RVA viscosity measurements were made and are presented in the table below.

As a result:

comparative study

The analysis was performed by comparing the product according to the invention with commercial products of the same category. The products derived from the invention were treated according to the following protocol:

resuspension of starch at 36.5% SC

Neutralization with 20% hydrochloric acid to pH 5.5. + -. 1

-filtering, washing to obtain a conductivity of less than 500 μ S, drying to a normal moisture content of between 10% and 15% of starch

Each of the examples F-1, F-2 and F-3 of thermally modified tapioca starch according to the invention has an improved stability during the use process compared to native starch: less viscosity increase and less retrogradation was observed during the use of these starches. This is seen by measuring the droplets with an RVA viscometer: the more negative the droplets, the more resistant the starch is to shear, acidity of the medium and heat treatment.

Each of examples F-1, F-2 and F-3 of thermally modified tapioca starch according to the invention can be compared with other prior art thermal inhibition products based on tapioca starch, such as C L ARIA Bliss 570, the most resistant products are those derived from the invention according to the results of RVA viscometer.

Similarly, each of examples F-1, F-2 and F-3 of thermally modified tapioca starch according to the invention can be compared to examples on waxy maize and notably family D: family D has a higher peak viscosity for the same measured solids content and is more process tolerant. The choice of the use of these starches will therefore be made according to the intended application and therefore according to the shear, acidity and temperature conditions used.

Example 14: preparation of thermally modified pea starch

1) The alkalization of pea starch is carried out according to the following steps:

-preparation of a pea starch suspension with a Solid Content (SC) of 33%

-addition of powdered sodium carbonate to obtain a final conductivity between 0.7 and 1.1mS on the powder resuspended to 20% SC

Ensure a contact time of 1 hour

-filtering and drying to between 10% and 15% starch equilibrium moisture

2) Thermal treatment

The product thus obtained is subjected to a thermal treatment in successive VOMM continuous turbo-reactors, the nominal temperature of which is set at 210 ℃, and configured so as to subject the product to a residence time of about 10-25 minutes, and so that the temperature difference between the nominal temperature and the temperature at which the product exits the reactor (called Δ Τ) is of a value of about 21 ℃ -25 ℃.

Process parameters

RVA viscosity measurements were made and are presented in the table below.

As a result:

comparative study:

the analysis was performed by comparing the product according to the invention with commercial products of the same category. The products derived from the invention were treated according to the following protocol:

resuspension of starch at 36.5% SC

Neutralization with 20% hydrochloric acid to pH 5.5. + -. 1

-filtration, washing to obtain a conductivity of less than 500 μ S, drying to a conventional moisture content of starch of between 14% and 18%

Each example G-1 and G-2 of pea starch thermally modified according to the invention has an improved stability during the use process compared to native starch: less viscosity increase and less retrogradation was observed during the use of these starches. This is seen by measuring the droplets with an RVA viscometer: the more negative the droplets, the more resistant the starch is to shear, acidity of the medium and heat treatment.

Each example G-1 and G-2 of pea starch thermally modified according to the invention can be compared with examples on waxy maize and notably family D: each of examples G-1 and G-2 had a lower peak viscosity for the same measured solids content and were equally tolerant to the process as family D. A particular feature of pea starch is the production of an extremely resistant product by means of shorter residence times than other starting materials. The choice of the use of these starches will therefore be made according to the intended application and therefore according to the shear, acidity and temperature conditions used.

Example 15: use of thermally modified starch "C" in tomato sauce-tomato paste

The analysis was based on the following control formula:

the process for preparing tomato paste tomato sauce is as follows:

for a 2kg batch:

4. cooking steps on a 2L Hotmix Pro Combi cooker:

e. mixing all ingredients together in the bowl of the Hotmix machine

f. Cooking at 100 ℃ for 30 minutes. As the mixture became too viscous, the first 10 minutes at speed 3(800rpm) followed by the last 20 minutes at speed 1E (480rpm) were performed using a mixing spindle (butterfly).

5. packaging/Conditioning

A375 ml glass bottle was filled with 330g at a temperature of 60 ℃ to 65 ℃.

6. Pasteurization

Autoclaving at 85 ℃ for 45 minutes (apparatus: Steriflow rotation double Process)900mm-1 basket-reference NS911R MP F L W STEAM,2017,www.steriflow.com/en；rotating: no (static) -Heat treatment with Water Cascade by pasteurization)

Finally, the formulation is characterized in that:

-total water content: 43 percent

-pH：3.7

-brix: 29.5

The various starches tested were as follows:

thermally modified starch "C-3" according to the invention (example 3)

Sold by the applicant companyCH2020 (acetylated adipate cross-linked waxy corn starch)

Sold by the company Yiruian2300

By means ofThe following measurements were evaluated for various tomato sauces:

5.cooking level of starch

The cooking level was determined by light microscopy (L eica microscope- × 20 lens and × 150 magnification.) the sample was dispersed in demineralized water and then stained with L ugol for the purpose of revealing the starch granules.

Optical microscopy gave a variety of information:

→ check for the presence and appearance of starch particles. They may be "uncooked"; "slightly cooked"; "medium cooked"; "well cooked"; "fragmented"; or "dissolved (absent)" is present.

6.Rheology of

Several methods are used to evaluate the rheological properties of the sauce obtained.

a.Flow measurement

Equipment: antopa MCR301 rheometer

Characterization of the behavior of non-Newtonian fluids. The instrument applies a specific stress field or strain on the fluid and monitors the resulting strain or stress. The results are expressed as a log scale plot of viscosity (pa.s) as a function of shear rate (γ). The results of this study are highlighted by the viscosity at γ ═ 40s "1 (equivalent texture shear measured in the mouth).

Geometry: concentric cylinder

And (3) analysis: oscillation

Temperature: 20 deg.C (+1 minute temperature stabilization)

Time: 10 minutes

Oscillating stress: 0.1 to 1000Pa

Repeatability: average of three measurements

Precision: 5 percent of

b.Bostwick consistometer

The Bostwick machine is a consistometer, it consists of a rectangular stainless steel trough divided into two parts by a sluice, the smaller part serves as a repository for the material to be evaluated, the larger part is equipped with 1/2cm graduations from the door and to the other end, the door is driven by a spring, it is held in the bottom position by means of a lever arm.

To make this evaluation, the tank was filled to full capacity. Flow was measured at 30s and 40 s. The average of the values (at 20 ℃) of two replicates per serving of sauce was then determined (i.e. at 35 s).

Results and discussion:

5. cooking level of starch

The microscope allows a qualitative analysis of the cooking level of the starch granules.

By using2300 microscopic observation of the prepared tomato paste showed well cooked starch granules and some less cooked granules.

By usingMicroscopic observation of tomato paste in CH2020 showed well cooked starch granules and also a certain amount of crumbs.

Microscopic observation of the thermally modified starch "C-3" according to the invention showed well cooked starch granules. The behavior of the particles is close to2300. Both starches were observed to be almost free of debris. Under these conditions, they seem to be comparedCH2020 is more tolerant.

6. Rheological Properties

a. Flow measurement

The following table summarizes the flow measurements:

the viscosity developed by the thermally modified starch "C3" is slightly lowerCH2020 and2300 viscosity.

b. Consistency (Bostwick)

The following table summarizes the consistency measurements:

tomato paste prepared with thermally modified starch "C3" had higher flow than the other two. This confirms the flow data described previously.

Tomato paste prepared from thermally modified starch "C3" is more convenient than tomato paste prepared from thermally modified starchCH2020 and2300 the paste is more fluid.

And (4) conclusion:

in tomato paste sauce applications, the thermally modified starch "C3" according to the invention has a behavior close to that of the control: however, although the swelling level is equivalent, it is not clear thatCH2020 (acetylated adipate cross-linked waxy maize starch) and Heat inhibited starch2300 developed a lower viscosity under the same conditions (see microscopy analysis).