阅读说明：本技术 改性淀粉、其用途及改性淀粉的制造方法 (Modified starch, use thereof, and method for producing modified starch ) 是由 村松大辅 竹本纮基 森本和树 高口均 于 2019-08-15 设计创作，主要内容包括：廉价且简便地提供具有新性质的改性淀粉。一种改性淀粉,其是粒径分布波形显示单一峰的改性淀粉,10质量％糊液的RVA峰值粘度为作为原料的未改性淀粉的RVA峰值粘度的5％以下,且最大粒径与最小粒径之差为2μm以下。该改性淀粉适合用作食品用添加剂、食品用口感改良剂、粉末化基材、粘合剂用添加剂、造纸用添加剂、建材用添加剂等。(A modified starch having novel properties is provided inexpensively and easily. A modified starch having a particle size distribution waveform showing a single peak, wherein the RVA peak viscosity of a 10 mass% paste is 5% or less of the RVA peak viscosity of an unmodified starch as a raw material, and the difference between the maximum particle size and the minimum particle size is 2 μm or less. The modified starch is suitably used as an additive for foods, an improver for food texture, a powdered base material, an additive for adhesives, an additive for paper making, an additive for building materials, and the like.)

1. A modified starch having a particle size distribution waveform showing a single peak, wherein the RVA peak viscosity of a 10 mass% paste is 5% or less of the RVA peak viscosity of an unmodified starch as a raw material, and the difference between the maximum particle size and the minimum particle size is 2 μm or less.

2. The modified starch according to claim 1, having an average particle diameter of 1 μm or less.

3. An additive for food comprising the modified starch of claim 1 or 2.

4. A mouthfeel improving agent for food comprising the modified starch of claim 1 or 2.

5. A powdered substrate comprising the modified starch of claim 1 or 2.

6. An additive for adhesives comprising the modified starch of claim 1 or 2.

7. An additive for papermaking comprising the modified starch of claim 1 or 2.

8. An additive for building materials, comprising the modified starch of claim 1 or 2.

9. A process for producing a modified starch, which comprises adding a halide salt to a starch and subjecting the mixture to a heat-modifying treatment,

in the production method, a heat-modifying treatment is performed so that the RVA peak viscosity of a 10 mass% paste of the obtained modified starch is 5% or less of the RVA peak viscosity of the unmodified starch as a raw material and the difference between the maximum particle diameter and the minimum particle diameter is 2 [ mu ] m or less.

10. The method for producing a modified starch according to claim 9, wherein the heat modification treatment is performed so that the average particle diameter of the obtained modified starch is 1 μm or less.

11. The method for producing a modified starch according to claim 9 or 10, wherein the halide salt is added in an amount of 0.1 to 20 parts by mass per 100 parts by mass of the starch.

12. The method for producing a modified starch according to any one of claims 9 to 11, wherein the halide salt is 1 or 2 or more selected from the group consisting of ferrous chloride, ferric chloride, calcium chloride, magnesium chloride, ammonium chloride, lithium chloride, sodium chloride, ferrous bromide, ferric bromide, calcium bromide, magnesium bromide, ammonium bromide, lithium bromide, sodium bromide, ferrous iodide, calcium iodide, magnesium iodide, ammonium iodide, lithium iodide and sodium iodide.

13. The method for producing a modified starch according to any one of claims 9 to 12, wherein the halide salt is calcium chloride.

14. The method for producing a modified starch according to any one of claims 9 to 13, wherein the heat modification treatment is performed at 50 ℃ to 200 ℃ for 0.5 hours to 30 days.

15. The method for producing a modified starch according to any one of claims 9 to 14, wherein an α -formation treatment is further performed after the heat modification treatment.

Technical Field

The present invention relates to modified starch, use thereof, and a method for producing modified starch.

Background

Methods for modifying the properties of starch by processing are roughly classified into 3 types of enzymatic processing, chemical processing, and physical processing. Wherein, the physical processing treatment has the following characteristics: compared with the enzyme processing treatment, the method can be carried out at low cost and simply, and compared with the chemical processing treatment, the method has low worry about safety and high degree of legal freedom.

As one of physical processing methods of starch, there are several reports on a method of adding a metal salt to starch and heating the starch. For example, patent document 1 describes: a method for producing a heat-moisture treated starch, which comprises adding a metal salt as a heat-moisture treatment accelerator to a starchy material for the purpose of improving the efficiency of the heat-moisture treatment. Patent document 2 describes: a method for producing potato starch, which comprises adding calcium chloride to a potato starch suspension having a pH of about 6 to about 8 and heating the suspension at about 45 to about 55 ℃ for the purpose of increasing the temperature at which the highest viscosity of potato starch is exhibited and suppressing the decrease in viscosity. Patent document 3 describes a method for producing a modified starch, which aims to provide a modified starch that is low in viscosity, non-reducing, less likely to undergo a maillard reaction, and widely usable in the food field, and which is obtained by subjecting a wet mixture containing starch, water, and salts to a heat treatment.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. H06-145203

Patent document 2: japanese laid-open patent publication No. H07-196701

Patent document 3: japanese patent laid-open No. 2001-275585

Disclosure of Invention

Problems to be solved by the invention

Starch is required to have various physical properties depending on its use. The purpose of the present invention is to provide a modified starch having novel properties at low cost and simply, and to provide the use of the modified starch and a method for producing the modified starch.

Means for solving the problems

The present inventors have conducted extensive studies to achieve the above object, and as a result, the present invention has been completed.

That is, the present invention provides, in view 1 thereof, a modified starch having a particle size distribution waveform showing a single peak, wherein the RVA peak viscosity of a 10 mass% paste is 5% or less of the RVA peak viscosity of an unmodified starch as a raw material, and the difference between the maximum particle size and the minimum particle size is 2 μm or less.

In the modified starch of the present invention, the average particle diameter is preferably 1 μm or less.

The present invention provides, in its 2 nd aspect, an additive for food comprising the above-mentioned modified starch.

The present invention provides, in its 3 rd aspect, a texture-improving agent for food, which comprises the above-mentioned modified starch.

The present invention provides, in its 4 th aspect, a powdered substrate comprising the above-mentioned modified starch.

The present invention provides, in its 5 th aspect, an additive for adhesives, which comprises the above-mentioned modified starch.

The present invention provides, in its 6 th aspect, an additive for papermaking, which comprises the above-mentioned modified starch.

The present invention provides, in its 7 th aspect, an additive for building materials, which comprises the above-mentioned modified starch.

In another aspect, the present invention provides a method for producing a modified starch by adding a halide salt to a starch and subjecting the starch to a heat-modifying treatment, wherein the heat-modifying treatment is carried out so that the RVA peak viscosity of a 10 mass% paste of the obtained modified starch is 5% or less of the RVA peak viscosity of an unmodified starch as a raw material and the difference between the maximum particle diameter and the minimum particle diameter is 2 μm or less.

In the method for producing modified starch of the present invention, it is preferable to perform heat modification treatment so that the average particle size of the obtained modified starch becomes 1 μm or less.

In the method for producing a modified starch of the present invention, it is preferable to add 0.1 to 20 parts by mass of the halide salt per 100 parts by mass of the starch.

In the method for producing a modified starch of the present invention, it is preferable that the halide salt is 1 or 2 or more selected from the group consisting of iron (II, III) chloride, calcium chloride, magnesium chloride, ammonium chloride, lithium chloride, iron (II, III) bromide, calcium bromide, magnesium bromide, ammonium bromide, lithium bromide, sodium bromide, iron (II) iodide, calcium iodide, magnesium iodide, ammonium iodide, lithium iodide, and sodium iodide.

In the method for producing a modified starch of the present invention, the halide salt is preferably calcium chloride.

In the method for producing modified starch of the present invention, the heat-modifying treatment is preferably performed at 50 to 200 ℃ for 0.5 hours to 30 days.

Further, it is preferable to further perform an α -forming treatment after the heat-modifying treatment.

ADVANTAGEOUS EFFECTS OF INVENTION

The modified starch provided by the present invention is characterized by being capable of being produced inexpensively and easily, having a low viscosity, and having a uniform particle diameter of a starch paste, and is capable of improving the physical properties thereof when added to a food. Specifically, the taste improving effect such as improvement in mouth solubility or improvement in smoothness can be exhibited. In addition, the resin composition can be used as a raw material for chemical industrial products such as powdered substrates, adhesives, papers, and building materials.

Drawings

FIG. 1 is a graph showing the particle size distribution waveforms obtained for each of the starch samples of samples 1-2, 1-6 and comparative sample 1-1 (unmodified corn starch) evaluated in test example 1.

Detailed Description

The present invention relates to a modified starch having a particle size distribution waveform showing a single peak, wherein the RVA peak viscosity of a 10 mass% paste is 5% or less of the RVA peak viscosity of an unmodified starch as a raw material, and the difference between the maximum particle size and the minimum particle size is 2 [ mu ] m or less.

That is, the modified starch of the present invention has a characteristic that the particle size distribution waveform shows a single peak. The particle size of the starch is a particle size obtained when the particle size distribution of the paste is measured. The particle size distribution waveform is a histogram showing the presence ratio of particles of each particle size. The particle size distribution waveform can be measured, for example, as follows.

(particle size distribution waveform)

The starch sample paste is dispersed in water so that the solid content concentration becomes 0.02 mass% to prepare a dispersion, which can be measured, for example, with a dynamic light scattering measuring instrument such as ELSZ-2000ZS available from Otsuka Denshi. The particle size distribution waveform was calculated from the scattering intensity distribution. In the present invention, the particle size distribution waveform "shows a single peak" means a state where the peak of the scattering intensity distribution does not exist at a plurality of particle size values. As in the examples described later, even if a plurality of peaks are not recognized, the peaks are not regarded as a single peak when a plurality of peaks are clearly mixed, such as when the peaks are broadened or when a shoulder peak is recognized.

The modified starch of the present invention is characterized in that the RVA peak viscosity of a 10 mass% paste is 5% or less of the peak viscosity of the unmodified starch as the raw material. In the present specification, the ratio (%) of the RVA peak viscosity of a 10 mass% paste of a modified starch when the RVA peak viscosity of a 10 mass% paste of an unmodified starch is 100% may be abbreviated as "peak viscosity ratio". In addition, the term "peak viscosity" refers to the RVA peak viscosity. The RVA peak viscosity can be determined, for example, as follows.

(RVA Peak viscosity)

A starch sample was dispersed in water to 10 mass% to prepare 30g of a dispersion, which was kept at 50 ℃ for 1 minute while stirring with a paddle at 160rpm, and was kept at 95 ℃ for 3 minutes and 42 seconds from 50 ℃, kept at 95 ℃ for 2 minutes and 30 seconds, kept at 50 ℃ for 3 minutes and 48 seconds, and kept at 50 ℃ for 2 minutes. Under these conditions, the peak viscosity (highest viscosity) was measured. The peak viscosity can be measured using a Rapid Viscoanalyzer (RVA), and for example, a rapid viscoanalyzer manufactured by Perten Instruments can be used as the Rapid Viscoanalyzer (RVA).

The modified starch of the present invention is characterized in that the difference between the maximum particle size and the minimum particle size is 2 μm or less. The maximum particle diameter and the minimum particle diameter can be measured by the same method as that for obtaining the above-described particle diameter distribution waveform.

More typically, the paste immediately after measurement by the above Rapid Viscometric Analyzer (RVA) is diluted with distilled water to a solid content concentration of 0.02 mass% to prepare a dispersion, which is filled in a glass standard cuvette and analyzed by a dynamic light scattering measuring instrument (for example, ELSZ-2000ZS available from Otsuka Co., Ltd.). The measurement can be performed at room temperature with 25 times of integration, and the refractive index, viscosity, and dielectric constant of the solvent can be measured using the values of water.

The measurement of the particle size distribution waveform, the RVA peak viscosity, the maximum particle size, the minimum particle size, and the average particle size described later is carried out using a modified starch which is washed (washed) with water after the modification treatment, in the case where a halide salt is used for the production of the modified starch as described later.

As described above, the modified starch of the present invention has a low viscosity and is characterized by uniform particle size of starch grains, and it is considered that this characteristic exerts a significant taste improvement effect of a food. The modified starch of the present invention may have a feature that the particle size in the starch paste is extremely small to the order of nanometers, and thus, the modified starch has both of the above-described features, and thus, particularly remarkable performance is exhibited, which is preferable. For example, the modified starch of the present invention may have an average particle diameter of 1 μm or less. The average particle size of the modified starch can be measured by the same method as that for obtaining the above-mentioned particle size distribution waveform, the above-mentioned maximum particle size and minimum particle size, and calculated by cumulant analysis, for example.

It is to be noted that there is no reason to exclude the case where the processing treatment such as the α formation treatment is performed, in particular, from the technical scope of the present invention. Namely, it may include: modified starches using processed starches by alphatization or the like as raw materials, and modified starches subjected to processing such as alphatization after preparation using a halide salt or the like described later.

When the modified starch of the present invention is used as a food material, the food can be modified by the above-described features. For example, it can be used as a raw material for food and can be used for the purpose of improving the mouth solubility and improving the smoothness. When the food material is used as an additive for food, the amount of the additive is not particularly limited, and may be appropriately determined depending on the properties required for the food to be added and other materials, and may be added to the food material in an amount of 0.1 to 99% by mass, for example.

The food to which the modified starch of the present invention is added is preferably cheese, chocolate, soft candy (Japanese: グミ), candy, powdered butter, roux, ice cream, rice, fried rice, pilaf, processed marine livestock meat, etc., and the modified starch of the present invention can be used in place of relatively expensive fish meat, livestock meat, milk components, cocoa mass, gelatin, etc.

The modified starch of the present invention can be used as a raw material for chemical industrial products such as powdered substrates, adhesives, papers, and building materials, in addition to foods, by taking advantage of the above characteristics. Examples of the binder include an adhesive (next agent) and a binder (next agent), examples of the paper include offset paper and corrugated paper, and examples of the building material include gypsum board and cement. The amount of the modified starch to be added in this application is not particularly limited, and may be appropriately determined depending on the application and other raw materials, and may be added so as to be 0.1 to 99 mass% in the raw materials, for example.

The modified starch of the present invention has a low viscosity due to the above characteristics when used as a base material to be powdered, and thus has high powdering efficiency. The modified starch of the present invention can exhibit high homogeneity and cohesiveness due to the above-mentioned characteristics when used as an additive for adhesives. The modified starch of the present invention has high solubility due to the above characteristics when used as an additive for papermaking, and can be uniformly mixed with other components. The modified starch of the present invention can be uniformly mixed with other components due to the above-mentioned characteristics when used as an additive for building materials.

The method for producing the modified starch of the present invention will be described below. However, the following description does not intend to limit the technical scope of the modified starch of the present invention by its production method.

The method for producing the modified starch is a method of adding a halide salt to starch and subjecting the starch to a heat modification treatment, and the heat modification method is not particularly limited as long as a modified starch having desired properties can be obtained, and heating by a dry reaction is preferable in terms of production efficiency and environmental load. In the present specification, the term "dry reaction" means that the heat-modifying treatment is performed with a moisture content of less than 40 mass%. Conditions of the heating temperature and the heating time are also not particularly limited, but the heat modification treatment needs to be performed so that the peak viscosity ratio of the obtained modified starch is 5% or less and the difference between the maximum particle diameter and the minimum particle diameter is 2 μm or less. By performing the heat modification treatment so that the modified starch satisfies the above parameters, it is possible to obtain a modified starch having a single peak in the particle size distribution waveform and uniform particle size of starch grains. The heating modification conditions are enhanced by increasing the amount of the halide salt to be added, increasing the heating temperature, decreasing the pH during heating, or extending the heating time, and the peak viscosity ratio of the modified starch tends to decrease. Similarly, if the heat-modifying condition is increased, the difference between the maximum particle size and the minimum particle size of the modified starch is decreased, and if the heat-modifying condition exceeds a certain range, the difference between the maximum particle size and the minimum particle size tends to be increased. The degree of decrease in the peak viscosity ratio is slightly different depending on the kind of the halide salt to be added. Therefore, by appropriately adjusting the conditions of the heat-modifying treatment such as the kind of the halide salt used, the amount added, the heating temperature, the pH, and the heating time, the desired modified starch can be obtained using the above-mentioned points as indices.

The starch used as a raw material for the preparation of the modified starch is not particularly limited as long as it is a starch used in general food and chemical applications, and corn starch, tapioca starch, potato starch, sweet potato starch, wheat starch, sago starch, bean starch, and the like can be used, and any of japonica rice (waxy rice) seed, waxy rice (waxy rice) seed, high amylose seed, and the like can be used. In addition, a plurality of starches may be used in combination. In addition, various processed starches can be used as the starch as the raw material. That is, starch subjected to chemical modification treatment such as oxidation treatment, esterification treatment, etherification treatment, and crosslinking treatment, alphatization treatment, granulation treatment, wet heat treatment, ball mill treatment, fine pulverization treatment, heating treatment, warm water treatment, bleaching treatment, sterilization treatment, acid treatment, alkali treatment, enzyme treatment, or 2 or more kinds of these treatments can be used.

The halide salt used for the preparation of the modified starch is not particularly limited as long as it is an industrially available halide salt, and examples thereof include chloride salts (iron (II, III) chloride, calcium chloride, magnesium chloride, ammonium chloride, lithium chloride, sodium chloride, etc.), bromide salts (iron (II, III) bromide, calcium bromide, magnesium bromide, ammonium bromide, lithium bromide, sodium bromide, etc.), iodide salts (iron (II) iodide, calcium iodide, magnesium iodide, ammonium iodide, lithium iodide, sodium iodide, etc.), etc. from the viewpoint of the effect thereof, chloride salts are preferable, calcium chloride, ammonium chloride, magnesium chloride are more preferable, and calcium chloride is particularly preferable from the viewpoint of particle size distribution and taste. The halide salt may be used in combination of plural kinds.

In the preparation of the modified starch, the heating modification conditions may be appropriately adjusted as described above using the peak viscosity ratio and the difference between the maximum particle diameter and the minimum particle diameter as an index, and for example, in the case of adding calcium chloride, the addition rate of calcium chloride to 100 parts by mass of starch may be 0.8 to 15 parts by mass, and the heating modification treatment may be performed at 50 to 200 ℃ for 0.5 to 30 days, in the case of adding ammonium chloride, the addition rate of ammonium chloride to 100 parts by mass of starch may be 0.1 to 5 parts by mass, and the heating modification treatment may be performed at 50 to 200 ℃ for 0.5 to 30 days, and in the case of adding magnesium chloride, the addition rate of magnesium chloride to 100 parts by mass of starch may be 0.1 to 8 parts by mass, and the heating modification treatment may be performed at 50 to 200 ℃ for 0.5 to 30 days.

The modified starch subjected to the heat modification treatment may be subjected to water washing and drying treatment as needed. That is, depending on the use of the modified starch, there may be a disadvantage that the taste of the food is adversely affected by the residual halogenated salt, and therefore, it is preferable to remove the residual salt by washing with water and drying. On the other hand, depending on the application, the washing and drying treatment may not be performed, and in this case, the production cost can be suppressed.

After the preparation of the modified starch described above, other processing such as α -formation may be further performed. The treatment may be carried out according to a usual starch treatment method, and examples of the treatment for gelatinization include a drum dryer treatment method, a spray dryer treatment method, and an extrusion method.

Examples

The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.

(analysis of sample)

In the test examples shown below, (1) the RVA peak viscosity, (2) the particle size distribution waveform (number of peaks), (3) the average particle size, (4) the maximum particle size and the minimum particle size of each sample were measured by the following methods.

(1) RVA Peak viscosity

The measurement was carried out using a Rapid Viscoanalyzer (RVA) (Perten Instruments Co., Ltd.) as follows.

Each sample was dispersed in water to be 10 mass% to prepare 30g of a dispersion, which was kept at 50 ℃ for 1 minute while stirring with a paddle at 160rpm, and was kept in a continuously heated state at 50 ℃ for 3 minutes and 42 seconds to 95 ℃, and was kept at 95 ℃ for 2 minutes and 30 seconds, and was kept at 50 ℃ for 3 minutes and 48 seconds to 50 ℃ for continuous cooling, and the peak viscosity (maximum viscosity) was measured under the condition of keeping at 50 ℃ for 2 minutes.

(2) Particle size distribution waveform (Peak number)

The particle size distribution was analyzed by using a dynamic light scattering measuring instrument (ELSZ-2000 ZS available from Otsuka Denshi Co., Ltd.) as follows.

The paste immediately after measurement by a Rapid Visco Analyzer (RVA) was diluted with distilled water to a solid content concentration of 0.02 mass% to prepare a dispersion, which was filled in a glass standard cuvette and subjected to measurement using water as a solvent for refractive index, viscosity, and dielectric constant under conditions of an integrated number of 25 times at room temperature. The number of peaks was determined from the obtained particle size distribution waveform.

(3) Average particle diameter

In the particle size measurement of the above (2), the average particle size was calculated by cumulant analysis.

(4) Maximum and minimum particle sizes

The maximum particle size value and the minimum particle size value are obtained from the particle size distribution waveform obtained by the particle size distribution measurement of the above (2).

[ test example 1] (test groups derived from corn starch)

Calcium chloride was added to 20 parts by mass of water so as to be in the ratio (per unit mass of starch) shown in table 1, and the mixture was dissolved in advance. Adding the calcium chloride aqueous solution into 100 parts by mass of the corn starch, and stirring the mixture by using a stirrer until the mixture is homogeneous. After stirring, the mixture was transferred to a stainless steel pan, and starch was dispersed so as to have a thickness of 10mm or less (the water content of starch in each sample was 30 mass%). The aluminum plate was transferred to an oven previously heated to 130 ℃ and subjected to heat modification treatment as shown in table 1. After the heat modification treatment, the mixture was allowed to cool at room temperature for 30 minutes. After cooling, 2000 parts by mass of water was added to 100 parts by mass of the dried starch, and the mixture was washed with water, dehydrated and dried to obtain modified starches of comparative sample 1-2 and samples 1-1 to 1-9.

The resulting modified starch was subjected to analysis based on the above-mentioned measurement. The results are shown in table 1. In addition, fig. 1 shows: among the evaluated samples, as a typical example, the particle size distribution waveform obtained for each of the starch samples of sample 1-2, sample 1-6 and comparative sample 1-1 (unmodified corn starch).

[ Table 1]

As shown in Table 1, by adding calcium chloride and performing a certain degree of heat-modifying treatment, modified starch having a peak viscosity ratio of 5% or less to unmodified starch (comparative sample 1-1) as raw corn starch and a B-A of 2000nm or less was obtained. The particle size distribution waveform of the modified starch having the above parameters shows a single peak (see fig. 1). On the other hand, the modified starch which does not satisfy the parameters that the peak viscosity ratio to the unmodified starch (comparative sample 1-1) is 5% or less and B-A is 2000nm or less does not show a single peak in the particle size distribution waveform (see FIG. 1). In particular, comparative sample 1-2, which is a modified starch described in examples of Japanese patent application laid-open No. 2001-275585, has a peak viscosity ratio of 5% or less, but B-A is a value exceeding 2000nm, and the particle size distribution waveform does not show a single peak. Therefore, it was revealed that the modified starch described in Japanese patent laid-open No. 2001-275585 is not a starch satisfying the parameters of the present invention.

[ test example 2] (test groups derived from waxy corn starch)

Calcium chloride was added to 20 parts by mass of water so as to be in the ratio (per unit mass of starch) shown in table 2, and was dissolved in advance. Adding the calcium chloride aqueous solution into 100 parts by mass of waxy corn starch, and stirring by using a stirrer until the mixture is homogeneous. After stirring, the mixture was transferred to a stainless steel pan, and starch was dispersed so as to have a thickness of 10mm or less (the water content of starch in each sample was 30 mass%). The aluminum plate was transferred to an oven previously warmed to 130 ℃ and subjected to heat modification treatment as shown in table 2. After the heat modification treatment, the mixture was allowed to cool at room temperature for 30 minutes. After cooling, 2000 parts by mass of water was added to 100 parts by mass of the dried starch, and the mixture was washed with water, dehydrated and dried to obtain modified starches of comparative samples 2-2 to 2-3 and samples 2-1 to 2-4.

The resulting modified starch was subjected to analysis based on the above-mentioned measurement. The results are shown in Table 2.

[ Table 2]

As shown in Table 2, by adding calcium chloride and subjecting the mixture to a certain degree of heat-modifying treatment, a modified starch having a peak viscosity ratio of 5% or less to an unmodified starch (comparative sample 2-1) as a raw waxy corn starch and a B-A of 2000nm or less was obtained. In addition, the particle size distribution waveform of the modified starch having this parameter shows a single peak. On the other hand, the modified starches (comparative samples 2-2 and 2-3) modified without adding calcium chloride did not satisfy the above parameters, and the particle size distribution waveform did not show a single peak.

[ test example 3] (test groups derived from tapioca starch)

Calcium chloride was added to 20 parts by mass of water so as to be in the ratio (per unit mass of starch) shown in table 3, and the mixture was dissolved in advance. Adding the calcium chloride aqueous solution into 100 parts by mass of the cassava starch, and stirring by using a stirrer until the cassava starch is homogeneous. After stirring, the mixture was transferred to a stainless steel pan, and starch was dispersed so as to have a thickness of 10mm or less (the water content of starch in each sample was 30 mass%). The aluminum plate was transferred to an oven previously warmed to 130 ℃ and subjected to heat modification treatment as shown in table 3. After the heat modification treatment, the mixture was allowed to cool at room temperature for 30 minutes. After cooling, 2000 parts by mass of water was added to 100 parts by mass of the dried starch, and the mixture was washed with water, dehydrated and dried to obtain modified starches of comparative sample 3-2 and samples 3-1 to 3-2.

The resulting modified starch was subjected to analysis based on the above-mentioned measurement. The results are shown in Table 3.

[ Table 3]

As shown in Table 3, by adding calcium chloride and performing a certain degree of heat-modifying treatment, modified starch having a peak viscosity ratio of 5% or less and a B-A of 2000nm or less was obtained as unmodified starch of raw tapioca (comparative sample 3-1). In addition, the particle size distribution waveform of the modified starch having this parameter shows a single peak. On the other hand, the particle size distribution waveform of the modified starch which does not satisfy the parameters that the peak viscosity ratio to the unmodified starch (comparative sample 3-1) is 5% or less and B-A is 2000nm or less does not show a single peak. In addition, the modified starch (comparative sample 3-2) which had been modified without adding calcium chloride did not satisfy the above parameters in the same manner, and the particle size distribution waveform did not show a single peak.

[ test example 4] (test groups in which the salt species were changed)

To 20 parts by mass of water, each salt was added in a proportion (per unit mass of starch) shown in table 4 and dissolved in advance. The aqueous solution of each salt was added to 100 parts by mass of corn starch, and stirred with a stirrer until the mixture was homogeneous. After stirring, the mixture was transferred to a stainless steel pan, and starch was dispersed so as to have a thickness of 10mm or less (the water content of starch in each sample was 30 mass%). The aluminum plate was transferred to an oven previously heated to 130 ℃ and subjected to heat modification treatment as shown in table 4. After the heat modification treatment, the mixture was allowed to cool at room temperature for 30 minutes. After cooling, 2000 parts by mass of water was added to 100 parts by mass of the dried starch, and the mixture was washed with water, dehydrated and dried to obtain modified starches of samples 4-1 to 4-9.

The resulting modified starch was subjected to analysis based on the above-mentioned measurement. The results are shown in Table 4.

[ Table 4]

As shown in Table 4, by adding ammonium chloride and magnesium chloride and subjecting the mixture to a certain degree of heat-modifying treatment, modified starch having a peak viscosity ratio of 5% or less to unmodified starch (comparative sample 4) as raw corn starch and a B-A of 2000nm or less was obtained. In addition, the particle size distribution waveform of the modified starch having this parameter shows a single peak. On the other hand, the modified starch which does not satisfy the parameters that the peak viscosity ratio to the unmodified starch (comparative sample 4) is 5% or less and B-A is 2000nm or less does not show a single peak in the particle size distribution waveform.

From these results, it was confirmed that: modified starches satisfying the above parameters can be obtained by a desired modification treatment without being limited to calcium chloride as long as they are halogenated salts.

[ test example 5] (masa)

Putting whole egg into glass bowl, adding granulated sugar, stirring, adding milk protein, milk, rapeseed oil, syrup, and citric acid, and stirring with a beater. The mixture was transferred to a mixing bowl and homogenized for 5 minutes at 5000rpm with a homomixer while heating. Then, adding a small amount of starch raw material into the liquid each time, stirring until the starch raw material is uniformly dispersed, heating for 4-5 minutes at the temperature of more than 90 ℃, boiling until the yield reaches 90%, taking down from the fire, and adding vanilla oil. The obtained flour paste was vacuum-packed and cooled with running water. The compounding ratio of each raw material is shown in table 5.

[ Table 5]

TABLE 5

	Mixing ratio
		Starch raw material	6.5
Citric acid	0.5
		Milk protein	2.0
Granulated sugar	10.0
		Whole egg	5.0
Syrup	25.0
		Rapeseed oil	15.0
Milk	35.0
		Vanilla oil	1.0
Total up to	100

As starch raw materials, used were the sample 1-3 (modified starch) prepared in test example 1, the comparative sample 1-1 (unmodified corn starch), and acetylated oxidized starch (TSK-13, Japan food chemical Co., Ltd.) as a commercially available low-viscosity starch.

The obtained flour paste was subjected to sensory evaluation after production (ordinary temperature) and after 7 days of cold storage. Sensory evaluation was conducted by 5 panelists on the basis of the following criteria, and the average score of the evaluation scores of the panelists was calculated.

< mouth feel >

The mouth-soluble feeling when the batter was put into the mouth was evaluated on 6 scales of 1 to 6 points (the higher the evaluation score, the better the mouth-soluble feeling).

< degree of screw slip >

The degree of silkiness when the batter was put into the mouth was evaluated on 6 scales of 1 to 6 points (silkiness was observed as the evaluation score was higher).

< Water (Japanese: Water) inhibition Effect >

The dehydration-inhibiting effect of the batter itself was evaluated on 4 scales of 1 to 4 points (the higher the evaluation point is, the less dehydration is). Since dehydration did not occur immediately after production, the dehydration-inhibiting effect was evaluated only for the batter after refrigeration.

The sensory evaluation results of the roux containing each starch material are shown in table 6.

[ Table 6]

TABLE 6

As shown in Table 6, the roux using the modified starch of sample 1-3 was superior in mouth feel and smoothness immediately after production, compared to the case using unmodified corn starch (comparative sample 1-1). In addition, the starch has excellent performance compared with the commercially available low viscosity starch (acetylated oxidized starch). In addition, in the evaluation after the refrigerated storage, the batter using the modified starch of samples 1 to 3 was remarkably excellent in both the mouth-dissolving feeling and the smoothness and also excellent in the dehydration property, as compared with the case of using the unmodified corn starch (comparative sample 1 to 1).

[ test example 6] (Soft candy)

Measuring gelatin and dissolving water, blanching with hot water for 20 min to dissolve gelatin, adding syrup, fine white sugar, and starch raw materials (pre-gelatinized paste), and heating to 117 deg.C. Cooling the pot bottom with water to adjust the liquid temperature to 100 deg.C, adding dissolved gelatin and stirring, adding citric acid solution, orange juice, and perfume, and stirring for 3 min. The resulting soft candy liquid was transferred into a plastic bag for deaeration, and was allowed to stand in an oven set at 80 ℃ for 20 minutes to be deaerated. 15g each of the degassed soft sweets was dispensed into a silicone round mold, and while filtering with tea, corn starch was scattered from above, and the mixture was cooled and solidified in a refrigerator. After cooling and solidifying overnight, the fondant was removed from the mold to obtain a fondant. The compounding ratio of each raw material is shown in table 7.

[ Table 7]

TABLE 7

	Mixing ratio
		Starch raw material	3.0
Water (for starch gelatinization)	15.0
		Gelatin	3.0
Water (for dissolving gelatin)	8.0
		Syrup	45.0
Fine white granulated sugar	20.0
		Citric acid	1.0
Water (for dissolving citric acid)	1.5
		Concentrated fruit juice	3.0
Perfume	0.5
		Total up to	100

As starch raw materials, used were the sample 1-3 (modified starch) prepared in test example 1, the comparative sample 1-1 (unmodified corn starch), and acetylated oxidized starch (TSK-13, Japan food chemical Co., Ltd.) as a commercially available low-viscosity starch.

The obtained soft candy was subjected to measurement of breaking load and sensory evaluation as follows. The evaluation of hardness and elastic force was performed by 5 panelists based on the following criteria, and the average score of the evaluation scores of the panelists was calculated, and the evaluation of workability was judged by the manufacturer of the soft candy based on the following criteria.

< breaking load >

The oval jelly was cut out with a ring having a diameter of 3cm and subjected to measurement. The measurement was carried out using a creep gauge (product name: ReonerIcreEP METER RE2-33005B, manufactured by SHAN ELECTRIC CORPORATION) under the following conditions (n: 3).

Plunger (Japanese: プランジャー): knife tool back (Japanese カッター back)

Setting the deformation rate: 300 percent

A force sensor: 200N

Hardness

The hardness at the time of chewing the soft candy was evaluated on a 7-point scale of-3 to 3 points (the higher the evaluation score, the harder) with the comparative group containing no starch sample (water was added instead of starch).

< elasticity >

The elastic force when chewing the soft candy was evaluated on a 7-point scale of-3 to 3 points (the higher the evaluation score, the more elastic force).

< workability >

Workability in the production of soft candy was evaluated on the basis of the following criteria in 3 grades of ×, "x" and ∈.

X: the boiling time is long, the stringiness of the soft candy solution is high, and the filling of the mold is difficult

O: the boiling time is short, the stringiness of the soft candy solution is low, and the mold is easy to fill

Very good: short boiling time, low stringiness of soft candy solution, and easy filling into mold

The results of measurement and evaluation of the fondants containing the starch materials are shown in table 8.

[ Table 8]

TABLE 8

As shown in Table 8, the results of evaluation of breaking load and hardness of the fondant using the modified starch of samples 1 to 3 were particularly excellent as compared with the case of using unmodified corn starch (comparative sample 1 to 1), and also excellent in workability. On the other hand, the soft candy using the commercially available low viscosity starch (acetylated oxidized starch) was superior in the evaluation results of breaking load and hardness, but was greatly inferior in elasticity, compared to the case of using the unmodified corn starch (comparative sample 1-1).

[ blending example 1]

(Marine extract powder)

Marine extract powder can be produced by adding modified starch of the present invention as a base material for powdering, to water according to the formulation shown in table 9, gelatinizing the starch, adding marine extract to the paste solution, and powdering the solution by a spray dryer.

[ Table 9]

TABLE 9

	Mixing ratio (% by mass)
		Marine product extract	15.0
Modified starch	20.0
		Distilled water	65.0

[ COMPLEX EXAMPLE 2] (adhesive for ceiling tile decorative plate)

A modified starch (in a paste state), a crosslinking agent, an accelerator, and a surfactant were mixed in the formulation shown in table 10, and the mixture was sprayed on a ceiling tile using a sprayer and dried to obtain a ceiling tile adhesive containing the modified starch of the present invention as an additive.

[ Table 10]

Watch 10

	Mixing ratio (% by mass)
		Modified starch	65 to 70 (solid content)
Crosslinking agent	25～30
		Accelerator	2～5
Surface active agent	0.1～0.3

[ COMPATIVE EXAMPLE 3] (coated paper)

Coated paper can be obtained by adding modified starch of the present invention as an additive to water to gelatinize the starch according to the formulation shown in table 11, adding synthetic latex and heavy sodium carbonate to the paste, applying the mixture to base paper using a blade coater, and drying the coated paper.

[ Table 11]

TABLE 11

	Mixing ratio (parts by mass)
		Modified starch	6.0
Synthetic latex	1.8
		Ground calcium carbonate	100.0
Water (W)	70.0

[ COMPLEX EXAMPLE 4] (building Material)

A building material can be obtained by mixing modified starch (paste), vermiculite and allophane in the formulation shown in table 12 using a Hobart mixer, coating the mixture on a calcium silicate board to a thickness of 2mm by a roll coating method, and drying the coated product.

[ Table 12]

TABLE 12

	Mixing ratio (% by mass)
		Vermiculite	40.0
Modified starch	20 (solid component)
		Allophane	40.0