Preparation method of hydrogenated starch hydrolysate as well as product and application thereof

Abstract

The invention relates to a preparation method of hydrogenated starch hydrolysate, which comprises the following steps: (1) mixing plant starch with water to obtain gelatinized plant starch; (2) mixing the gelatinized plant starch with a compound enzyme, carrying out an enzymolysis reaction, and carrying out deactivation treatment on the enzyme after the reaction to obtain a polysaccharide slurry; (3) decolorizing the polysaccharide slurry obtained in the step (2); (4) carrying out hydrotreatment on the decolorized polysaccharide slurry to obtain a crude hydrogenated starch hydrolysate; (5) filtering and concentrating the crude hydrogenated starch hydrolysate obtained in the step (4) to obtain hydrogenated starch hydrolysate; wherein the compound enzyme in the step (2) comprises gamma-amylase, isoamylase, glycogen phosphorylase and alpha-amylase. According to the preparation method, gelatinized plant starch is comprehensively and efficiently hydrolyzed, and the starch is decomposed into products with proper sizes and structures, so that the prepared hydrogenated starch hydrolysate has excellent stability and moisturizing performance.

Description

Technical Field

[0001] The invention belongs to the field of cosmetics, and in particular relates to a preparation method of hydrogenated starch hydrolysate and a product and application thereof. Background Art

[0002] The main use of hydrogenated starch hydrolysate in cosmetics is as a moisturizer, which has the advantages of high moisturizing and permeability. Hydrogenated starch hydrolysate is easily absorbed by the skin, can form hydrogen bonds with water molecules, maintain the normal moisture content of the stratum corneum, and can capture trace moisture in the air in a dry environment. By improving the osmotic pressure of the stratum corneum of the skin, a layer of sugar film is formed on the surface of the skin, which can strengthen the skin barrier function, reduce the function of transepidermal water loss of the skin, achieve long-lasting moisturizing and have a refreshing and pleasant skin feel. Since hydrogenated starch hydrolysate is extracted from plant sources, it generally does not have adverse effects on the human body and the environment, and is a cosmetic raw material with great application prospects.

[0003] However, due to the different preparation methods of hydrogenated starch hydrolysates, their moisturizing properties vary greatly, the effects of hydrogenated starch hydrolysates are affected to a certain extent, and the product application is also limited.

[0004] CN106798312A discloses a hydrogenated starch hydrolysate and a preparation method thereof, comprising sequentially adding high-temperature α-amylase, medium-temperature α-amylase and β-amylase to a corn starch suspension to obtain a saccharified liquid, decolorizing, hydrogenating, purifying and concentrating the saccharified liquid; the obtained product is of high quality, with a sweetness of about half that of sucrose, and has good properties such as non-coloring, anti-crystallization, and moisture retention, and has good application prospects in the field of food production, especially in weight loss foods, anti-caries foods, and special foods for diabetic patients. However, the method does not improve the moisture retention and stability of hydrogenated starch hydrolysate from multiple dimensions.

[0005] Therefore, developing a method for preparing hydrogenated starch hydrolysate so that the prepared hydrogenated starch hydrolysate has excellent moisture retention and stability has become a technical problem that needs to be solved urgently. Summary of the invention

[0006] In view of the deficiencies in the prior art, the object of the present invention is to provide a method for preparing a hydrogenated starch hydrolysate and a product and application thereof.

[0007] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides a method for preparing a hydrogenated starch hydrolysate, the preparation method comprising the following steps:

[0009] (1) mixing plant starch with water to obtain gelatinized plant starch;

[0010] (2) mixing gelatinized plant starch with a composite enzyme for enzymatic hydrolysis, and deactivating the enzyme after the reaction to obtain a polysaccharide slurry;

[0011] (3) decolorizing the polysaccharide slurry obtained in step (2);

[0012] (4) hydrogenating the decolorized polysaccharide slurry to obtain a crude hydrogenated starch hydrolyzate;

[0013] (5) filtering and concentrating the crude hydrogenated starch hydrolysate obtained in step (4) to obtain hydrogenated starch hydrolysate.

[0014] Wherein, the complex enzyme in step (2) comprises γ-amylase, isoamylase, glycogen phosphorylase and α-amylase.

[0015] In the method, γ-amylase can hydrolyze the α-1,4-glycosidic bonds inside and at the ends of starch molecules, breaking down starch into smaller sugar molecules; isoamylase can break the α-1,6-glycosidic bonds in starch molecules, thereby producing dextrins and maltose of different lengths and branch structures; glycogen phosphorylase can degrade the glucose molecules on the branch chains on the surface of glycogen molecules, providing more basic units for the reaction; α-amylase can randomly act on the α-1,4-glycosidic bonds inside starch molecules, randomly degrading straight-chain starch to produce glucose, maltose and maltotriose.

[0016] The method uses a composite enzyme including γ-amylase, isoamylase, glycogen phosphorylase and α-amylase, and multiple enzymes work synergistically to hydrolyze gelatinized plant starch more comprehensively and efficiently, decompose the starch into products of suitable size and structure, and ultimately improve the stability and moisturizing performance of hydrogenated starch hydrolase, which is not easily affected by external environmental factors and can maintain good activity and efficacy in cosmetics.

[0017] Preferably, the plant starch in step (1) comprises any one of corn starch, cassava starch or sweet potato starch, or a combination of at least two of them.

[0018] Preferably, the plant starch in step (1) includes corn starch, cassava starch and sweet potato starch.

[0019] In the present invention, corn starch, cassava starch and sweet potato starch can synergistically enhance the effect. When the plant starch includes corn starch, cassava starch and sweet potato starch, the moisture retention performance and stability of the prepared hydrogenated starch hydrolase can be improved.

[0020] Preferably, the mass ratio of the corn starch, cassava starch and sweet potato starch is 1:(0.3-0.8):(0.5-1.5).

[0021] When corn starch, cassava starch and sweet potato starch are compounded in a specific ratio, the synergistic relationship among the three can be optimized, and the viscosity, transparency, moisturizing properties and other performance indicators of the hydrogenated starch hydrolysate can be accurately adjusted, thereby improving the moisturizing properties and glossiness of the hydrogenated starch hydrolysate.

[0022] Among them, the specific point values ​​in 0.3-0.8 can be selected from 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, etc., and the specific point values ​​in 0.5-1.5 can be selected from 0.5, 0.7, 0.9, 1.1, 1.3, 1.5, etc.

[0023] Preferably, the mass ratio of the plant starch to water in step (1) is 1:(20-100).

[0024] Among them, the specific point values ​​between 20 and 100 can be selected as 20, 30, 40, 50, 60, 70, 80, 90, 100, etc.

[0025] Preferably, the temperature for mixing the plant starch and water in step (1) is 90 to 120° C., and the time for mixing the plant starch and water is 15 to 50 minutes.

[0026] Among them, the specific point values ​​in 90-120℃ can be selected from 90℃, 95℃, 100℃, 105℃, 110℃, 115℃, 120℃, etc., and the specific point values ​​in 15-50min can be selected from 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, etc.

[0027] Controlling the temperature at 90-120°C can fully gelatinize the plant starch, help form a starch structure that is more suitable for the subsequent action of complex enzymes, and ultimately improve the moisture retention properties of hydrogenated starch hydrolysates.

[0028] Preferably, in the composite enzyme of step (2), the mass ratio of γ-amylase, isoamylase, glycogen phosphorylase and α-amylase is 1:(0.5-1.5):(0.5-1.5):(0.2-1.2).

[0029] Among them, the specific point values ​​in 0.5-1.5 can be selected from 0.5, 0.7, 0.9, 1.1, 1.3, 1.5, etc., and the specific point values ​​in (0.2-1.2) can be selected from 0.2, 0.4, 0.6, 0.8, 1, 1.2, etc.

[0030] When γ-amylase, isoamylase, glycogen phosphorylase and α-amylase are compounded in a specific ratio, the degree of starch hydrolysis can be better controlled, thereby obtaining a hydrogenated starch hydrolysate with a specific molecular weight and structure, thereby improving the moisture retention, penetration and other properties of the hydrogenated starch hydrolysate.

[0031] Preferably, the mass ratio of the gelatinized plant starch to the complex enzyme in step (2) is 100:(1-5).

[0032] Among them, the specific point values ​​1 to 5 can be selected from 1, 2, 3, 4, 5, etc.

[0033] Preferably, the temperature of the enzymatic hydrolysis reaction in step (2) is 45 to 60° C., and the time of the enzymatic hydrolysis reaction is 20 to 50 min.

[0034] Among them, the specific point values ​​in 45-60°C can be selected from 45°C, 48°C, 51°C, 54°C, 57°C, 60°C, etc., and the specific point values ​​in 20-50min can be selected from 20min, 30min, 40min, 50min, etc.

[0035] Preferably, the deactivation treatment in step (2) is performed by high-temperature enzyme inactivation, the enzyme inactivation temperature is 70 to 90° C., and the enzyme inactivation time is 25 to 35 minutes.

[0036] Among them, the specific point values ​​in 70-90°C can be selected from 70°C, 75°C, 80°C, 85°C, 90°C, etc., and the specific point values ​​in 25-35min can be selected from 25min, 28min, 31min, 33min, 35min, etc.

[0037] Preferably, the decolorization treatment in step (3) comprises the following steps:

[0038] The polysaccharide slurry is cooled to 60-75° C., the pH value is adjusted to 3-5, 0.1-0.5% of the mass of the polysaccharide slurry of activated carbon is added, stirred for 3-15 minutes, and filtered.

[0039] Among them, the specific point values ​​in 3-5 can be selected from 3, 3.5, 4, 4.5, 5, etc., the specific point values ​​in 60-75℃ can be selected from 60℃, 65℃, 70℃, 75℃, etc., the specific point values ​​in 0.1-0.5% can be selected from 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, etc., and the specific point values ​​in 3-15min can be selected from 3min, 6min, 9min, 12min, 15min, etc.

[0040] Preferably, the hydrogenation treatment in step (4) comprises the following steps: mixing the decolorized polysaccharide slurry with hydrogen and performing hydrogenation treatment under the action of a catalyst.

[0041] Preferably, the catalyst comprises cadmium hydroxide and nickel hydroxide.

[0042] In the present invention, a catalyst including cadmium hydroxide and nickel hydroxide is selected to catalyze the hydrogenation reaction, so that the degree of the hydrogenation reaction can be better controlled to obtain a hydrogenated starch hydrolyzate with a specific hydrogen content, thereby improving the moisture retention performance of the prepared hydrogenated starch hydrolyzate.

[0043] Preferably, the temperature of the hydrotreatment is 100-130° C., and the pressure of the hydrotreatment is 2-5 MPa.

[0044] Among them, the specific point values ​​in 100-130°C can be selected from 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, etc., and the specific point values ​​in 2-5MPa can be selected from 2MPa, 3MPa, 4MPa, 5MPa, etc.

[0045] Preferably, the filtering in step (5) comprises the following steps:

[0046] (I) filtering the crude hydrogenated starch hydrolysate using an ion exchange resin to obtain a filtrate;

[0047] (II) ultrafiltration of the filtrate obtained in step (I) using a filter membrane.

[0048] Preferably, the filter membrane comprises a polyethersulfone filter membrane.

[0049] Preferably, the ultrafiltration membrane has a molecular weight cutoff of 8000 to 12000 Da.

[0050] Among them, the specific point values ​​in 8000-12000Da can be selected from 8000Da, 9000Da, 10000Da, 11000Da, 12000Da, etc.

[0051] Preferably, the step (5) further comprises sterilizing the crude hydrogenated starch hydrolysate before filtering.

[0052] Preferably, the temperature of the sterilization treatment is 120-140° C., and the pressure of the sterilization treatment is 2-4 MPa.

[0053] Among them, the specific point values ​​in 120-140°C can be selected from 120°C, 125°C, 130°C, 135°C, 140°C, etc., and the specific point values ​​in 2-4MPa can be selected from 2MPa, 2.5MPa, 3MPa, 3.5MPa, 4MPa, etc.

[0054] Sterilization treatment under specific temperature and pressure can effectively destroy the physiological structure of microorganisms, thereby achieving the purpose of sterilization and ensuring the safety and effectiveness of the product.

[0055] Preferably, the method for preparing the hydrogenated starch hydrolysate comprises the following steps:

[0056] (1) corn starch, cassava starch and sweet potato starch are mixed in a mass ratio of 1:(0.3-0.8):(0.5-1.5) to obtain plant starch, and the plant starch and water are mixed in a mass ratio of 1:(20-100) at 90-120° C. for 15-50 minutes to obtain gelatinized plant starch;

[0057] (2) mixing gelatinized plant starch with a composite enzyme in a mass ratio of 100:(1-5), performing enzymatic hydrolysis at 45-60° C. for 20-50 min, heating the mixture to 70-90° C. after the reaction, and deactivating the enzyme for 25-35 min to obtain a polysaccharide slurry; wherein the composite enzyme comprises γ-amylase, isoamylase, glycogen phosphorylase and α-amylase in a mass ratio of 1:(0.5-1.5):(0.5-1.5):(0.2-1.2);

[0058] (3) decolorizing the polysaccharide slurry obtained in step (2);

[0059] (4) mixing the decolorized polysaccharide slurry with hydrogen at a temperature of 100 to 130° C. and a pressure of 2 to 5 MPa, and performing a hydrogenation treatment under the action of a catalyst including cadmium hydroxide and nickel hydroxide to obtain a crude hydrogenated starch hydrolyzate;

[0060] (5) sterilizing the crude hydrogenated starch hydrolysate, filtering the sterilized crude hydrogenated starch hydrolysate using an ion exchange resin to obtain a filtrate, ultrafiltering the obtained filtrate using a polyethersulfone filter membrane, and concentrating it to obtain a hydrogenated starch hydrolysate; the ultrafiltration membrane has a molecular weight cutoff of 8000 to 12000 Da.

[0061] In a second aspect, the present invention provides a hydrogenated starch hydrolysate prepared by the method for preparing the hydrogenated starch hydrolysate according to the first aspect.

[0062] In a third aspect, the present invention provides a use of the hydrogenated starch hydrolysate described in the second aspect in cosmetics.

[0063] Compared with the prior art, the present invention has the following beneficial effects:

[0064] The method uses a composite enzyme including γ-amylase, isoamylase, glycogen phosphorylase and α-amylase to enzymatically hydrolyze gelatinized plant starch. The synergistic effect of multiple enzymes can more comprehensively and efficiently hydrolyze gelatinized plant starch, decompose the starch into products of suitable size and structure, and ultimately improve the stability and moisturizing performance of hydrogenated starch hydrolase, which is not easily affected by external environmental factors and can maintain good activity and efficacy in cosmetics.

[0065] Furthermore, when γ-amylase, isoamylase, glycogen phosphorylase and α-amylase are compounded in a specific mass ratio, the degree of starch hydrolysis can be better controlled, and the moisture retention and penetration capacity of the hydrogenated starch hydrolysate can be improved.

[0066] Furthermore, the corn starch, cassava starch and sweet potato starch in the plant starch work synergistically to improve the moisture retention and stability of the prepared hydrogenated starch hydrolysate; controlling the gelatinization temperature at 90-120°C can fully gelatinize the plant starch, ultimately improving the moisture retention of the hydrogenated starch hydrolyzate.

[0067] Furthermore, by selecting a catalyst including cadmium hydroxide and nickel hydroxide to catalyze the hydrogenation reaction, the extent of the hydrogenation reaction can be better controlled to obtain a hydrogenated starch hydrolyzate with a specific hydrogen content, thereby improving the moisture retention properties of the prepared hydrogenated starch hydrolyzate. DETAILED DESCRIPTION

[0068] In order to further explain the technical means and effects adopted by the present invention, the technical solution of the present invention is further described below in conjunction with the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.

[0069] The sources of the raw materials in the following examples are shown in Table 1:

[0070] Table 1

[0071] raw material factory Brand γ-Amylase Beijing Dream Beauty M10113 Isoamylase Shanghai Tiankuo 234 Glycogen phosphorylase Shanghai Zeye Glycogen phosphorylase α-Amylase Ningxia Summer FFY-4503 β-Amylase Zhengzhou Wanbo 0358 Cadmium hydroxide Shanghai Liming 8543 Nickel Hydroxide Shanghai Gaoming 755 Dimethicone Shandong Youso U31101115 Isohexadecane Shandong Youso O44116118 Hyaluronic acid Sanhe SH-HZP-060 Glyceryl Stearate Mingya MY965

[0072] Example 1

[0073] This embodiment provides a hydrogenated starch hydrolysate, which is prepared by the following method:

[0074] (1) Wash corn, sweet potato and cassava respectively, dry them, peel them and grind them into fine pieces to obtain corn starch, cassava starch and sweet potato starch respectively; mix the obtained corn starch, cassava starch and sweet potato starch in a mass ratio of 1:0.5:1.2 to obtain plant starch. Mix 10 g of plant starch with 500 g of water and heat them at 100° C. for 25 min to obtain gelatinized plant starch.

[0075] (2) 50 g of gelatinized plant starch was mixed with 1.5 g of complex enzyme (the mass ratio of γ-amylase, isoamylase, glycogen phosphorylase and α-amylase was 1:1:1:1), and enzymatic hydrolysis was performed at 50°C for 30 min. After the reaction, the temperature was raised to 80°C, and the enzyme was deactivated for 30 min to obtain a polysaccharide slurry; water and the polysaccharide slurry were mixed in a mass ratio of 1:3 to dilute the polysaccharide slurry.

[0076] (3) The diluted polysaccharide slurry was cooled to 70° C., the pH value was adjusted to 4, 0.25% of the mass of the polysaccharide slurry was added with 2 mm particle size activated carbon, stirred for 5 minutes, and filtered through a plate and frame filter press to achieve a decolorization effect.

[0077] (4) Hydrogen was introduced into the decolorized polysaccharide slurry, the temperature was adjusted to 115° C., the pressure was adjusted to 3 MPa, 3 g of catalyst (1.5 g each of cadmium hydroxide and nickel hydroxide) was added, and hydrogenation treatment was carried out for 2 h to obtain a crude hydrogenated starch hydrolyzate.

[0078] (5) The crude hydrogenated starch hydrolysate is placed in a sterilization container, the temperature environment is set to 120° C., the air pressure value is 3 MPa, and the crude hydrogenated starch hydrolysate is subjected to hot pressure sterilization.

[0079] (6) A styrene divinylbenzene copolymer modified with a sulfonic acid group was used for purification by a cation exchange resin; and an ultrafiltration membrane polyethersulfone filter membrane (molecular weight cutoff of 10,000 Da) was used for filtration, and the filtrate was concentrated to 30% of the volume to obtain a hydrogenated starch hydrolysate, which was tested for indicators (the solid content in the hydrogenated starch hydrolysate was determined to be above 75%, and the pH value of the 10% aqueous solution was between 6.0 and 7.5), which showed that it was qualified.

[0080] Example 2

[0081] This embodiment provides a hydrogenated starch hydrolysate, which is prepared by the following method:

[0082] (1) Wash corn, sweet potato and cassava respectively, dry them, peel them and grind them into fine pieces to obtain corn starch, cassava starch and sweet potato starch respectively; mix the obtained corn starch, cassava starch and sweet potato starch in a mass ratio of 1:0.3:1.5 to obtain plant starch. Mix 10 g of plant starch with 500 g of water and heat them at 90° C. for 40 min to obtain gelatinized plant starch.

[0083] (2) 50 g of gelatinized plant starch was mixed with 1 g of complex enzyme (the mass ratio of γ-amylase, isoamylase, glycogen phosphorylase and α-amylase was 1:0.5:1:0.8), and enzymatic hydrolysis was performed at 45°C for 40 min. After the reaction, the temperature was raised to 90°C, and the enzyme was deactivated for 25 min to obtain a polysaccharide slurry; water and the polysaccharide slurry were mixed in a mass ratio of 1:3 to dilute the polysaccharide slurry.

[0084] (3) The diluted polysaccharide slurry was cooled to 75° C., the pH value was adjusted to 4.5, 0.15% of the mass of the polysaccharide slurry was added with 2 mm particle size activated carbon, stirred for 10 minutes, and then filtered through a plate and frame filter press to achieve a decolorization effect.

[0085] (4) Hydrogen is introduced into the decolorized polysaccharide slurry, the temperature is adjusted to 120° C., the pressure is adjusted to 3.5 MPa, 2 g of catalyst (1 g each of cadmium hydroxide and nickel hydroxide) is added, and hydrogenation treatment is performed for 2 h to obtain a crude hydrogenated starch hydrolyzate.

[0086] (5) The crude hydrogenated starch hydrolysate is placed in a sterilization container, the temperature environment is set to 130° C., the air pressure value is 4 MPa, and the crude hydrogenated starch hydrolysate is subjected to hot pressure sterilization.

[0087] (6) A styrene divinylbenzene copolymer modified with a sulfonic acid group was used for purification by a cation exchange resin; and an ultrafiltration membrane polyethersulfone filter membrane (molecular weight cutoff of 9000Da) was used for filtration, and the filtrate was concentrated to 30% of the volume to obtain a hydrogenated starch hydrolysate, which was tested for indicators (the solid content in the hydrogenated starch hydrolysate was determined to be above 75%, and the pH value of the 10% aqueous solution was between 6.0 and 7.5), which showed that it was qualified.

[0088] Example 3

[0089] This embodiment provides a hydrogenated starch hydrolysate, which is prepared by the following method:

[0090] (1) Wash corn, sweet potato and cassava respectively, dry them, peel them and grind them into fine pieces to obtain corn starch, cassava starch and sweet potato starch respectively; mix the obtained corn starch, cassava starch and sweet potato starch in a mass ratio of 1:0.8:0.5 to obtain plant starch. Mix 10 g of plant starch with 500 g of water and heat them at 120° C. for 20 min to obtain gelatinized plant starch.

[0091] (2) 50 g of gelatinized plant starch was mixed with 2 g of complex enzyme (the mass ratio of γ-amylase, isoamylase, glycogen phosphorylase and α-amylase was 1:1.5:0.6:0.2), and enzymatic hydrolysis was performed at 40°C for 30 min. After the reaction, the temperature was raised to 80°C, and the enzyme was deactivated for 25 min to obtain a polysaccharide slurry; water and the polysaccharide slurry were mixed in a mass ratio of 1:3 to dilute the polysaccharide slurry.

[0092] (3) The diluted polysaccharide slurry was cooled to 60° C., the pH value was adjusted to 3.5, 0.3% of the mass of the polysaccharide slurry was added with activated carbon having a particle size of 2 mm, and after stirring for 12 minutes, the mixture was filtered through a plate and frame filter press to achieve a decolorization effect.

[0093] (4) Hydrogen is introduced into the decolorized polysaccharide slurry, the temperature is adjusted to 125° C., the pressure is adjusted to 2.5 MPa, 2 g of catalyst (1 g each of cadmium hydroxide and nickel hydroxide) is added, and hydrogenation treatment is performed for 2 h to obtain a crude hydrogenated starch hydrolyzate.

[0094] (5) The crude hydrogenated starch hydrolysate is placed in a sterilization container, the temperature environment is set to 110° C., the air pressure value is 2.5 MPa, and the crude hydrogenated starch hydrolysate is subjected to hot pressure sterilization.

[0095] (6) A styrene divinylbenzene copolymer modified with a sulfonic acid group was used for purification by a cation exchange resin; and an ultrafiltration membrane polyethersulfone filter membrane (molecular weight cutoff of 12000Da) was used for filtration, and the filtrate was concentrated to 30% of the volume to obtain a hydrogenated starch hydrolysate, which was tested for indicators (the solid content in the hydrogenated starch hydrolysate was determined to be above 75%, and the pH value of the 10% aqueous solution was between 6.0 and 7.5), which showed that it was qualified.

[0096] Example 4

[0097] The present embodiment provides a hydrogenated starch hydrolyzate, which differs from the embodiment 1 only in that the total mass of the plant starch is kept unchanged, and the corn starch, cassava starch, and sweet potato starch in the preparation method step (1) are mixed in a mass ratio of 1:0.3:1.0 and replaced by corn starch and cassava starch mixed in a mass ratio of 1:0.3.

[0098] Example 5

[0099] The present embodiment provides a hydrogenated starch hydrolyzate, which differs from the embodiment 1 only in that the total mass of the plant starch is kept unchanged, and the corn starch, cassava starch, and sweet potato starch in the preparation method step (1) are mixed in a mass ratio of 1:0.3:1 and replaced by corn starch and sweet potato starch mixed in a mass ratio of 1:1.

[0100] Example 6

[0101] The present embodiment provides a hydrogenated starch hydrolyzate, which differs from the embodiment 1 only in that the total mass of the plant starch is kept unchanged, and the corn starch, cassava starch, and sweet potato starch in the preparation method step (1) are mixed in a mass ratio of 1:0.3:1 and replaced by cassava starch and sweet potato starch mixed in a mass ratio of 0.3:1.

[0102] Example 7

[0103] This embodiment provides a hydrogenated starch hydrolyzate, which differs from Embodiment 1 only in that heating at 80° C. is replaced by heating at 100° C. in step (1) of the preparation method.

[0104] Example 8

[0105] This embodiment provides a hydrogenated starch hydrolyzate, which differs from Embodiment 1 only in that heating at 140° C. is replaced by heating at 100° C. in step (1) of the preparation method.

[0106] Example 9

[0107] This embodiment provides a hydrogenated starch hydrolyzate, which differs from Embodiment 1 only in that the mass ratio of γ-amylase, isoamylase, glycogen phosphorylase and α-amylase in step (1) of the preparation method is replaced from 1:1:1:1 to 1:2:0.3:1.5.

[0108] Example 10

[0109] This embodiment provides a hydrogenated starch hydrolyzate, which differs from Embodiment 1 only in that the mass ratio of γ-amylase, isoamylase, glycogen phosphorylase and α-amylase in step (1) of the preparation method is replaced from 1:1:1:1 to 1:0.3:1.7:0.1.

[0110] Embodiment 11

[0111] This embodiment provides a hydrogenated starch hydrolyzate, which differs from Embodiment 1 only in that 3 g of catalyst (1.5 g each of cadmium hydroxide and nickel hydroxide) in step (4) of the preparation method is replaced by 3 g of cadmium hydroxide catalyst.

[0112] Comparative Example 1

[0113] This comparative example provides a hydrogenated starch hydrolyzate, which differs from Example 1 only in that the 1.5 g of the composite enzyme (the mass ratio of γ-amylase, isoamylase, glycogen phosphorylase and α-amylase is 1:1:1:1) in step (1) of the preparation method is replaced by 1.5 g of the composite enzyme (the mass ratio of γ-amylase, isoamylase and glycogen phosphorylase is 1:1:1).

[0114] Comparative Example 2

[0115] This comparative example provides a hydrogenated starch hydrolyzate, which differs from Example 1 only in that 1.5 g of the composite enzyme (the mass ratio of γ-amylase, isoamylase, glycogen phosphorylase and α-amylase is 1:1:1:1) in step (1) of the preparation method is replaced by 1.5 g of the composite enzyme (the mass ratio of γ-amylase, isoamylase and α-amylase is 1:1:1).

[0116] Comparative Example 3

[0117] This comparative example provides a hydrogenated starch hydrolyzate, which differs from Example 1 only in that the 1.5 g of the composite enzyme (the mass ratio of γ-amylase, isoamylase, glycogen phosphorylase and α-amylase is 1:1:1:1) in step (1) of the preparation method is replaced by 1.5 g of the composite enzyme (the mass ratio of γ-amylase, glycogen phosphorylase and α-amylase is 1:1:1).

[0118] Comparative Example 4

[0119] This comparative example provides a hydrogenated starch hydrolyzate, which differs from Example 1 only in that the 1.5 g of the composite enzyme (the mass ratio of γ-amylase, isoamylase, glycogen phosphorylase and α-amylase is 1:1:1:1) in step (1) of the preparation method is replaced by 1.5 g of the composite enzyme (the mass ratio of isoamylase, glycogen phosphorylase and α-amylase is 1:1:1).

[0120] Comparative Example 5

[0121] This comparative example provides a hydrogenated starch hydrolysate, which differs from Example 1 only in that the γ-amylase in step (1) of the preparation method is replaced by β-amylase of the same mass.

[0122] Application Example 1

[0123] This application example provides a facial cream, which includes, by weight percentage, 5% of the hydrogenated starch hydrolyzate prepared in Example 1, 10% of polydimethylsiloxane, 4% of squalane, 5% of isohexadecane, 3% of glycerol, 5% of butylene glycol, 3% of hyaluronic acid, 5% of glyceryl stearate, and the balance is water.

[0124] Application Example 2-11

[0125] Application Examples 2-11 each provide a facial cream, which differs from Application Example 1 only in that the hydrogenated starch hydrolysate prepared in Example 1 is replaced by the hydrogenated starch hydrolysate prepared in Examples 2-11.

[0126] Comparative Application Examples 1-5

[0127] Comparative Application Examples 1-5 each provide a facial cream, which differs from Application Example 1 only in that the hydrogenated starch hydrolysate prepared in Example 1 is replaced by the hydrogenated starch hydrolysate prepared in Comparative Examples 1-5.

[0128] Test Example 1

[0129] Stratum corneum moisture content test and transepidermal water loss test

[0130] 40 healthy female volunteers aged 25-45 with no history of allergies were selected to test the creams of the application examples and comparison examples. All subjects have signed informed consent. During the test, the inner side of the left and right forearms of the subjects were used as the test site for immediate testing, and the water content of the stratum corneum of the skin was compared before and 30 minutes after using the product. The test product was tested according to 2.0±0.1mg / cm 2 Use a latex finger cot to evenly coat the sample on (2cm 2 ×2cm 2 ) In the test area, MPA580-CM825 and MPA4-CM825 instruments were used for testing.

[0131] The data of the stratum corneum water content growth rate (%) and transepidermal water loss rate (TEWL) after the trial users used the application examples and the comparative application examples are shown in Table 2:

[0132] Table 2

[0133]

[0134]

[0135] It can be seen from the test data in Table 2 that the hydrogenated starch hydrolysate prepared by the method for preparing the hydrogenated starch hydrolysate of the present invention has excellent moisturizing performance, with the increase rate of stratum corneum water content reaching 79.2% in 30 minutes and the transepidermal water loss rate as low as 10.5%.

[0136] By comparing Example 1 with Comparative Examples 1 to 5, it can be seen that when any one of γ-amylase, isoamylase, glycogen phosphorylase or α-amylase is missing from the composite enzyme or is replaced by other amylases, the moisturizing ability is significantly reduced, indicating that γ-amylase, isoamylase, glycogen phosphorylase and α-amylase have a good synergistic effect on the moisturizing properties of the prepared hydrogenated starch hydrolysate.

[0137] By comparing Example 1 with Examples 4 to 6, it can be seen that when the plant starch lacks any one of corn starch, cassava starch or sweet potato starch, the moisturizing performance of the prepared hydrogenated starch hydrolyzate is reduced to a certain extent; by comparing Example 1 with Examples 7 to 8, it can be seen that when the starch gelatinization temperature is outside the range of 90 to 120°C, the moisturizing and water-locking ability of the prepared hydrogenated starch hydrolyzate can also be reduced; by comparing Example 1 with Examples 9 to 10, it can be seen that when the mass ratio of γ-amylase, isoamylase, glycogen phosphorylase and α-amylase is outside the range of 1:(0.5 to 1.5):(0.5 to 1.5):(0.2 to 1.2), the moisturizing and water-locking ability of the prepared hydrogenated starch hydrolyzate will be reduced to a certain extent; by comparing Example 1 with Example 11, it can be seen that the catalyst comprising cadmium hydroxide and nickel hydroxide can better improve the hydrating performance of the prepared hydrogenated starch hydrolyzate.

[0138] Test Example 2

[0139] Safety evaluation test

[0140] The same batch of 40 subjects as in Test Example 1 were selected and the following Anxingxing evaluation test was performed on the subjects: After cleaning the back of the subjects, the spot tester with the sample was applied to the selected position on the back with a non-irritating tape. After the patch was applied, it was gently pressed with fingers to make it evenly attached to the skin for 48 hours. The subjects kept the patch area dry within 48 hours, and avoided intense exercise, scratching the patch area, and long-term sunlight exposure. After 48 hours, the tester was removed and marked. After 30 minutes, the indentation disappeared and the evaluation was performed under sufficient light.

[0141] The grading standards for skin adverse reactions are shown in Table 3:

[0142] Table 3

[0143]

[0144]

[0145] The results are shown in Table 4:

[0146] Table 4

[0147]

[0148] It can be seen from the data in Table 4 that all the subjects had negative reactions, which indicates that the facial cream of hydrogenated starch hydrolysate prepared by the present invention has no irritation to the skin and no positive reaction, indicating that the product of the present invention is safer and milder.

[0149] Test Example 3

[0150] Stability test

[0151] The hydrogenated starch hydrolysates of the embodiments and comparative examples were subjected to stability tests. The test method was as follows: 10 g of each hydrogenated starch hydrolysate sample was placed in a test tube, sealed, and placed at 50° C. for 30 days to observe changes in appearance; another sample was irradiated with a cool fluorescent lamp at 25° C. for 24 hours with a light intensity of 2000 Lux to observe changes in appearance. The results are shown in Table 5.

[0152] Table 5

[0153] sample Thermal stability Photostability Application Example 1 No color change No color change Application Example 2 No color change No color change Application Example 3 No color change No color change Application Example 4 No color change No color change Application Example 5 No color change No color change Application Example 6 The product turns slightly yellow No color change Application Example 7 No color change No color change Application Example 8 The product turns slightly yellow The product turns slightly yellow Application Example 9 No color change No color change Application Example 10 No color change The product turns slightly yellow Application Example 11 The product turns slightly yellow The product turns slightly yellow Comparative application example 1 No color change No color change Comparative Application Example 2 No color change The product turns slightly yellow Comparative Application Example 3 The product turns slightly yellow The product turns yellow Comparative Application Example 4 The product turns slightly yellow The product turns slightly yellow Comparative Application Example 5 The product turns slightly yellow The product turns yellow

[0154] It can be seen from Table 5 that the present invention significantly improves the stability of the product by improving the preparation method of hydrogenated starch hydrolysate.

[0155] The applicant declares that the present invention illustrates the technical solution of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

[0156] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0157] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

Claims

1. A method for preparing a hydrogenated starch hydrolysate, characterized in that: The preparation method comprises the following steps: (1) mixing plant starch with water to obtain gelatinized plant starch; (2) mixing gelatinized plant starch with a composite enzyme for enzymatic hydrolysis, and deactivating the enzyme after the reaction to obtain a polysaccharide slurry; (3) decolorizing the polysaccharide slurry obtained in step (2); (4) hydrogenating the decolorized polysaccharide slurry to obtain a crude hydrogenated starch hydrolyzate; (5) filtering and concentrating the crude hydrogenated starch hydrolysate obtained in step (4) to obtain a hydrogenated starch hydrolysate; Wherein, the complex enzyme in step (2) comprises γ-amylase, isoamylase, glycogen phosphorylase and α-amylase.

2. The method for preparing hydrogenated starch hydrolysate according to claim 1, characterized in that: The plant starch in step (1) includes any one of corn starch, cassava starch or sweet potato starch, or a combination of at least two thereof; Preferably, the plant starch in step (1) includes corn starch, cassava starch and sweet potato starch; Preferably, the mass ratio of the corn starch, cassava starch and sweet potato starch is 1:(0.3-0.8):(0.5-1.5).

3. The method for preparing a hydrogenated starch hydrolysate according to claim 1 or 2, characterized in that: The mass ratio of the plant starch to water in step (1) is 1:(20-100); Preferably, the temperature for mixing the plant starch and water in step (1) is 90 to 120° C., and the time for mixing the plant starch and water is 15 to 50 minutes.

4. The method for preparing hydrogenated starch hydrolysate according to any one of claims 1 to 3, characterized in that: In the composite enzyme of step (2), the mass ratio of γ-amylase, isoamylase, glycogen phosphorylase and α-amylase is 1:(0.5-1.5):(0.5-1.5):(0.2-1.2); Preferably, the mass ratio of the gelatinized plant starch to the complex enzyme in step (2) is 100:(1-5); Preferably, the temperature of the enzymatic hydrolysis reaction in step (2) is 45 to 60° C., and the time of the enzymatic hydrolysis reaction is 20 to 50 min; Preferably, the deactivation treatment in step (2) is performed by high-temperature enzyme inactivation, the enzyme inactivation temperature is 70 to 90° C., and the enzyme inactivation time is 25 to 35 minutes.

5. The method for preparing hydrogenated starch hydrolysate according to any one of claims 1 to 4, characterized in that: The decolorization process in step (3) comprises the following steps: The polysaccharide slurry is cooled to 60-75° C., the pH value is adjusted to 3-5, 0.1-0.5% of the mass of the polysaccharide slurry of activated carbon is added, stirred for 3-15 minutes, and filtered.

6. The method for preparing hydrogenated starch hydrolysate according to any one of claims 1 to 5, characterized in that: The hydrogenation treatment in step (4) comprises the following steps: mixing the decolorized polysaccharide slurry with hydrogen and performing hydrogenation treatment under the action of a catalyst; Preferably, the catalyst comprises cadmium hydroxide and nickel hydroxide; Preferably, the temperature of the hydrotreatment is 100-130° C., and the pressure of the hydrotreatment is 2-5 MPa.

7. The method for preparing hydrogenated starch hydrolysate according to any one of claims 1 to 6, characterized in that: The filtering in step (5) comprises the following steps: (I) filtering the crude hydrogenated starch hydrolysate using an ion exchange resin to obtain a filtrate; (II) ultrafiltration of the filtrate obtained in step (I) using a filter membrane; Preferably, the filter membrane comprises a polyethersulfone filter membrane; Preferably, the ultrafiltration membrane has a molecular weight cutoff of 8000 to 12000 Da; Preferably, the step (5) further comprises sterilizing the crude hydrogenated starch hydrolysate before filtering; Preferably, the temperature of the sterilization treatment is 120-140° C., and the pressure of the sterilization treatment is 2-4 MPa.

8. The method for preparing hydrogenated starch hydrolysate according to any one of claims 1 to 7, characterized in that: The preparation method of the hydrogenated starch hydrolysate comprises the following steps: (1) corn starch, cassava starch and sweet potato starch are mixed in a mass ratio of 1:(0.3-0.8):(0.5-1.5) to obtain plant starch, and the plant starch and water are mixed in a mass ratio of 1:(20-100) at 90-120° C. for 15-50 minutes to obtain gelatinized plant starch; (2) mixing gelatinized plant starch with a composite enzyme in a mass ratio of 100:(1-5), performing enzymatic hydrolysis at 45-60° C. for 20-50 min, heating the mixture to 70-90° C. after the reaction, and deactivating the enzyme for 25-35 min to obtain a polysaccharide slurry; wherein the composite enzyme comprises γ-amylase, isoamylase, glycogen phosphorylase and α-amylase in a mass ratio of 1:(0.5-1.5):(0.5-1.5):(0.2-1.2); (3) decolorizing the polysaccharide slurry obtained in step (2); (4) mixing the decolorized polysaccharide slurry with hydrogen at a temperature of 100 to 130° C. and a pressure of 2 to 5 MPa, and performing a hydrogenation treatment under the action of a catalyst including cadmium hydroxide and nickel hydroxide to obtain a crude hydrogenated starch hydrolyzate; (5) sterilizing the crude hydrogenated starch hydrolysate, filtering the sterilized crude hydrogenated starch hydrolysate using an ion exchange resin to obtain a filtrate, ultrafiltering the obtained filtrate using a polyethersulfone filter membrane, and concentrating it to obtain a hydrogenated starch hydrolysate; the ultrafiltration membrane has a molecular weight cutoff of 8000 to 12000 Da.

9. A hydrogenated starch hydrolysate prepared by the method for preparing a hydrogenated starch hydrolysate according to any one of claims 1 to 8.

10. Use of the hydrogenated starch hydrolysate according to claim 9 in cosmetics.

Images