Pre-gelatinized hydrophilically modified pulse starches with increased hydrophobicity and their use as water resistant film formers

Abstract

This application provides a pregelatinized hydroxypropylated pea starch that exhibits improved water-resistant film-forming properties compared to previously known film-forming pea starches. The starch can be characterized by its Relative Aspect Ratio (RVA) viscosity characteristics. This can be achieved through the pregelatinization of the hydroxypropylated pea starch, particularly in a drum dryer. The improved water resistance is illustrated in films immersed in water and is further characterized by the determination of the starch's hydrophobicity values ​​using tensile testing, angular measurement, and the Young-Laplace and Fowkes model.

Description

Technical Field

[0001] This invention relates to the field of film-forming modified starch for forming water-resistant films. Background Technology

[0002] In many applications across various fields, there is a search for film-forming components that can withstand water solubility for a sufficiently long period to suit the intended use, while also being removable by water or ultimately dissolved by acidic or alkaline aqueous media.

[0003] In the cosmetics industry, waterproof cosmetics require, on the one hand, that the film formed by the film-forming composition is water-resistant, for example, when immersed in water for an extended period of time, and on the other hand, that the film can be removed from the skin by wiping with a damp cloth without the use of corrosive organic solvents.

[0004] Film-forming modified legume starch and its use in cosmetics or pharmaceuticals are known from the prior art.

[0005] In the cosmetics field, specifically from WO2020 / 128253, hydroxypropylated and hydrolyzed pea starch is known for its excellent film-forming properties and good solubility in water. Films formed with these pea starches are easily removed from the skin by gentle washing with still water. Therefore, it is clear that such films cannot be water-resistant.

[0006] The barrier and fixation properties of hydrolyzed and hydroxypropylated pea starch are also known from WO2020 / 201071. The fixation properties on hair are known from WO2022 / 199889.

[0007] Hydrophobic film-forming modified starches, known from the prior art, are present in various technical fields. In the paper and paperboard industry, film-forming hydrophobic grafted starches are used to replace styrene-butadiene latex in the coating of paper and paperboard.

[0008] Technical issues

[0009] In the field of water-resistant film-forming agents, the well-known and established polymers are synthetic polymers, such as styrene-butadiene copolymers, polyvinylpyrrolidone polymers, and copolymers of vinylpyrrolidone with acrylates or methacrylates. Despite their excellent properties, these synthetic polymers have a major drawback that fails to meet two key requirements of today's consumer products: they are not natural or of natural origin (i.e., "naturalness"), and they are not biodegradable.

[0010] To address these two market demands, naturally sourced and biodegradable film-forming agents are available and are still being improved. Examples of such natural polymers include gums such as pullulan, gum arabic, alginate, and carrageenan; cellulose materials; and starches. In starches, it is not easy to simultaneously satisfy both film-forming and water-resistant properties.

[0011] Starch has long been known for its film-forming properties.

[0012] The most well-known use of this property of starch is to stiffen clothing, a practice dating back to ancient times. This relies on the ability of a starch suspension to form a film on the surface of fibers by drying. Starch films are quite soluble in water and have low water resistance.

[0013] Another well-known and recent application of this film-forming property is in paper coating, where hydrolyzed starch forms a smooth, continuous film on the paper surface, and its printability is determined by its affinity for ink. All commonly used natural starches can be used, but the preferred plant source is waxy starch, which is starch with an amylopectin content greater than 99% by weight. This is due to the ease of processing amylopectin, particularly its ease of cooking and post-cooking stability, as well as its excellent film-forming properties. Those waxy starch films have a very high affinity for water, which is desirable for making paper printable, but this is also a major drawback when water resistance is required.

[0014] To improve the water resistance of films formed from waxy starch, synthetic polymers must be added. For example, synthetic polymers such as styrene-butadiene latex are often added to starch-based coating solutions for paper, which introduces problems such as a lack of biodegradability and naturalness.

[0015] Other methods for obtaining starch-based water-resistant films include functionalizing common starches (wheat, corn) with hydrophobic groups, such as by fatty acid esterification, or by the use of fatty acid anhydrides, such as by transesterification with commonly and widely used alkenyl succinic anhydrides, or by etherification with fatty alcohols. The common sodium and calcium salts of these starches are highly soluble in water and do not produce sufficiently water-resistant films. Highly functionalized substitutes with a degree of substitution greater than 1 or 2 lose their naturalness and biodegradability. The aluminum salts of such alkenyl succinic starches, existing only in particulate form, are sufficiently hydrophobic and thus water-repellent. To some extent, forming films with those particulate, hydrophobically functionalized starches is very difficult due to their very poor film-forming inherent properties, making them unsuitable for forming films on surfaces, such as skin.

[0016] Another method for obtaining a water-resistant film is to use starch rich in amylose. Natural high-amylose starches are very difficult to use because they require cooking at temperatures above 80°C and rapidly gel when cooled to room temperature, which readily leads to phase separation called dehydration shrinkage. This instability makes formulated products unstable over time during storage. These natural high-amylose starches are unusable. They must be modified to be sufficiently stable.

[0017] As an example, Roquette has developed a film-forming starch with a high natural source index (INO). The pregelatinized, hydrolyzed, hydroxypropylated pea starch marketed by Roquette under the brand name "Beauté by Roquette ST 720" has an INO of 0.93. Due to hydroxypropylation, this starch is stable and very easy to use and incorporate into formulated products. This film-forming agent is highly effective in forming a non-occlusive film on skin or hair that protects the skin or hair from external aggressors (Patent Citation 1), and also has a makeup-setting effect for cosmetics (Patent Citation 1) and a styling effect for hair (Patent Citation 2). This type of starch is also readily soluble in water, which may be advantageous for easy removal by washing, but may also be disadvantageous, for example, when bleached from its carrier when exposed to moisture or immersed in water. This starch does not allow the formation of water-resistant or waterproof films.

[0018] The applicant continues his research to obtain a new starch that possesses all of the following desired properties:

[0019] - It has a high natural source index (INO) according to ISO 16128-2:2017.

[0020] - Easy to use, especially easy to disperse or incorporate into water or oil.

[0021] - It is a film-forming agent that forms a water-resistant film when used alone, or a waterproof film when used in combination with other hydrophobic materials.

[0022] - It is stable when used in formulated products, which specifically means that it does not produce any phase separation or dehydration shrinkage, and it also means chemical and physical compatibility with other conventional ingredients used in formulated products.

[0023] - Forms a washable film that is easily removed by rubbing with water or wiping with a fabric or cellulose material.

[0024] - It is biodegradable according to the OECD method selected from 301B, 301D or 301F.

[0025] In a surprising and unexpected way, the present invention satisfies all these prior properties. The inventors have discovered that a known but still difficult-to-master physical method, namely pregelatinization, particularly on a drum dryer, can be used to obtain starch with those properties. This results in increased resistance of the film formed by the aqueous formulation containing said starch to dissolution in water. This is due to the specific selection of operating conditions previously unknown for such physical methods. This starch allows for a good balance between its ability to dissolve in water and its resistance to dissolving in water. Attached Figure Description

[0026] Other features, details, and advantages will be shown in the following detailed description and accompanying drawings, wherein:

[0027] Figure 1

[0028] [ Figure 1 The modified legume starch according to the present invention and commercially available modified legume starch (Beauté by Roquette) are shown. ® Water resistance according to the "glass plate test" compared to ST 720 and to the hydrophobic film-forming synthetic polymer polyvinylpyrrolidone.

[0029] Figure 2

[0030] [ Figure 2 The modified legume starch according to the present invention and commercially available modified legume starch (Beauté by Roquette) are shown. ® Water resistance according to the "bandage test" compared to ST 720 and to the hydrophobic film-forming synthetic polymer polyvinylpyrrolidone.

[0031] Figure 3

[0032] [ Figure 3 The water resistance of the modified legume starch according to the present invention compared with that of the hydrophobic film-forming synthetic polymer polyvinylpyrrolidone, according to the "mascara test", is shown. Detailed Implementation

[0033] Implementation Scheme 1: Pregelatinized hydrophilically modified legume starch, wherein the pregelatinized hydrophilically modified legume starch has an RVA viscosity characteristic characterized by a final cold viscosity of 100 cPo to 2000 cPo, or 125 cPo to 1750 cPo, or 150 cPo to 1500 cPo, or 200 cPo to 1200 cPo, or 600 cPo to 1000 cPo, or 650 cPo to 950 cPo.

[0034] The RVA temperature and stirring procedure are as follows:

[0035] - At time = 0 seconds: temperature = 25℃; stirring speed = 100 rpm.

[0036] - At time = 10 seconds: temperature = 25℃; stirring speed = 500 rpm

[0037] - At time = 30 seconds: temperature = 25℃; stirring speed = 160 rpm.

[0038] - At time = 10 minutes: temperature = 25℃; stirring speed = 160 rpm.

[0039] - At time = 18 minutes: temperature = 90℃; stirring speed = 160 rpm.

[0040] - At time = 21 minutes: temperature = 90℃; stirring speed = 160 rpm.

[0041] - At time = 29 minutes: temperature = 30℃; stirring speed = 160 rpm.

[0042] - At time = 34 minutes: temperature = 30℃; stirring speed = 160 rpm.

[0043] Implementation Scheme 2: The starch according to Implementation Scheme 1, wherein its RVA viscosity characteristics are characterized by an initial cold viscosity of 250 cPo to 4000 cPo, or 400 cPo to 3500 cPo, or 500 cPo to 3000 cPo.

[0044] Implementation Scheme 3: The starch according to Implementation Scheme 1 or 2, wherein its RVA viscosity characteristics are characterized by thermal viscosity of 50 cPo to 900 cPo, or 75 cPo to 800 cPo, or 100 cPo to 700 cPo.

[0045] Implementation Scheme 4: The starch according to any one of Implementation Schemes 1 to 3, wherein the RVA viscosity characteristics are characterized by the following:

[0046] - The viscosity initially increases at a rate of at least 1500 cPo / min.

[0047] - The viscosity decreases at a rate of at least 100 cPo / min during the heating step.

[0048] - The viscosity increases at a rate of at least 25 cPo / min during the cooling step.

[0049] Implementation Scheme 5: The starch according to any one of Implementation Schemes 1 to 4, wherein the legume starch has a content of greater than or equal to 20% by weight, or 24% by weight, or 30% by weight, or 34% by weight, preferably 30% by weight to 40% by weight of amylose.

[0050] Implementation Scheme 6: The starch according to Implementation Scheme 5, wherein the legume starch is selected from pea starch, kidney bean starch, broad bean starch, fava bean starch, lentil starch, alfalfa starch, clover starch, lupin starch or soybean starch, preferably pea starch.

[0051] Implementation Scheme 7: The starch according to any one of Implementation Schemes 1 to 6, wherein the starch is hydroxyalkylated and / or carboxyalkylated, preferably hydroxyalkylated.

[0052] Implementation Scheme 8: The starch according to Implementation Scheme 7, wherein the starch is hydroxypropylated.

[0053] Implementation Scheme 9: The starch according to any one of Implementation Schemes 1 to 8, wherein the degree of substitution is 0.01 to 3, or 0.05 to 0.8, or 0.05 to 0.6, or 0.05 to 0.21, preferably 0.15 to 0.19.

[0054] Implementation Scheme 10: The starch according to any one of Implementation Schemes 1 to 9, wherein the starch is not hydrolyzed, preferably not hydrolyzed by chemical or enzymatic means.

[0055] Implementation Scheme 11: The starch according to any one of Implementation Schemes 1 to 10, wherein the starch has a solubility in water at 22°C of 25% to 80%, or 30% to 75%, or 35% to 60%, or 45% to 55%.

[0056] Implementation Scheme 12: The starch according to any one of Implementation Schemes 1 to 11, wherein the starch has a particle size distribution having a volume-averaged average diameter D(4,3) of 25 micrometers to 200 micrometers, or 40 micrometers to 150 micrometers, or 50 micrometers to 100 micrometers.

[0057] Implementation Scheme 13: The starch according to any one of Implementation Schemes 1 to 12, wherein the starch has a hydrophobicity value equal to or greater than 30%, or 35%, preferably 30% to 55%, or 35% to 50%, as measured according to the Young-Laplace and Fowkes model.

[0058] Implementation Scheme 14: A method for manufacturing pregelatinized hydrophilically modified legume starch as described in any one of Implementation Schemes 1 to 13, said method comprising the following steps, preferably consisting of the following steps:

[0059] a) Provides natural legume starch.

[0060] b) The natural legume starch described in step a) is hydrophilically modified, preferentially by hydroxypropylation.

[0061] c) Pregelatinize the hydrophilic modified legume starch described in step b.

[0062] d) Grinding the pregelatinized hydrophilic modified legume starch from step c).

[0063] Implementation Scheme 15: The method according to Implementation Scheme 14, wherein the pregelatinization step is carried out using a drum dryer or an extruder, or a combination of a jet cooker and a spray dryer, with preference given to using a drum dryer.

[0064] Implementation Scheme 16: The method according to any one of Implementation Schemes 14 or 15, wherein there is no step of hydrolyzing the starch by chemical or enzymatic means.

[0065] Implementation Scheme 17: Use of pregelatinized hydrophilic modified legume starch as described in any one of Implementation Schemes 1 to 13 in formulations selected from cosmetic products, pharmaceutical products, dermatological products, veterinary products, industrial products, plant care products, or food products.

[0066] Implementation Scheme 18: The use according to Implementation Scheme 17, wherein the starch is a water-resistant film-forming agent.

[0067] Implementation Scheme 19: The use according to any one of Implementation Schemes 17 or 18, for increasing the water resistance of the film formed by the formulated product on a surface, preferably on human skin or human hair.

[0068] Implementation Scheme 20: According to any one of Implementation Schemes 17 to 19, the beauty product is selected from skin care products, hair care products, cosmetic products, oral care products, or hygiene products.

[0069] Implementation Scheme 21: According to the use described in Implementation Scheme 20, the skin care product is selected from sun protection products.

[0070] Implementation Scheme 22: According to the use described in Implementation Scheme 20, the hygiene product is soap or deodorant.

[0071] Implementation Scheme 23: According to the use described in Implementation Scheme 20, the cosmetic product is selected from mascara, eyeshadow, eyeliner, foundation, tattoo makeup, and nail polish.

[0072] Implementation Scheme 24: A film-forming composition comprising pregelatinized hydrophilically modified legume starch as described in any one of Implementation Schemes 1 to 13 in a physiologically acceptable medium.

[0073] Implementation Scheme 25: The film-forming composition according to Implementation Scheme 24, wherein the content of the pregelatinized hydrophilic modified legume starch is 0.5% to 10% by weight, or 3% to 7% by weight, or 4% to 6% by weight of the total weight of the film-forming composition.

[0074] Implementation Scheme 26: The film-forming composition according to any one of Implementation Schemes 24 or 25, wherein the film-forming composition comprises at least one other starch selected from natural granular starch, natural cooked starch, and modified starch.

[0075] Implementation Scheme 27: The film-forming composition according to Implementation Scheme 26, wherein the modified starch is selected from hydroxyalkylated starch and hydrolyzed starch.

[0076] Implementation Scheme 28: The film-forming composition according to any one of Implementation Schemes 24 to 27, wherein the film-forming composition comprises a plasticizer, the plasticizer being preferably selected from polyols, urea, organic acids and their salts, betaine or combinations thereof, and preferably selected from glycols, glycerol, sorbitol, xylitol, mannitol, and isosorbide.

[0077] Implementation Scheme 29: The film-forming composition according to any one of Implementation Schemes 24 to 28, wherein the film-forming composition comprises an alcohol, preferably ethanol.

[0078] Implementation Scheme 30: The film-forming composition according to any one of Implementation Schemes 24 to 29, wherein the film-forming composition comprises:

[0079] - A film-forming polymer, wherein the film-forming polymer is selected from synthetic polymers, semi-synthetic polymers, and natural polymers.

[0080] - and / or thickeners or gelling agents.

[0081] Implementation Scheme 31: A film formed on the surface of human or animal skin, mucous membrane or hair, said film comprising or composed of pregelatinized hydrophilically modified legume starch as described in any one of Implementation Schemes 1 to 13, or obtained by applying a film-forming composition as described in any one of Implementation Schemes 24 to 30.

[0082] Implementation Scheme 32: The membrane according to Implementation Scheme 31 has water resistance according to Test A for 1 minute or more, or 2 minutes or more, or 3 minutes or more, or 4 minutes or more, or 5 minutes or more.

[0083] Implementation Scheme 33: The membrane according to any one of Implementation Schemes 31 or 32 has a contact angle with the water droplet equal to or greater than 70° after 1 minute of contact between the water droplet and the membrane, and / or equal to or greater than 60° after 5 minutes of contact between the water droplet and the membrane, as measured by goniometric method.

[0084] Implementation Scheme 34: A cosmetic product comprising pregelatinized hydrophilically modified legume starch as described in any one of Implementation Schemes 1 to 13, forming a film as described in any one of Implementation Schemes 31 to 33.

[0085] Implementation Scheme 35: A sunscreen product comprising pregelatinized hydrophilically modified legume starch as described in any one of Implementation Schemes 1 to 13, forming a film as described in any one of Implementation Schemes 31 to 33.

[0086] The accompanying drawings and the following detailed description essentially contain some specific elements. They can be used to enhance the understanding of the invention and, if necessary, to define the invention.

[0087] The starch according to the present invention, referred to herein as "starch," is a pregelatinized hydrophilically modified legume starch, which can be characterized by a specific viscosity value using a viscosity measurement called "RVA." Each of these characteristics of starch is described below.

[0088] Legume starch :

[0089] The term "legume starch" refers to any composition extracted from legumes, particularly those belonging to the Papilionaceae family, and containing a starch content greater than 40%, preferably greater than 50%, and even more preferably greater than 75%, wherein these percentages are expressed on a dry weight basis relative to the dry weight of the composition. Advantageously, the starch content is greater than 90% (dry / dry). It can be particularly greater than 95%, including greater than 98%.

[0090] As used in this application, “legumes” refers to any plant belonging to the families Cesalpiniaceae, Mimosaceae, or Fabaceae, and particularly any plant belonging to the family Fabaceae, such as, for example, peas, common beans, broad beans, fava beans, lentils, alfalfa, clover, lupins, or soybeans. This definition specifically includes all plants described in any of the tables contained in the article by R. HOOVER et al. entitled “Composition, structure, functionality and chemical modification of legume starches: a review” (Can. J. Physiol. Pharmacol. 1991, 69, pp. 79-92).

[0091] Preferably, the legumes are selected from the group consisting of peas, kidney beans, broad beans, and fava beans. Advantageously, it is peas, wherein the term "pea" is considered in its broadest sense herein and specifically includes:

[0092] - All wild varieties of "smooth-skinned peas", and

[0093] - All mutant varieties of "smooth-skinned peas" and "wrinkled-skinned peas" are unrelated to the intended use of the varieties (human food, animal feed and / or other uses).

[0094] The mutant varieties mentioned above, especially those referred to as "mutant r", "mutant rb", "mutant rug 3", "mutant rug 4", "mutant rug 5" and "mutant lam", are described, as in the article by CL Heydley et al. entitled "Developing novel pea starches", Proceedings of the Symposium of the Industrial Biochemistry and Biotechnology Group of the Biochemical Society, 1996, pp. 77-87.

[0095] hydrophilic modification :

[0096] The starch according to the present invention is a hydrophilically modified legume starch. This means that the legume starch is modified by at least one chemical treatment that replaces some of the hydroxyl groups of the starch with other hydrophilic groups.

[0097] Chemical treatments include functionalizing starch, specifically by etherifying or esterifying the hydroxyl groups of dehydrated glucose units, replacing the hydroxyl groups with other chemical groups not naturally present in starch. Such functionalization alters the physicochemical properties of starch.

[0098] The chemical modifications used in this invention, also known as "chemical functionalization," are hydrophilic modifications, thus producing hydrophilic modified starch. Specifically, these can be selected from hydroxyalkylation, carboxymethylation, or combinations thereof.

[0099] According to one embodiment of the invention, the hydrophilic functionalization is hydroxyalkylation, such as hydroxypropylation, which is also often referred to as "stabilization" due to its beneficial effect on the retrogradation of gels formed from starch. Therefore, according to one embodiment, the starch is hydroxypropylated.

[0100] As used in this invention, "hydroxypropylated" refers to starch substituted with hydroxypropyl groups by any technique known to those skilled in the art, such as by etherification with propylene oxide, particularly having a hydroxypropyl group content characterized by a degree of substitution of 0.01 to 3, or 0.05 to 0.8, or 0.05 to 0.6, or 0.05 to 0.21, preferably 0.15 to 0.19. This content can be determined, in particular, by proton nuclear magnetic resonance spectroscopy, especially according to standard EN ISO 11543:2002 F.

[0101] Unhydrophobic modified :

[0102] The starch according to the present invention is unhydrophobically modified. This means that the starch has not been chemically modified or functionalized by any hydrophobic or amphiphilic groups (such as alkenyl succinate groups).

[0103] Very slightly hydrolyzed or unhydrolyzed :

[0104] The starch according to the present invention has a molecular weight equal to or slightly lower than that of natural starch.

[0105] Pregelatinized :

[0106] Pregelatinized starch is a dry powder of partially or fully gelatinized starch. It is usually obtained by subjecting the starch to gelatinization and drying simultaneously or subsequently.

[0107] Gelatinization is a physical process that involves altering the physical structure of starch granules by subjecting them to thermal and / or mechanical processes. Gelatinization transforms starch granules into a starch paste, also known as starch gum due to its adhesive properties. Through the action of temperature in a suspension in water (which triggers the swelling of the starch granules by absorbing water), the granules almost completely break down, releasing their contents into the aqueous phase and thus forming a colloidal suspension. The starch suspension obtained through gelatinization is called gelatinized starch, and it can be further converted into powder by drying. This produces a powder that is easily dispersed in water without any cooking, and sometimes even easily dispersed in cold water without any heating, such as without heating. The powder of gelatinized starch is called pregelatinized starch. The method for preparing pregelatinized starch is called pregelatinization.

[0108] Pregelatinization

[0109] Pregelatinization can be carried out in a single process step involving both gelatinization and drying, or through a series of sequential process steps, typically a first gelatinization step followed by a second drying step. It can be performed on any technical equipment capable of heating an aqueous suspension of starch at temperatures above the starch's gelatinization temperature (typically above 70°C), processing the resulting high-viscosity gelatinized starch, and drying the resulting gelatinized starch.

[0110] Gelatinization can be carried out in a stirred tank or in a spray cooker. Pregelatinization can be carried out in a drum dryer or in an extruder. Another pregelatinization method is spray drying, for example, gelatinized starch obtained by spray cooking.

[0111] According to one implementation scheme, the starch is pregelatinized on a drum dryer.

[0112] A typical device used to gelatinize starch and simultaneously dry the resulting gelatinized starch is called a drum dryer, also known as a drum cooker, as described in Chapter XXII, pp. 523-536 of Eugene L. Powell's *Starch: Chemistry and Technology, Volume II Industrial Aspects*, written by Whistler and Paschall, 1967. A drum dryer can comprise one heated rotating drum (single-drum dryer) or two heated drums rotating toward each other (double-drum dryer) or away from each other (twin-drum dryer). The drum dryer converts an aqueous suspension of starch into a dry powder of gelatinized starch (referred to as pregelatinized starch).

[0113] According to one embodiment of the method for obtaining modified legume starch according to the present invention, pregelatinization is carried out as follows:

[0114] - It is carried out on a suspension of natural granular starch in water, the concentration of which is 5% to 50% by weight, or 10% to 40% by weight, or 20% to 35% by weight relative to the total weight of the aqueous starch suspension. Due to the milky texture of the suspension, it is also called "starch milk".

[0115] - The process is carried out at a temperature above 70°C, or 80°C, or 90°C, where the temperature is set for the heated surface or for the starch suspension.

[0116] - Continue for a duration of at least 1 second.

[0117] Grinding :

[0118] Pregelatinized starch can be ground into powder through a grinding step, which shapes the pregelatinized starch into granules and controls the particle size of these granules.

[0119] During pregelatinization on a drum dryer, the pregelatinized starch film recovered at the scraper is fed into a mill to convert the film into granules. The milled pregelatinized starch can be packaged and used appropriately, for example, added to formulated products.

[0120] According to one embodiment, the starch according to the invention is ground in a hammer crusher (also known as a hammer mill) or in an impact and friction mill or a combination thereof.

[0121] RVA viscosity characteristics :

[0122] Unbound by theory, the applicant believes that the specific modified legume starch according to the invention undergoes a recombination of its constituent macromolecules during its retrogradation, which allows for the formation of a membrane exhibiting unprecedented hydrophobicity compared to membranes formed from non-hydrophobic modified legume starch.

[0123] The selected analytical method for characterizing starch retrogradation is to measure viscosity characteristics using a rapid viscosity analyzer. This measurement involves measuring the viscosity of an aqueous suspension of starch during a controlled heating and cooling process, with a mixer acting as the viscometer.

[0124] According to one embodiment, the modified legume starch according to the present invention is characterized by the following:

[0125] - During the first stage of stable heating at 25°C: the viscosity initially increases at a rate of at least 1500 cPo / min; and a viscosity plateau of at least 2000 cPo.

[0126] - During the second phase of constant increase in temperature, from 25°C to 90°C over 8 minutes: the viscosity is reduced to a value in the range of 250 cPo to 750 cPo at a rate of at least 100 cPo / min, referred to as "thermal viscosity".

[0127] - During the third stage, in which the temperature is constantly reduced from 90°C to 30°C over 8 minutes: increase the viscosity at a rate of at least 25 cPo / min to a viscosity at least 250 cPo higher than the thermal viscosity.

[0128] - At the end of the third stage of stable heating at 30°C: a viscosity of at least 500 cPo, or a viscosity of 500 cPo to 1000 cPo.

[0129] The starch production method according to the present invention :

[0130] The modified legume starch according to the present invention can be obtained by a method comprising or consisting of the following steps:

[0131] - Step a) of chemical functionalization by at least one of hydroxyalkylation and / or carboxylation.

[0132] - Step b of pre-gelatinization.

[0133] According to one embodiment of a method for obtaining modified legume starch according to the present invention, the method includes or comprises the following steps:

[0134] -The first step a) involves hydroxypropylating the natural pea starch in the particulate phase to a degree of substitution of up to 0.05 to 0.21, or up to 0.16 to 0.19.

[0135] - In a drum dryer, at a temperature of at least 90°C, the hydroxypropylated granulated pea starch obtained in step a) is pregelatinized in step b) at a starch content of 27% by weight.

[0136] -The third step (c) involves grinding the membrane from the pre-gelatinized hydroxypropylated starch obtained in step b.

[0137] - Collect the pregelatinized hydroxypropylated pea starch powder obtained in step c), and then cool it at 20°C-25°C in the fourth step d). This powder is referred to as pregelatinized hydroxypropylated starch.

[0138] Preferably, the method does not include any acidic or enzymatic hydrolysis steps of the starch, whether the starch is natural granular pea starch, hydroxypropylated granular pea starch or pregelatinized hydroxypropylated pea starch.

[0139] Water-resistant film-forming agent

[0140] In this application, "water-resistant film-forming agent" means a film-forming agent capable of forming a film that is water-resistant (i.e., it is water-resistant). This film is typically formed by applying a formulation containing starch according to the invention to a surface and allowing the formulation to dry or be allowed to dry.

[0141] Water resistance :

[0142] In this application, "water resistance" means the ability to withstand exposure to moisture and / or immersion in water for minutes or hours without being immediately washed away by the moisture or water.

[0143] According to one embodiment, "water resistance" means the ability of a film formed on the surface of a glass plate to withstand immersion in agitated tap water at 21°C for at least 1 minute, or at least 2 minutes, or at least 3 minutes, or at least 4 minutes, or at least 5 minutes. The film is formed by spreading an aqueous solution of 6% by weight of the film-forming agent, prepared by dissolving the film-forming agent at 21°C, onto the glass plate and allowing it to dry at 21°C for 12 hours.

[0144] Other properties of films formed with starch according to the invention :

[0145] In addition to being water-resistant, the film formed from the starch according to the invention or from a formulation containing said starch provides a taut effect and is elastic and non-brittle.

[0146] application :

[0147] Due to its water-resistant film-forming properties, the starch according to the present invention can be used in various fields, such as pharmaceuticals, healthcare, food, personal care or cosmetics, home care, and industrial applications. In cosmetics, applications include, for example, skin care, makeup, and sun protection. Examples of cosmetic formulations (in which the water-resistant film-forming starch according to the present invention is useful) are eyeshadow, eyeliner, mascara, and foundation.

[0148] Examples of skin care preparations (in which the water-resistant film-forming starch according to the invention is useful) are soothing creams or soothing serums, eye serums, firming serums, and sunscreens.

[0149] Sunscreen application

[0150] The water resistance of the starch according to the invention can be very useful in enhancing the protection of skin or hair against sunlight. When incorporated into a sunscreen formulation, this water-resistant starch imparts water resistance to the formulation, thus allowing the sunscreen formulation to remain on the application site (skin or hair) for a longer period. The longer the sunscreen formulation remains on the skin, the longer the sun protection lasts, resulting in more effective protection.

[0151] Cosmetic preparations :

[0152] Co-film-forming agents can be added to the starch according to the invention to improve water resistance, such as copolymers of vinylpyrrolidone and (meth)acrylates, like Antaron. ™ V-220F (Ganex) ™ Polymers such as V-220F, or copolymers of vinylpyrrolidone and olefins, such as VP / eicosane copolymers.

[0153] Analytical methods :

[0154] Viscosity characteristics measured by RVA

[0155] RVA stands for Rapid Viscosity Analyzer. It is a physical measurement technique that has been used for decades in the field of starch and modified starch. A viscometer called the RVA 4500 from Perkin Elmer is used to measure the evolution of the viscosity of a starch suspension subjected to a defined temperature profile under agitation over time. This evolution of viscosity, also known as the "RVA viscosity characteristic," is characteristic of starch and is particularly dependent on its plant type and the physical and chemical modifications it has undergone.

[0156] The measurement plan is as follows:

[0157] 1) Add 1.7 g of dry starch and 4.5 g of glycerol directly into the bowl of the RVA viscometer and homogenize by manual mixing with a spatula.

[0158] 2) Additionally, prepare 21.8 g + / - 0.01 g of water at room temperature.

[0159] 3) Prepare the RVA device to display a message such as "Please press the cap" or similar.

[0160] 4) Pour the amount of water prepared in step 2 into the starch / glycerin blend in the bowl and start measuring immediately.

[0161] The starch suspension was subjected to stirring and temperature characteristics according to Table 1, and as... Figure 1 As shown, the viscosity was measured simultaneously by measuring the torque applied to the stirring shaft.

[0162] [Table 1]

[0163]

[0164] Viscosity measured by an RVA viscometer is expressed in RVU and converted to centipoise (cPo) using the following conversion: 1 RVU unit = 12 cPo. As a reminder, 1 cPo = 1 mPa·s.

[0165] The maximum viscosity that occurs during the initial stabilization phase at 20°C, from 30 seconds to 10 minutes, is called the initial cold viscosity, also known as the "peak viscosity." The minimum viscosity that occurs during the 90°C plateau, from 18 minutes to 21 minutes, is called the hot viscosity. Finally, the maximum viscosity that occurs during the final stabilization phase at 30°C, from 29 minutes to 34 minutes, is called the final cold viscosity.

[0166] Solubility in water at 22°C

[0167] The principle of this measurement is to disperse a starch sample in water, then centrifuge it to separate the solid and liquid supernatant, and then analyze the dry content of the supernatant. The procedure is as follows:

[0168] Step 1) In a 250ml beaker, add 200ml of distilled water. Stir magnetically and add approximately 5g of the sample to be analyzed, which should be accurately weighed using a 1 / 1000g precision balance and recorded as m_sample. Homogenize at 22°C for 15 minutes using a magnetic stirrer. Centrifuge at 4000rpm for 10 minutes.

[0169] Step 2) Take 25 ml of the supernatant and transfer it to a balanced crystallizer. Place it in an oven at 60°C until the water evaporates. Then place it in an oven at 103°C + / -2°C for 1 hour. Place it in a desiccator and allow it to cool to room temperature. Weigh the dried residue using a 1 / 1000 g precision balance and record it as m_dried residue. The content of soluble starch in the starch sample, expressed as a percentage by mass, is given by the following formula:

[0170] [Mathematical Formula 1]

[0171]

[0172] Therefore, solubility is expressed as a percentage, which is the percentage by mass of starch in a sample that can dissolve in water.

[0173] Size distribution measurement via dry powder laser diffraction

[0174] The volume-average diameter of pregelatinized hydrophilic modified legume starch was measured by laser diffraction in dry powder.

[0175] Hydrophobicity value

[0176] The hydrophobicity of starch in aqueous solution is determined based on the liquid-vapor surface tension (denoted as σa) of a starch-water solution in equilibrium with air. LV ) and their polar components ( LV P ,) and dispersion component ( LV D The determination of ).

[0177] In the first step, the liquid-vapor surface tension of the starch aqueous solution was measured using a tensiometer, model K100C, from KRÜSS. This gives the liquid-vapor surface tension. LVThe measurement was performed using a ring, and at room temperature due to the temperature-controlled cell. The ring, defined by its geometry, was cleaned with water and dried over a flame using a kitchen blowtorch for a few seconds. At least 50 mL of the liquid to be analyzed was placed into a glass crystallizer. Using a lift, the liquid was raised and brought into contact with the ring suspended on a precision balance. The ring was then immersed in the liquid. The force acting on the ring was measured until it stabilized, and this force was then used to calculate the liquid-vapor surface tension in mN / m. LV .

[0178] In the second step, the contact angle θ between the starch aqueous solution and the Teflon plate was measured using a goniometer (model DSA100) from KRÜSS. Five 3 μL droplets were placed on the Teflon plate. For each droplet, the average angle was given. To maintain droplet symmetry, measurements with gaps exceeding 5 degrees between the left and right angles were excluded. The contact angle was measured at the triple point, where solid, liquid, and vapor are present.

[0179] According to mathematical formula #2, using the Young-Laplace and Fowkes model, the liquid-vapor surface tension, as measured in the first step, can be utilized. LV The value, and utilize the solid-vapor surface tension of Teflon. SV D Given the known value of the dispersion component (22.4 mN / m), calculate the solid-liquid surface tension of the starch solution. LV D Dispersion component:

[0180] [Mathematical Formula 2]

[0181] .

[0182] Finally, the following relationship is used to calculate the liquid-vapor surface tension. LV P polar components:

[0183] [Mathematical Formula 3]

[0184]

[0185] Then, the hydrophobicity and hydrophilicity values ​​are calculated using the following formula:

[0186] [Mathematical Formula 4]

[0187]

[0188] [Mathematical Formula 5]

[0189]

[0190] Example

[0191] Example 1: Preparation of modified legume starch according to the present invention

[0192] The pregelatinized hydroxypropylated pea starch according to the present invention is prepared by first hydroxypropylating the natural pea starch in the granular phase, then simultaneously gelatinizing and drying the hydroxypropylated granular pea starch in a contact drum dryer, and finally grinding the pregelatinized hydroxypropylated pea starch to obtain a powder, which is generally referred to as pregelatinized starch, and more precisely, in our case, pregelatinized hydroxypropylated pea starch.

[0193] The natural pea starch was obtained from Roquette Frères, France.

[0194] A starch aqueous suspension containing 20%–30% by weight of 0.5M sodium sulfate was hydroxypropylated in a pressurized stirred tank by introducing propylene oxide using 0.5M sodium hydroxide as a catalyst until the desired degree of substitution was achieved. The hydroxypropylated starch was then recovered by filtration, washed with distilled water, and dried using a flash dryer to a moisture content of approximately 12% by weight.

[0195] A suspension of hydroxypropylated pea starch was then prepared by dispersing the starch in water at 27% by weight dry matter under mixing conditions, and then fed to a pregelatinization step. 10 ppm of hydrogen peroxide was added to the starch suspension.

[0196] Pregelatinization is performed on an indirect-heated contact single-drum dryer, designated "Model E 5 / 5," from manufacturer ANDRITZ Gouda (files available online at nplcit2 https: / / www.andritz.com / products-en / separation / contact-dryers / gouda-drum-dryer). This dryer is internally heated by pressurized steam and equipped with four top-applying rollers. Operating parameters are as follows:

[0197] - Feed flow rate of starch suspension: 55 L / h

[0198] - Main roller rotation speed: 3.5 rpm

[0199] - Steam pressure inside the drum: 7 bar, corresponding to a steam temperature of 165°C.

[0200] - The thickness of the pregelatinized starch film: from 1.2 mm at the leftmost application roller (which is the application roller located on the side of the blade) to 0.7 mm at the rightmost application roller (maintien des bourbiers)

[0201] - The rotational speed of the applied roller: driven by a mechanical connection with the main roller.

[0202] - Starch milk inlet temperature: 20℃ + / - 5℃ (room temperature)

[0203] - Blade / knife height: the lowest possible position.

[0204] The pregelatinized starch, obtained by scraping with a knife, is then fed at the outlet of the drum dryer to two mills placed in series:

[0205] First, a hammer mill from FITZ MILL, model SPV DKAS012, equipped with a 1000-micron mesh, operated at full speed of 4600 rpm according to the instruction manual.

[0206] - Secondly, the "Ultrafin" grinder from POITTEMILL operates at 60% of its full speed.

[0207] The pregelatinized hydroxypropyl pea starch was then characterized by measuring its viscosity characteristics using a Perkin Elmer Rapid Viscosity Analyzer (RVA) operated under the conditions specified above. Solubility in water at 22°C and its D(10), D(90), and D(4,3) diameters were also measured. The results are shown in Table 2.

[0208] [Table 2]

[0209]

[0210] According to existing technology, starch (Beauté by Roquette) ® The analytical properties of ST 720 (hereinafter referred to as BBR ST 720) were also measured according to the same analytical method. BBR ST 720 is hydrolyzed hydroxypropylated pregelatinized pea starch. It differs from starch #1 of the present invention only in that it is hydrolyzed. The characteristic values ​​of BBR ST 720 are significantly different from those of starch #1 of the present invention, which proves that the two starches are completely different.

[0211] In the following examples, the obtained starch was then characterized and used in cosmetic formulations, which showed improved water resistance compared to hydrolyzed starch and film-forming agent benchmarks.

[0212] Example 2: Characterizing hydrophobicity in aqueous solutions using tensile force measurement and angle measurement methods

[0213] The polar and dispersive components of the pregelatinized hydroxypropylated pea starch aqueous solution prepared according to Example 1 were determined using a combination of two analytical methods. Similarly, the hydroxypropylated hydrolyzed pregelatinized pea starch (Beauté by Roquette) was also characterized. ® Aqueous solutions of ST 720 and polyvinylpyrrolidone (hereinafter referred to as PVP) were prepared. Each aqueous solution was prepared by dissolving starch in water at 20°C with stirring. Table 3 presents the characterized aqueous solutions.

[0214] [Table 3]

[0215]

[0216] As detailed in the description of the method used to determine the hydrophobicity value, the polar and dispersive components of the starch aqueous solution were calculated using the Young-Laplace and Fowkes model from the liquid-vapor surface tension, Teflon surface tension, and contact angle. The results are presented in Table 4.

[0217] [Table 4]

[0218]

[0219] At both pH 4 and pH 7, the aqueous solution containing hydroxypropylated pregelatinized pea starch according to the present invention is significantly more hydrophobic than the aqueous solution containing hydroxypropylated hydrolyzed pregelatinized pea starch BBR ST 720. The resulting level of hydrophobicity is equivalent to that of an aqueous solution of polyvinylpyrrolidone.

[0220] Example 3: Characterizing the hydrophobicity of membrane strips using goniometric method (Test B)

[0221] At 1 minute and 5 minutes after deposition, the contact angle of water droplets deposited on the surface of a strip of film made of a film-forming agent selected from prior art starch, starch #1 of the present invention and a reference film-forming agent was monitored using a goniometer KRÜSS DSA 100.

[0222] The following strips are prepared :

[0223] 1) An aqueous solution of the film-forming agent is prepared by dissolving the film-forming agent in distilled water at an appropriate concentration at room temperature, and then degassing under vacuum for 5 minutes or until no more bubbles appear.

[0224] 2) Pour 4.5g of the film-forming agent aqueous solution into a 7×1×1cm silicone mold.

[0225] 3) Place the filled mold in a temperature and humidity controlled oven at 23℃ and 50% relative humidity for 72 hours to dry.

[0226] 4) This yields a rectangular strip of membrane ready for use.

[0227] The changes in the contact angle between the water droplet and the membrane at 1 minute and 5 minutes relative to the initial contact angle (meaning exactly after the water droplet deposition) were calculated and are presented in Table 5.

[0228] [Table 5]

[0229]

[0230] These changes are negative due to the affinity of water for the hydrophilic polymers that make up the membrane. The film-forming agents tested resulted in different momentum in this relative change. The membrane made with PVP exhibited the largest change, indicating that water droplets spread at the highest rate on the membrane tested. The membrane strips made with prior art starch exhibited lower changes, which were somewhat greater than the changes measured on the membrane made with the starch #1 of the present invention. The membrane made with the starch #1 of the present invention exhibited the lowest change. This indicates that water droplets spread much more slowly on the membrane made with the starch #1 of the present invention compared to membranes made with prior art starch and a reference. This means that the starch #1 of the present invention produces a more water-resistant membrane.

[0231] Example 4: Water resistance of the film on the surface (Test A)

[0232] For two types of surfaces: glass plates and bandages, the solubility of films formed on inert surfaces using starch according to the invention (starch #1 from Example 1), starch according to the prior art (BBR ST 720), and two film-forming agent benchmarks (PVP and pullulan) was visually evaluated. For each surface and each film-forming agent, the procedure was as follows:

[0233] 1) Prepare an aqueous solution containing pigment.

[0234] 2) Use a scraper to spread 0.3g onto the surface of a glass plate or bandage that is placed horizontally on a flat support.

[0235] 3) Dry horizontally on a flat support for 12 hours at 22℃ ± 3℃ and 55% relative humidity ± 5%.

[0236] 4) Immerse the magnetic heater and stirrer in a beaker filled with water, stirring at 600 rpm for the glass plate and 1000 rpm for the bandage, maintaining a temperature of 21°C.

[0237] 5) For the glass plate, take photos of the surface removed from the water at 1 minute and 5 minutes, and for the bandage, take photos at 3 minutes and 5 minutes.

[0238] The results obtained on the glass plate are presented as follows Figure 2 The results are described above and in Table 6. Films formed from the starch according to the present invention remained unchanged after immersion in water for 1 minute, while prior art starch and the reference film-forming agent largely disappeared. After immersion for 5 minutes, the film formed from the starch of the present invention retained approximately half, while the other two films almost completely disappeared. These results indicate that the films formed using the present invention have superior water solubility. Roughly speaking, the water resistance of the film formed from the starch of the present invention on a glass plate is 2.5 times that of the comparative films (prior art and reference).

[0239] [Table 6]

[0240]

[0241] The results obtained on the bandage are presented in Figure 3 The above is described in Table 7. Films formed with the starch of the present invention can withstand immersion in water for a duration of 5 minutes, while films formed with prior art starch or standard film-forming agents cannot withstand such immersion because they almost completely disappear from the bandage.

[0242] [Table 7]

[0243]

[0244] The starch of the present invention forms a film with significantly higher water resistance than the starch and film-forming agent benchmarks from the prior art.

[0245] Example 5: Water resistance on fibers

[0246] The mascara prepared according to the formulation in Table 8 was applied to synthetic pink eyelashes. The mascara contained 5% by weight of a film-forming agent selected from prior art starch, starch #1 according to the invention, PVP, pullulan, or contained no film-forming agent (placebo formulation). For each film-forming agent, the mascara's resistance to immersion in water and its resistance to further rubbing against dry paper were visually evaluated.

[0247] [Table 8] Mascara formulations used for water resistance testing of synthetic eyelashes

[0248]

[0249] Each type of mascara is prepared as follows:

[0250] 1 / Weighing and mixing phase A1,

[0251] 2 / Add phase A2 and heat at 75℃-80℃ for 25 minutes.

[0252] 3 / Add A3 and homogenize at 2200 rpm for 15 minutes at 80°C, then add pigment.

[0253] 4 / Weigh and heat phase B1 at 80℃.

[0254] 5 / Emulsify B1 in A (1-2 minutes).

[0255] 6. Add B2 and stir at 2500 rpm for 15 minutes at 80°C.

[0256] 7 / Cool at very low agitation (1100 rpm) and room temperature (ice-free).

[0257] 8 / Add vitamin C and adjust the pH to approximately 7.3.

[0258] The following steps apply each type of mascara to a synthetic pink lash:

[0259] 1 / Apply 0.04g of mascara to one set of eyelashes.

[0260] 2 / Allow it to dry at 22℃+ / -3℃ for 1 hour.

[0261] 3 / Take photos, referred to as "before immersion in water".

[0262] 3 / Immerse the eyelashes in 21°C water for 30 seconds without letting them move.

[0263] 4. Stir the eyelashes in the water for 30 seconds.

[0264] 5 / Insert and remove from the water multiple times during a 30-second period.

[0265] 6. Stir the eyelashes in the water for 30 seconds.

[0266] 7 / Take photos, referred to as "after immersion in water".

[0267] 8 / Allow it to dry at 22℃+ / -3℃, and rub the eyelashes back and forth on a tissue.

[0268] 9 / Take photos, referred to as "after drying and rubbing with a paper towel".

[0269] Photos of each type of mascara are presented in Figure 3 Above, and they are described in Table 9 below.

[0270] [Table 9]

[0271]

[0272] Eyelashes coated with mascara containing prior art starch showed visible mascara loss upon immersion in water, which was indeed significant after rubbing with a tissue. However, no mascara loss was observed in eyelashes coated with mascara containing starch #1 of the present invention. The starch #1 of the present invention produces a mascara with higher water resistance than starches according to the prior art.

[0273] Example 6: Application in cosmetics: skin care and cosmetic preparations

[0274] The starch of the present invention is used as a film-forming agent, which provides water resistance in several cosmetic formulations.

[0275] Eyeshadow formulation #1 :

[0276] The formulation shall be prepared according to the following procedure based on the composition in Table 10:

[0277] 1) Prepare the premixed phase A1 and heat it to 80℃.

[0278] 2) While stirring at a medium speed, add phase A2 to phase A1, and maintain stirring and a temperature of 80°C for 40 minutes.

[0279] 3) Heat phase B at 80°C with medium to strong stirring speed and add it to phase A1+A2, maintaining stirring and temperature for 15 minutes.

[0280] 4) Allow to cool to room temperature while gently stirring.

[0281] [Table 10] Eyeshadow Preparations

[0282]

[0283] Eyeshadow formulation #2:

[0284] Prepare the formulation according to the composition in Table 11, following the operating procedure below:

[0285] 1) At room temperature, disperse the starch #1 of the present invention in water while stirring at 1000 rpm using an anti-flocculation machine until a uniform dispersion is obtained.

[0286] 2) While stirring, add xanthan gum to phase A until a homogeneous mixture is obtained, ensuring no undissolved particles remain.

[0287] 3) Add Beauté by Roquette ST 118 and simultaneously stir at 2000 rpm for at least 10 minutes using an anti-flocculation mixer to form a gel.

[0288] 4) Add ethanol and Microcare PHC while stirring.

[0289] 5) Disperse the pearlescent pigments with slow stirring until a uniform color is obtained.

[0290] 6) Adjust the pH to 6.5.

[0291] [Table 11] Eyeshadow Preparations

[0292]

[0293] Skin care preparation #1:

[0294] Prepare the formulation according to the composition in Table 12, following the operating procedure below:

[0295] 1) Mix and heat the components of phase A to 85°C, while stirring at 1600 rpm using an anti-flocculation machine.

[0296] 2) Cool phase A to 35°C and add phase C.

[0297] 3) Homogenize phase B on one side, and then add it to phase A+C under vigorous stirring to emulsify.

[0298] 4) If necessary, adjust the pH to 6 using phase D.

[0299] [Table 12] Soothing Serum

[0300]

[0301] Mascara formulation MU-017-022 :

[0302] Prepare the formulation according to the composition in Table 13, following the operating procedure below:

[0303] 1 / Weighing and mixing phase A1,

[0304] 2 / Add phase A2 and heat at 75℃-80℃ for 25 minutes.

[0305] 3 / Add A3 and homogenize at 2200 rpm for 15 minutes at 80°C, then add pigment.

[0306] 4 / Weigh and heat phase B1 at 80℃.

[0307] 5 / Emulsify B1 in A (1-2 minutes).

[0308] 6. Add B2 and stir at 2500 rpm for 15 minutes at 80°C.

[0309] 7 / Cool at very low agitation (1100 rpm) and room temperature (ice-free).

[0310] 8 / Add C and adjust the pH to approximately 7.3.

[0311] [Table 13] Mascara Formulation MU-017-022

[0312]

[0313] Eyeliner preparation MU-050-002 :

[0314] The formulation shall be prepared according to the following procedure based on the composition in Table 14:

[0315] 1 / Disperse Avicel PC 611 in water for 5-10 minutes and heat at 80°C.

[0316] 2 / Dispersed bentonite,

[0317] 3 / Add starch #1 of the present invention at 2200 rpm at 80°C for 15 minutes.

[0318] 4 / Cool to 22℃,

[0319] 5. Add alcohol and preservatives and mix for 15 minutes.

[0320] [Table 14] Eyeliner Preparation MU-050-002

[0321]

[0322] Eyeshadow preparation MU-001-014 :

[0323] Prepare the formulation according to the composition in Table 15 using the following procedure:

[0324] 1 / Add the components of phase A to water and heat at 80°C for 40 minutes.

[0325] 2 / Add starch #1 of the present invention and mix at 80°C for 15 minutes.

[0326] 3 / Preparation of Phase C: Mix and heat at 80°C until homogeneous.

[0327] 4 / Emulsify phase B in phase A over a period of 15 minutes.

[0328] 5. Cool to 22°C.

[0329] [Table 15] Eyeshadow preparation MU-001-014

[0330]

[0331] Eye serum formulation SC-103-009 :

[0332] Prepare the formulation according to the composition in Table 16 using the following procedure:

[0333] 1 / Preparation of Phase A: Glycerol is dispersed in water and the mixture is heated to 80°C.

[0334] 2 / Preparation of phase A2: Sucraclear V2 and Keltrol ® The CG-SFT blend was then added to phase A with agitation using an anti-flocculation machine.

[0335] 3 / Mix at 80°C (stir vigorously) until a uniform gel without lumps is obtained.

[0336] 4 / Add starch #1 (A3) of the present invention and mix for 15 minutes with vigorous stirring.

[0337] 5. Cool to room temperature (below 25°C).

[0338] 6 / Add Beauté by Roquette ® PO 500 (phase B), and mix for 5 minutes with medium agitation.

[0339] 7 / Add preservatives,

[0340] 8 / Add phase D (beads) until evenly dispersed.

[0341] 9 / Slowly dispersed with vigorous agitation. Beauté by Roquette ® ST 118, and continue stirring (at low to medium speed) until fully hydrated.

[0342] [Table 16] Eye Serum Formulation SC-103-009

[0343]

[0344] Foundation formulation MU-037-021 :

[0345] Prepare the formulation according to the composition in Table 17, following the operating procedure below:

[0346] 1 / Prepare phase C (oil + pigment) to disperse the pigment by stirring with an anti-flocculation machine for 10-15 minutes.

[0347] 2 / Mixed C+D,

[0348] 3 / Heat A at 90°C until it is evenly dispersed, and then add B.

[0349] 4 / Add A+B to C+D.

[0350] 5 / Parallel preparation phase E was performed by dispersing the starch #1 of the present invention in water at 80°C over a period of 15 minutes at 2000 rpm.

[0351] 6 / Add the components of phase F sequentially to E.

[0352] 7 / F+E is emulsified very slowly in the oil phase (A+B+C+D).

[0353] [Table 17] Foundation Formulation MU-037-021

[0354]

[0355] Firming serum formulation SC-105-004 :

[0356] Prepare the formulation according to the composition in Table 18 using the following procedure:

[0357] 1 / The components of phase A2 are sequentially dispersed in phase A1, and simultaneously heated at 80°C.

[0358] 2 / Disperse the starch #1 of the present invention at 80°C for 15 minutes.

[0359] 3 / Heat phase C at 80°C and emulsify it in aqueous phase A1+A2+B at 80°C for 10 minutes.

[0360] 4 / Cool and add D, then add E.

[0361] [Table 18] Firming Serum Formulation SC-105-004

[0362]

[0363] Firming white cream formulation SC-106-008 :

[0364] Prepare the formulation according to the composition in Table 19, following the operating procedure below:

[0365] 1 / To prepare phase A, the thickener was dispersed in water without stirring, and simultaneously heated at 80°C.

[0366] 2 / Disperse the starch #1 of the present invention at 80°C (2200 rpm) for 15 minutes with stirring.

[0367] 3 / Heat phase C at 80°C and emulsify it in the aqueous phase at 80°C for 10 minutes.

[0368] 4 / Cool and add Beauté by Roquette ® ST 118 until a uniform appearance is achieved.

[0369] 5 / Add E, then add F.

[0370] [Table 19] Firming White Cream Formulation SC-106-008

[0371]

[0372] Firming Green Cream Formulation SC-106-002 :

[0373] Prepare the formulation according to the composition in Table 20, following the operating procedure below:

[0374] 1 / Preparation phase A1, dispersing glycerol,

[0375] 2 / Thickener A2 is added to the aqueous phase A1 without stirring for hydration, while heating at 80°C.

[0376] 3 / Disperse A3 in phase A1+A2 under stirring.

[0377] 4 / Under stirring, disperse the starch #1 of the present invention in phases A1+A2+A3 at 80°C for 15 minutes (2200 rpm).

[0378] 5 / Heat phase C at 80°C and emulsify it in aqueous phase A1+A2+A3+B at 80°C for 10 minutes.

[0379] 6. Cool and add D, E and F in sequence.

[0380] [Table 20] Firming Green Cream Formulation SC-106-002

[0381]

[0382] Sunscreen formulation SU-003-006 :

[0383] The formulation shall be prepared according to the following procedure based on the composition in Table 21:

[0384] 1 / Disperse xanthan gum in water and heat to 80°C, adding A2 during the 15-minute period.

[0385] 2 / Prepare phase B1 and mix it under magnetic stirring at 80°C.

[0386] 3 / Prepare phase B2 and mix it under magnetic stirring at room temperature.

[0387] 4 / Mix phases B1 and B2, and emulsify phase B in phase A under vigorous stirring (3000 rpm, over 10 minutes).

[0388] 5 / Cool at room temperature and add phase C,

[0389] 6 / Add phase D at pH 5.5.

[0390] [Table 21] Sunscreen formulation SU-003-006

[0391]

[0392] Sunscreen formulation SU-024-014 V2 :

[0393] Prepare the formulation according to the composition in Table 22, following the operating procedure below:

[0394] 1 / Prepare phase A and disperse bentonite in a beaker until a homogeneous solution is obtained.

[0395] 2 / Then disperse the xanthan gum, heat at 80°C and add the starch #1 of the present invention (15 minutes).

[0396] 3 / Prepare phase B and heat at 80℃.

[0397] 4 / Emulsify oil phase B in the aqueous phase under vigorous agitation (3000 rpm, 10 minutes).

[0398] 5 / Cool at room temperature (20℃-25℃).

[0399] 6 / Add phase C,

[0400] 7 / Adjust the pH to 7.5 if necessary.

[0401] [Table 22] Sunscreen formulation SU-024-014 V2

[0402]

[0403] Reference List

[0404] Non-patent literature

[0405] For any purpose, the following non-patented elements are referenced:

[0406] -nplcit1: Roy L. Whistler and Eugene F. Paschall, Starch: Chemistry and Technology, Volume II Industrial aspects; Academic Press, 1967, 733 pages (Library of Congress Catalog Card No.: 65-21330);

[0407] -nplcit2: https: / / www.andritz.com / products-en / separation / contact- dryers / gouda-drum-dryer .

Claims

1. A pregelatinized hydrophilically modified legume starch, wherein the pregelatinized hydrophilically modified legume starch has an RVA viscosity characteristic characterized by a final cold viscosity of 100 cPo to 2000 cPo, or 125 cPo to 1750 cPo, or 150 cPo to 1500 cPo, or 200 cPo to 1200 cPo. The RVA temperature and stirring procedure are as follows: - At time = 0 seconds: temperature = 25℃; stirring speed = 100 rpm. - At time = 10 seconds: temperature = 25℃; stirring speed = 500 rpm - At time = 30 seconds: temperature = 25℃; stirring speed = 160 rpm. - At time = 10 minutes: temperature = 25℃; stirring speed = 160 rpm. - At time = 18 minutes: temperature = 90℃; stirring speed = 160 rpm. - At time = 21 minutes: temperature = 90℃; stirring speed = 160 rpm. - At time = 29 minutes: temperature = 30℃; stirring speed = 160 rpm. - At time = 34 minutes: temperature = 30℃; stirring speed = 160 rpm.

2. The starch according to claim 1, wherein its RVA viscosity characteristics are characterized by an initial cold viscosity of 250 cPo to 4000 cPo, or 400 cPo to 3500 cPo, or 500 cPo to 3000 cPo.

3. The starch according to any one of claims 1 or 2, wherein the legume starch has an amylose content of greater than or equal to 20% by weight, or 24% by weight, or 30% by weight, or 34% by weight, preferably 30% by weight to 40% by weight.

4. The starch according to claim 3, wherein the legume starch is selected from pea starch, kidney bean starch, broad bean starch, fava bean starch, lentil starch, alfalfa starch, clover starch, lupin starch or soybean starch, preferably pea starch.

5. The starch according to any one of claims 1 to 4, wherein the starch is hydroxyalkylated and / or carboxyalkylated, preferably hydroxyalkylated.

6. The starch according to any one of claims 1 to 5, wherein the degree of substitution is 0.01 to 3, or 0.05 to 0.8, or 0.05 to 0.6, or 0.05 to 0.21, preferably 0.15 to 0.

19.

7. The starch according to any one of claims 1 to 6, wherein the starch has a solubility of 25% to 80%, or 30% to 75%, or 35% to 60%, or 45% to 55% in water at 22°C.

8. The starch according to any one of claims 1 to 7, wherein the starch has a particle size distribution having a volume-average diameter D(4,3) of 25 micrometers to 200 micrometers, or 40 micrometers to 150 micrometers, or 50 micrometers to 100 micrometers.

9. The starch according to any one of claims 1 to 8, wherein the starch has a hydrophobicity value equal to or greater than 30%, or 35%, preferably 30% to 55%, or 35% to 50%, as measured according to the Young-Laplace and Fowkes model.

10. A method for manufacturing pregelatinized hydrophilically modified legume starch according to any one of claims 1 to 9, the method comprising the following steps, preferably consisting of the following steps: a) Provides natural legume starch. b) The natural legume starch described in step a) is hydrophilically modified, preferentially by hydroxypropylation. c) Pregelatinize the hydrophilic modified legume starch described in step b. d) Grinding the pregelatinized hydrophilic modified legume starch from step c).

11. The method of claim 10, wherein the pregelatinization step is performed using a drum dryer or an extruder, or a combination of a jet cooker and a spray dryer, preferably using a drum dryer.

12. Use of the pregelatinized hydrophilic modified legume starch according to any one of claims 1 to 9 in the preparation of products, wherein the starch is a water-resistant film-forming agent.

13. The use according to claim 12, wherein the beauty product is selected from skin care products, hair care products, cosmetic products, oral care products, or hygiene products.

14. A film-forming composition comprising pregelatinized hydrophilically modified legume starch according to any one of claims 1 to 9 in a physiologically acceptable medium.

15. The film-forming composition according to claim 14, wherein the content of the pregelatinized hydrophilic modified legume starch is 0.5% to 10% by weight, or 3% to 7% by weight, or 4% to 6% by weight of the total weight of the film-forming composition.

Images