JP2021181088A - Biopolymer blend as emulsion stabilizer - Google Patents

Abstract

To provide an emulsion stabilizer containing a durable product, realizing good long-term stability and realizing touch sense quality allowable when used for personal care formulation.SOLUTION: An emulsion stabilizer contains a bio polymer blend of one or more cellulose ethers and one or more cross-linking modified starch. The one or more cellulose ethers or the one or more cross-linking modified starch is modified to be hydrophobic. The total amount of the cellulose ethers in the bio polymer blend is 50 wt.% or less. Further, this invention includes the emulsion stabilizer, especially oil-in-water emulsion and refers to an emulsion composition. In one embodiment, the emulsion is suitable for use in personal care formulation.SELECTED DRAWING: None

Description

The present invention relates to an emulsion stabilizer and an emulsion containing an emulsion stabilizer. More specifically, the present invention comprises one or more cellulose ethers.
An emulsion stabilizer comprising a biopolymer blend with one or more cross-linked, modified starches, wherein one or more of the cellulose ethers and the cross-linked starch are hydrophobic. Regarding modified emulsion stabilizers.

Emulsion stability is important to achieve the long-term storage required for commercial emulsions. In the personal care industry, emulsions that require long-term stability may include, for example, certain sunscreens, skin moisturizing formulations, skin creams, and hair styling formulations. In these types of personal care formulations, small molecule-containing synthetic materials have typically been used as emulsifiers. However, certain small molecule emulsifiers can cause irritation, toxicity, and unwanted interactions with cosmetic functional materials in the formulation. Moreover, certain small molecule emulsifiers may not be able to achieve the desired long-term emulsion stability.

Emulsion stabilizers for personal care compositions are insensitive to the salts that may be contained in the personal care composition, resulting in over-restriction by the person prescribing the composition in choosing the ingredients to be included in the personal care formulation. It is desirable not to receive.

Emulsion stabilizers with tactile quality that are attractive to consumers are desirable, especially for personal care formulations used on the skin.

Starch and starch derivatives are known to provide the desired tactile quality for personal care formulations. The starch used in such formulations must be at a concentration greater than about 3%, otherwise the starch undergoes a phenomenon known as retrogradation.
Can precipitate from the formulation.

Cellulose and its derivatives are known to act as emulsifiers, but can result in undesired tactile qualities when used as emulsifiers in personal care products, especially those used on the skin.

US Patent Application Publication No. 2012/0121519, assigned to the same assignee as this patent application, contains one or more cross-linking reagents and one or more ionic reagents from approximately 1 mol%.
A polymer emulsifier containing a polysaccharide modified to about 10 mol%, a method for preparing the same, and an emulsion containing the polymer emulsifier are disclosed.

International Publication No. 2009/080657 is an oil that is said to have long-term stability and good functional properties by using a combination of one or more hydrophobically modified polysaccharides and a fatty acid ester of a polyol. It is described to obtain a medium water emulsion. The hydrophobically modified polysaccharides described therein include inulin, cellulose and derivatives thereof, starch, and agar, and mixtures thereof, and preferred polyol fatty acid esters are polyglyceryl-4 / poly diisostearate. Hydroxyl stearate / sebacate. As described herein, an oily continuous phase is prepared from fatty acid esters of one or more polyols, and an aqueous phase is prepared from hydrophobically modified polysaccharides.
The two phases are then mixed to form a water-in-oil emulsion.

U.S. Patent Application Publication No. 2012/0121519 International Publication No. 2009/080657

One object of the present invention is to provide an emulsion stabilizer containing a durable product and achieving good long-term stability.

Another object of the present invention is to provide an emulsion stabilizer that achieves acceptable tactile quality when used in personal care formulations.

Yet another object of the present invention is an emulsion stabilizer that is salt-insensitive enough to facilitate the use of salt compounds in personal care formulations, for example for skin, hair, and other personal care applications. To provide.

In a first embodiment, the invention is generally an emulsion stabilizer comprising a biopolymer blend of one or more cellulose ethers and one or more crosslinked starches, one or more. The present invention relates to an emulsion stabilizer in which the further cellulose ether and the crosslinked starch are modified to be hydrophobic.

In certain embodiments, the present invention generally comprises an emulsion stabilizer comprising a biopolymer blend of one or more cellulose ethers and one or more crosslinked starches, said one or more thereof. The present invention relates to an emulsion stabilizer in which the above cellulose ether is modified to be hydrophobic.

In certain embodiments, the present invention is an emulsion stabilizer comprising a biopolymer blend of one or more cellulose ethers and one or more crosslinked modified starch, said one or more. The present invention relates to an emulsion stabilizer in which the cellulose ether is modified to be hydrophobic and the total amount of the cellulose ether in the biopolymer blend is 50% by weight or less.

In another embodiment, the invention is a method of making an emulsion stabilizer comprising a biopolymer blend of one or more cellulose ethers and one or more crosslinked starches, one or more. The present invention relates to a method for producing an emulsion stabilizer in which the cellulose ether and the crosslinked starch are further modified to be hydrophobic.

In another embodiment, the invention is a method of producing an emulsion stabilizer comprising a biopolymer blend of one or more cellulose ethers and one or more crosslinked starches, said one. The present invention relates to a method for producing an emulsion stabilizer in which or more cellulose ether is modified to be hydrophobic.

In another embodiment, the present invention is an emulsion formulation comprising a continuous phase, a discontinuous phase, and an emulsion stabilizer, wherein the emulsion stabilizer is one or more cellulose ethers and one. Emulsion formulations comprising a biopolymer blend with a seed or more modified starch and one or more of the cellulose ethers and the crosslinked modified starch being modified hydrophobically.

In another embodiment, the present invention is an emulsion preparation containing a continuous phase, a discontinuous phase, and an emulsion stabilizer, wherein the emulsion stabilizer is one or more cellulose ethers and one. With respect to an emulsion formulation comprising a biopolymer blend with a seed or higher modified starch and the above one or more cellulose ether being modified hydrophobically.

Since the blend of the present invention contains one or more cellulose ethers as components and one or more modified starches, and the cellulose ether component and the starch component are considered to be biopolymers, the blend of the present invention is bio. It is called a polymer blend.

The present invention, when read in conjunction with the accompanying drawings, is best understood from the following detailed description.
The drawings include the following figures.

FIG. 1 relates to the elastic properties of the aqueous phase of a composition containing a hydrophobically modified cellulose ether blended with crosslinked modified starch, non-crosslinked modified starch, and non-crosslinked modified starch according to Example 3, respectively. Graphs taken at the start and after storage for 1 month. FIG. 2 is a graph relating to the complex viscosity of the aqueous phase of the same composition as the subject of FIG. 1 according to Example 3, obtained at the start and after storage for 1 month. FIG. 3 shows the composition (in elastic modulus) with and without 0.2% EDTA disodium, which comprises a hydrophobically modified cellulose ether blended with crosslinked modified starch in an aqueous solution according to Example 5. It is a graph which shows the salt sensitivity (measured). FIG. 4 is a graph showing salt sensitivity (measured by complex viscosity) of the same composition as the subject of FIG. 3, according to Example 5. FIG. 5 is a graph showing the salt sensitivity (measured by shear viscosity) of a composition comprising the biopolymer blend of the present invention in an aqueous solution containing various concentrations of NaCl according to Example 5. FIG. 6 is a graph showing the functional order of the composition containing the biopolymer blend having different ratios of the hydrophobically modified cellulose ether and the crosslinked modified starch according to Example 6.

The present invention relates to emulsion stabilizers comprising durable products and achieving good long-term storage stability.

As used herein, the term "modification", when applied to starch, means a starch molecule that has reacted with one or more hydroxyl groups of the molecule.

As used herein, the term "hydrophobic modification", when applied to cellulose or starch, is one or more aliphatic or aromatic, saturated or unsaturated, straight lines,
It means a branched chain, or a cyclic, _{hydrocarbon-based chain of C 8 to} C ₃₀ , particularly a cellulose or starch molecule substituted with a hydrophobic group containing 8 to 30 carbon atoms.

As used herein, the "weight" of any starch or cellulosic material is.
Recorded on a dry weight basis.

As used herein, the term "long-term stability" is the room temperature measured using a TURBISCAN® LAB Stability Analyzer, as described in the section of Examples herein. And at 45 ° C., it means the stability of the emulsion for at least 28 days.

Starch is known to achieve desirable tactile properties when used in emulsions of personal care compositions. However, when starch is used as the only emulsion stabilizer, a phenomenon called retrogradation can occur, resulting in a phenomenon called retrogradation.
It is known that emulsions are typically unstable. Therefore, such a retro gradation is not desirable.

According to the present invention, the composition comprising the biopolymer blend of the cellulose ether and the crosslinked modified starch in which one or more cellulose ethers and the crosslinked modified starch are modified to be hydrophobic is based on a hydrocarbon. It can serve as an effective emulsion stabilizer composition for oil emulsions in water for long-term stability of both oils and natural oils. In one embodiment, the composition comprising a biopolymer blend of said cellulose ether and crosslinked modified starch, wherein one or more cellulose ethers have been modified hydrophobically, is both a hydrocarbon based oil and a natural oil. Can serve as an effective emulsion stabilizer composition for oil-in-water emulsions for long-term stability. In one embodiment, the weight ratio of cellulose ether to crosslinked modified starch is about 1: 1 or less. It has been found that such emulsion stabilizer compositions achieve good tactile quality but are not subject to retro-gradation.

The biopolymer blends of the present invention are particularly advantageous as emulsion stabilizers for personal care formulations, such as for skin care and hair styling applications. For example, in addition to durability, the natural tactile quality achieved by the biopolymer blends of the subject of the invention would be attractive compared to the tactile quality of synthetic stabilizers. Similarly, the strong salt tolerance of this biopolymer blend will allow the prescriber to blend into a variety of ingredients. The biopolymer blends of the invention are still used at low biopolymer concentrations when measured using the TURBISCAN® LAB Stability Analyzer and the methods described in the Examples section of the specification. , Shows long-term emulsion stability without causing retrogradation of starch components.

Cellulose Ether Cellulose is a polysaccharide made up of 1,4-anhydroglucose units. Cellulose molecules in natural cellulose are insoluble in water. In order to make cellulose soluble, cellulose derivatives such as hydroxyethyl cellulose (HEC), ethyl hydroxyethyl cellulose (EHEC), hydroxylpropyl cellulose (HPC), hydroxybutylmethyl cellulose (HBMC), hydroxypropylmethylcellulose (HPMC), methylethylhydroxy It needs to be modified to ethyl cellulose (MEHEC) and hydrophobically modified ethyl hydroxyethyl cellulose (HMEHEC).

To produce the modified cellulose, the cellulose is subjected to an alkalizing step, then reacted with ethylene oxide and ethyl chloride to produce EHEC, and similarly reacted with methyl chloride to produce MEHEC. Each anhydrous glucose unit of cellulose has three hydroxyl groups that can be used in the reaction. The number of reacted hydroxyl groups per anhydrous glucose unit is expressed as a degree of substitution (DS) and ranges from 0 to 3. The degree of molar substitution of ethylene oxide (MS _EO ) is the average of the total number of ethylene oxide groups per anhydrous glucose unit.

Cellulose ether materials suitable for use in the emulsion stabilizers of the present invention may be derived from any cellulosic source, such as cellulosic pulp, softwood pulp, cotton raw materials including cotton linters, bacterial cellulose, and regenerated cellulose. Examples include, but are not limited to, cellulose.

In one embodiment, the cellulose ether used in the biopolymer blend of the present invention is a nonionic cellulose ether. In certain embodiments, the cellulose ether is hydroxy _(C 1 _{~C 4)} alkyl cellulose.

Nonionic cellulose ethers include, for example, methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, methyl ethyl hydroxyethyl cellulose, propyl hydroxyethyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl ethyl cellulose, hydroxypropyl propyl. Cellulose, hydroxypropyl hydroxyethyl cellulose, methyl hydroxypropyl hydroxyethyl cellulose, hydroxypropyl cellulose, and mixtures thereof. In one embodiment, examples of the cellulose ether used in the biopolymer blend of the present invention include methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, methyl hydroxyethyl cellulose, methyl ethyl hydroxyethyl cellulose, hydroxypropylmethyl cellulose, and mixtures thereof. Not limited to.

In one embodiment, the cellulose ether used in the biopolymer blend of the present invention is methyl ethyl hydroxyethyl cellulose, which is described herein as "MEHEC".
Is called.

In one embodiment, the cellulose ether used in the biopolymer blend of the present invention is ethyl hydroxyethyl cellulose and is referred to herein as "EHEC".

Suitable nonionic cellulose ethers include Akzo Nobel Functi.
melon Chemicals, LLC (Chicago, Illinois) is a trademark of Bermocol.
The one sold as l (registered trademark) can be mentioned. Other suitable cellulose ethers include Ashland Inc. (Covington, Kentucky), trademark Natron
Examples include those sold as sol ™ hydroxyethyl cellulose.

Nonionic cellulose ethers can be particularly useful in applications where good salt tolerance is desired.

In one embodiment, the cellulose ether used in the biopolymer blend of the present invention is an anionic cellulose ether, especially in a formulation that does not require high resistance to salt compounds.

Anionic cellulose ethers include, for example, carboxymethyl cellulose, hydroxyethyl carboxymethyl cellulose, hydroxypropyl carboxymethyl cellulose, etc.
Sulfoethyl cellulose, hydroxyethyl sulfoethyl cellulose, hydroxypropyl sulfoethyl cellulose, and mixtures thereof.

Cellulose ethers can be prepared according to conventional methods known to those skilled in the art. For example, alkaline cellulose (activated cellulose) is obtained by first marceling the cellulose with an alkali in one step or several steps, and then subjecting the alkaline cellulose to ethylene oxide, propylene oxide, butylene oxide, or methyl chloride in one step or several steps. , Ethylene chloride, monochloroacetic acid (MCA), and one or more suitable amounts of etherifying agent selected from salts of MCA and organic reaction media such as ethyl chloride, acetone, alkyl or mono. Poly (ethylene glycol), isopropanol, tert-butanol, or ethers such as methyl tert-butyl ether,
It can be prepared by reacting in the presence of methyl sec-butyl ether, or dimethoxyethane, or a mixture thereof, at temperatures in the range of about 50 to about 120 ° C.

Cellulose ethers are characterized by the presence of one or more substituents on the cellulose chain.

In one embodiment, the cellulose ether is substituted with hydroxyalkyl, eg ethylene oxide, and is characterized as _{MS EO.} In one embodiment, the MS _EO is
1.0 or more, 1.5 or more in one embodiment, 2.0 or more in one embodiment, 2.4 or more in one embodiment.

In one embodiment, the cellulose ether is methyl and / or _{ethyl-substituted, DS ethyl} and _DS total _methyl is 0.1 or more, in one embodiment 0.
2 or more, 0.4 or more in one embodiment, 0.6 or more in one embodiment, and 0.8 or more in one embodiment.

In one method for producing an alkyl-substituted cellulose ether, cellulose is marsell-processed in one step or several steps with an aqueous alkali having a total amount of alkali of about 0.8 to about 1.8 mol per mole of sugar unit. The total amount of the cellulose obtained per 1 mol of sugar unit is about 2.
React with 6 to about 5.5 mol of ethylene oxide. The reaction product is then reacted with about 0.2 to about 1.5 mol of ethyl chloride per mole of sugar unit to produce EHEC, or the total amount of about 0.2 to about 1.5 mol per mole of sugar unit. MEHEC is either produced by reacting with molars of ethyl chloride and methyl chloride. These components are added to the marcel-processed cellulose and reacted at a temperature of about 50 to about 120 ° C. in the presence of an organic reaction medium in one step or several steps. In one embodiment of the invention, the weight ratio of reaction medium to cellulose may be from about 1: 1 to about 10: 1, and in another embodiment, from about 4: 3 to about 3: 1. You may.

In one embodiment, the methyl chloride or ethyl chloride serves as both an etherifying agent and a reaction medium, in which case the required amount of methyl chloride or ethyl chloride is already present in the reaction mixture and the methyl chloride. Or it is not necessary to add more ethyl chloride. Alkylation can be adjusted by the cellulose source, the amount of alkali used, the reaction temperature, and the reaction time. If desired, a portion of the alkali may be added later during the reaction to further activate the cellulose. The total degree of substitution with methyl and ethyl can be controlled by the amount of alkali used in the Marcel processing step, as a corresponding equivalent of NaOH is consumed to produce sodium chloride. However, due to side reactions, the yield of alkyl substitutions is about 40-60%. U.S. Patent No. 7
, 319, 146, which is incorporated herein by reference in its entirety.
A general description of the method used to make the cellulose ether polymer is provided.

One method of making cellulose ethers suitable for use in the present invention is disclosed in US Patent Application Publication No. 2009/0326217, which is incorporated herein by reference in its entirety. Is prepared in the presence of an ethereal solvent.

Hydrophobic Modification In one embodiment, the cellulose ether contains one or more, aliphatic or aromatic, saturated or unsaturated, linear, branched, or containing 8-30 carbon atoms. It may be modified to be hydrophobic by substituting with a cyclic hydrophobic group. In one embodiment, the hydrophobic substituents used are C _{8 to} C _{30 , preferably C 8} to C 30 in another embodiment.
Examples of C ₂₂ include an alkyl group, an arylalkyl group, or an alkylaryl group, and combinations thereof. In certain embodiments, the hydrophobic substituents of C _{8 to} C ₂₂ are
Saturated alkyl chains of C _{16 to} C ₂₀ , such as cetyl (C ₁₆ ), stearyl (C ₁₈ ), or behenyl (C ₂₀ ) groups. In certain embodiments, the hydrophobic substituent according to the invention is a cetyl group or a stearyl group. In certain embodiments, the hydrophobic groups are derived from natural sources such as tall oil, tallow, soybeans, coconut palm, and palm oil.

The hydrophobic modifier may be attached to the cellulose ether substrate by an ether bond, an ester bond, or a urethane bond. The most commonly used reagents for etherification are readily available and the reaction is similar to that commonly used for initial etherification.
Ether binding is preferred because the reagent is usually easier to handle than reagents used for modification by other binding. The resulting binding is also usually more resistant to further reactions. In one embodiment, the nonionic cellulose ether is slurryed into an inert organic diluent such as a lower fatty alcohol, a ketone, or a hydrocarbon, to the resulting slurry.
At low temperature, add the alkali metal hydroxide solution, then add the C _10- C ₂₄ epoxides.
The reaction can be carried out by continuing stirring until the reaction is complete.

Hydrophobically modified cellulose ethers and methods for preparing them are known in the art.
For example, US Pat. No. 6,627,751 (incorporated herein by reference).
Discloses a hydrophobically modified anionic cellulose ether that can be obtained by a process comprising reacting an alkali metal cellulose having no hydroxyalkyl group with at least three types of alkylating reagents. The alkylating reagent of one or more is selected from the group of haloacetic acid, alkali metal haloacetate, alkali metal vinyl sulfonate, and vinyl sulfonic acid, and one or more of the alkylating reagents are
Formula R ¹ − (OCH ₂ CH (R ² )) _{n −} P (R ¹ represents a group of C _{2 to} C ₇ ^{, R 2} is a hydrogen or methyl group, n is 0 to 2 and P is. , Glycidyl ether group, 3-halo-2-
A hydroxypropyl ether group, a 1,2-epoxy group, or a halide), and one or more reagents are of the formula R ^3- (OCH ₂ CH (R ² )) _m- P (R).
³ represents a group of C _{8 to} C ₃₀ , m is 0 to 10, and R ² and P have the same meaning as described above). U.S. Patent Application Publication No. 2009/0326217 (incorporated herein by reference) discloses a process for preparing cellulose ethers.
The cellulose ether can be the same as the formula ^{R 1 -O-R 2 (R} 1 and ^{R 2,} or different, an alkyl group, preferably a _C 1 -C straight or branched chain _{It is prepared in the presence of an ether (selected independently of the 6} alkyl groups) having a boiling point of 40-90 ° C., or a solvent mixture containing the ether and having a boiling point of 40-90 ° C.

In one embodiment, examples of the hydrophobically modified cellulose ether include ethyl hydroxyethyl cellulose ether (HM-EHEC). In one embodiment, the hydrophobically modified cellulose ether is a hydrophobically modified hydroxyethyl cellulose (
HM-HEC) may be used.

Another factor to consider is the molecular weight of the hydrophobically modified cellulose ether. The molecular weight can be determined by physical properties, such as intrinsic viscosity, or by spectrophotometric analysis, such as light scattering. For the present invention, all molecular weights are determined by light scattering methods known in the art and are expressed in weight average molecular weight (Mw) demonstrated by the procedure described in the Examples section of the present application below. .. The unit recorded is by Dalton (Da).

In one embodiment of the invention, the hydrophobically modified cellulose ether has a molecular weight of 9
It will be 100,000 or more, more preferably 1,000,000 or more. In one embodiment of the invention, the molecular weight is about 2,000,000 or less, and in one embodiment about 1,500.
It will be 000 or less, about 1,200,000 or less in one embodiment.

In another embodiment of the invention, the hydrophobically modified cellulose ether has a molecular weight of 9
It will be less than 100,000, 800,000 or less in one embodiment. In one embodiment of the invention, the molecular weight is about 200,000 or more, and in one embodiment about 300,000.
That would be all.

Starch The starch component of the present invention can be isolated from any plant source of starch, such as corn, wheat, rice, morokoshi, pea, potato, tapioca (cassava), sweet potato, and sago. Can be given. In certain embodiments of the invention, starch comprises greater than about 90% amylopectin. In another embodiment, the starch comprises more than 95% amylopectin. In yet another embodiment, starch is
Contains over 97% amylopectin.

This high amylopectin starch has been conventionally known as waxy in the art, and many types of waxy starch are commercially available. In certain embodiments of the invention
Waxy starch is corn, rice, potato, or tapioca waxy starch.

In a preferred embodiment of the invention, the starch will have a high molecular weight. For the present invention, high molecular weight is defined as the molecular weight of natural starch that has not been deliberately decomposed into low molecular weight. That is, some decomposition will occur during the isolation of the starch, and further during the chemical treatment and drying of the starch, but for the present invention, the high molecular weight starch has the highest possible pristine molecular weight. Maintained high molecular weight starch. In another embodiment, the starch may be partially degraded in a controlled manner by means known in the art including, but not limited to, acid-catalyzed hydrolysis, enzyme-catalyzed hydrolysis, and oxidative degradation. good. If the starch is intentionally partially decomposed, the water fluidity (WF) of the decomposed starch is 7.
It will be less than 0, preferably less than 60, most preferably less than 45.

Suitable starches for use in the present invention are crosslinked starches. Cross-linking of starch chains
It can be realized by a suitable cross-linking agent, for example, a bifunctional compound. In a further embodiment
Crosslinking is achieved by the reaction of starch with epichlorohydrin. In a further embodiment, the preferred cross-linking method is phosphorylation, in which the starch is cross-linked by anionic PO groups, such as phosphorus oxychloride, pentoxidrin, and /.
Or react with sodium trimethaphosphate. The anionic properties of the cross-linking site facilitate the emulsion stabilizing action of starch. In a further embodiment, further preferred crosslinking method is a method by C ₄ -C ₁₈ alkane dicarboxylic acids or alkene carboxylic acid, preferably in another embodiment a method according to C ₄ -C ₈ alkane dicarboxylic acids, particularly adipic This is an acid method. The alkanedicarboxylic acid or alkenedicarboxylic acid connects the two starch chains with an ester bond. It may have a linear shape or a branched chain shape. In a further embodiment, for example, starch is reacted with a mixture of dicarboxylic acid anhydride and acetic anhydride to give crosslinked starch. Starch
It may be crosslinked with about 15 ppm to about 400 ppm of cross-linking reagent, preferably with about 50 to about 300 ppm of cross-linking reagent in another embodiment, and more preferably about 100 ppm to about 100 ppm in yet another embodiment. It may be crosslinked with a 200 ppm crosslinking reagent.

In a further embodiment, cross-linked starch, by the addition of C ₂ -C ₅ hydroxyalkyl component, it is further modified. I don't want to be bound by theory, but 2-5
It is believed that the presence of hydroxyl groups attached to the starch skeleton by alkyl groups with carbon atoms provides the proper hydrophilic-lipophilic balance of starch. The position of the hydroxyl group in the alkyl group is not very important, and the α-position to ω
It may be a place. The degree of substitution is the average number of substituted OH groups in the starch molecule per anhydrous glucose unit. In one embodiment, the degree of substitution of hydroxyalkylation is preferably about 0.08 to 0.3, and in another embodiment, the degree of substitution of hydroxyalkylation is more preferably about 0.15-0.25. Is. Hydroxyalkylation of natural starch can be triggered by reacting natural starch with an alkylene oxide having the appropriate number of carbon atoms. In certain embodiments, hydroxyethylated starch and / or hydroxypropylated starch, obtained by reacting starch with ethylene oxide or propylene oxide, is particularly preferred. Starch to be used according to the present invention may also contain more than one hydroxyl group per alkyl group.
In certain embodiments, a particularly preferred modified starch for the present invention is crosslinked hydroxypropyl phosphate distarch or crosslinked acetylated adipate distarch.

The crosslinked starches of the invention may be hydrophobically modified and are themselves one or more aliphatic or aromatic, saturated or unsaturated, straight chain, branched chain, or cyclic. of,
It _{may be substituted by a hydrocarbon-based chain of C 8 to} C ₃₀ , particularly by a hydrophobic group containing 8 to 30 carbon atoms. In another embodiment, the hydrophobic substituent used is C _{8 to} C ₃₀ , preferably C _{8 to} C ₂₂ in another embodiment, an alkyl group, an alkenyl group, an arylalkyl group, or an alkylaryl group. , And combinations thereof. In certain embodiments, the hydrophobic substituents are C _{8 to} C ₂₂ alkenyl chains, preferably C _{8 to} C ₁₂ alkenyl chains, such as octenyl (unsaturated C ₈ ) groups and straight or branched dodecenyl (unsaturated). Saturated C ₁₂ ) groups and the like. In certain embodiments, the hydrophobic groups are derived from natural sources, including, but not limited to, tall oil, tallow, soybeans, coconut palm, and palm oil. In certain embodiments, the hydrophobic substituent according to the invention is an octenyl group or a dodecenyl group. The hydrophobic modifier may be attached to the starch substrate by an ether bond, an ester bond, or a urethane bond. Ester bonds are preferred. Modification reagents include, but are not limited to, octenyl succinic anhydride and dodecenyl anhydride.

In certain embodiments, the crosslinked modified starch to be used according to the present invention is gelatinized. For the present invention, the term "gelatinized starch" includes "pre-gelatinized starch", "pre-pasted starch", and "cold water swollen starch". The term "gelatinized" starch refers to swollen starch granules that have lost their birefringent crosses in polarized light. The gelatinized modified starch is soluble in cold water without heating. In this context, "soluble" does not necessarily mean the formation of a true molecular solution, but also means that a colloidal dispersion can be obtained. The crosslinked modified starch to be used according to the present invention is preferably completely gelatinized.

The modified granular starch can be gelatinized in water by heating above the gelatinization temperature.
Some non-limiting examples of gelatinization are bath heating, steam injection heating, jet heating (at a pressure of about 10 to about 150 PSI), and extrusion. By gelatinizing granular starch
It is believed that the functionality as a component of the emulsion stabilizer can be obtained.
The starch of the present invention can be heated at various temperatures and concentrations to give a functional colloidal suspension. In one embodiment of the invention, the starch is heated at about 90 ° C to about 200 ° C. In another embodiment, the starch is heated at about 100 ° C to about 150 ° C. Depending on the heating method, the limits of starch concentration in water will depend on factors such as viscosity, heat transfer, and solution stability. In certain embodiments of the invention, starch is about 1-
Heated to a concentration of about 40% by weight (% by weight), in another embodiment the starch is heated to a concentration of about 2% by weight to about 30% by weight, and in yet another embodiment from about 3% by weight. About 1
It will be heated to a concentration of 5% by weight, or by yet another embodiment defined by combining the upper and lower limits of these ranges.

The usual processes used to produce such gelatinized starch include, among others, drum drying, extrusion, and spray drying.

Drum drying involves simultaneously heating and drying a very viscous, semi-solid starch paste on a heated drum. The dried film is peeled from the drum with a metal blade and then ground. This process can be carried out until a very high solid content is reached.

The extrusion can also be used to simultaneously heat and dry the starch (see US Pat. No. 3,137,592, which is incorporated herein by reference in its entirety). This process causes starch gelatinization at high temperature and pressure.
It utilizes the physical treatment of the water mixture, which subsequently leaves the nozzle and then rapidly evaporates and expands the water.

The use of gelatinized crosslinked modified starch makes it possible to produce the starch at ambient temperature or at a temperature significantly lower than the production conditions used for known starch-containing compositions. In certain embodiments, the gelatinized crosslinked starch is preferably produced by spray drying.

In certain embodiments, the crosslinked modified starch to be used according to the present invention is mostly intact starch granules. An aqueous dispersion of gelatinized crosslinked starch having a mostly intact granular structure is, for example, an aqueous dispersion of non-granular starch obtained by a dry starch solution in which the dispersion has a slightly grainy feel. Has a more homogeneous and smooth feel. In the case of gelatinized starch having an intact granular structure, the original internal structure of hydrogen bonds is destroyed, but the outer shape or shape is maintained.

A particularly preferred spray-dried gelatinized starch production process is U.S. Pat. No. 4,280,8.
It is described in the specification No. 51 (which is incorporated herein by reference in its entirety). Equipment adapted to perform the process is described in US Pat. No. 4,600,472 (US Pat. No. 4,600,472).
By reference in its entirety is also incorporated herein). In this process, the mixture of granular starch or modified starch is heated or gelatinized in a sprayed state.
The starch to be heated is sprayed into the nozzle device through the spray port to form a relatively finely divided spray material. In addition, the heating medium is sprayed into the sprayed material through an opening in the nozzle device to heat the starch to the temperature required for gelatinization.
The closed chamber surrounds the inlet for the spray and heating medium and shapes the vents arranged so that the heated starch spray material exits the chamber. The device is designed to define the gelatinization time of starch while the starch spray material passes through the chamber, i.e., from the spray port to the ventilation port. The resulting spray-dried gelatinized starch contains pitted, spherical, uniformly gelatinized starch granules, most of which are complete, undamaged and swell after hydration. Nozzles that can be used to make such starches are also described in US Pat. No. 4,610,760, which is incorporated herein by reference in its entirety.

U.S. Pat. No. 5,149,7 to produce suitable gelatinized or modified starch
You can also use the process of specification 99, which is incorporated herein by reference in its entirety. In this process, the starch is uniformly sprayed and heated by a single spraying step in the presence of an aqueous medium. The spraying step is performed in a device equipped with an internal mixed two-fluid spray drying nozzle, which is connected to a device for drying the heated spray starch.

Spray-dried, gelatinized or modified starch with suitable properties is continuous,
It can also be manufactured by a process in which jet heating and spray drying are combined. The starch suspension is gelatinized at 138 ° C to 160 ° C in a jet heating device with direct steam injection. The starch suspension stream and the steam stream are mixed in a heating or boiling chamber.
The latter outlet is connected to a compressed air spray nozzle or a high pressure nozzle installed in a normal spray dryer. The jet-heated starch is guided into the spray nozzle at high temperature and high pressure,
It may be sprayed with cold air, hot air, or preferably steam. After spraying, the hot, jet-heated starch solution is treated in the same manner as regular spray-dried starch. The drying process is fast enough to prevent the starch molecules from retrograding while cooling and drying the droplets. The spray-dried starch is an amorphous material (ie, substantially amorphous) and can be soluble in water or dispersed colloidally.

In certain embodiments, the crosslinked modified starch according to the invention can be provided as a dry powdery composition that is reconstituted in an aqueous medium upon use.

Cross-linked modified starches suitable for use in accordance with the present invention have dermatologically desirable use properties and tactile qualities. The cross-linked modified starch enhances the water retention capacity of the skin and helps to make the skin smooth and supple. Cosmetics containing the emulsion stabilizer of the present invention along with the crosslinked modified starch can be spread very well on the skin without leaving a sticky feel.

Biopolymer Blend In another embodiment, the present invention provides a method for producing an emulsion stabilizer. The method comprises blending a cellulose ether with a crosslinked modified starch to produce a biopolymer blend, wherein one or more of the modified cellulose ethers and the crosslinked modified starch have been modified to be hydrophobic. In certain embodiments, the method comprises cross-linking the starch with one or more cross-linking reagents and, for example, by hydroxyalkylation, prior to blending the cross-linked modified starch with a hydrophobically modified cellulose ether. It may include further modification of the crosslinked starch. In another embodiment, the method comprises modifying the cellulose ether or the crosslinked starch to be hydrophobic with one or more hydrophobic reagents prior to blending the cellulose ether with the starch component. include.

In one embodiment, the total amount of cellulose ether in the biopolymer blend is 5.
It is 0% by weight or less. In one embodiment, the total amount of cellulose ether in the blend is
It is about 5% by weight or more, about 10% by weight or more in one embodiment, and about 20% by weight or more in one embodiment. In one embodiment, the total amount of cellulose ether in the blend is about 45.
By weight or less, about 40% by weight or less in one embodiment, about 30% by weight in another embodiment
Hereinafter, in another embodiment, it is about 25% by weight or less.

Emulsified Personal Care Formulation In general, an emulsion contains a mixture of two immiscible liquid substances, one of which is dispersed in the other (continuous phase). For the present invention, an emulsion is defined as a plurality of oil droplets that are substantially uniformly distributed or dispersed in a liquid medium. Emulsions are usually in this form at room temperature. For some oils whose freezing point is below 100 ° C., the emulsion may be a formulation in which the oil is first dispersed in water, but when cooled to room temperature, the oil solidifies to some extent. There may be. The liquid medium forms a continuous phase and the oil is not soluble in the liquid medium. In certain embodiments, the solubility in a liquid medium is 0.
.. 1% by weight, preferably 0.05% by weight or less. Some non-limiting examples of suitable liquid media include water, ethanol, methanol, isopropanol, glycerol, propylene glycol, or acetone, or mixtures thereof. In one embodiment of the invention, the liquid medium is a mixture of water and one or more of ethanol, methanol, isopropanol, glycerol, glycol, such as propylene glycol, or acetone.

In certain embodiments, the emulsion stabilizers of the present invention can be used to form emulsions containing cosmetically acceptable oils dispersed in water or water-based media.

In another embodiment, the invention comprises an emulsion stabilizer, a surfactant, a cosmetically acceptable oil, and a water or water-based liquid medium, wherein the water or water-based liquid medium is a continuous phase. I will provide a.

In one embodiment of the invention, the emulsion is a personal care composition. In one embodiment of the invention, the personal care composition is a skin care composition. In one embodiment of the invention, the personal care composition is a hair care or hair styling composition. In one embodiment of the invention, the emulsion is a hair styling composition selected from gels, mousses, pomades, and waxes.

In one embodiment of the invention, the emulsion is a skin care composition, a skin cleansing composition,
Makeup, facial lotion, cream moisturizer, body soap, body lotion, foot care products such as foot cream, hand cream, lipstick, lip gloss, lip pencil, eye shadow, gel eye color, eyeliner, eye pencil, nail polish, Concealer, foundation, facial powder, liquid rouge, blusher, deodorant, shaving cream composition, nail polish, gel nail polish remover, cuticle remover, cuticle cream, acne cream,
Acne cleansing scrub, toothpaste, shaving lotion, cream hair remover, lotion hair remover, wax hair remover, facial pack made from clay materials, anti-aging products, shampoos, hair care products such as conditioners, hair treatment creams, styling gels, styling Foams, hair mousses, hair sprays, set lotions, blow styling lotions, hair color lotions and hair dies, hair bleaching creams, hair relaxing compositions, curl-promoting gels, aromatic hair glosses, sun care products such as sun sticks and sunscreens, soaps, hand wash , Hand disinfectant gel, antibacterial hand cleaner, body scrub, hand scrub, foam bath, bath oil, instant hand disinfectant, baby lotion, diaper rash cream, hand wipe, baby bath, and vitamin cream It is a personal care composition.

In certain embodiments of the present invention, the oil is present in at least 10% of the emulsion.
In another embodiment, it is present in an amount of 20% or more of the emulsion, and in yet another embodiment, it is present in an amount of about 30% or more of the emulsion. In one embodiment of the present invention, oil is present in 50% or less of the emulsion and in yet another embodiment 40% or less of the emulsion.

In one embodiment of the invention, the oil droplets in the emulsion have an average particle size of about 0.2 μm.
~ About 100 μm. In another embodiment, the oil droplets have an average particle size of about 0.5 μm to 3
It is 5 μm. In yet another embodiment, the oil droplets have an average particle size of about 1 μm to about 25 μm.
m. In the embodiment of the present invention, the lower limit of the average particle size is 0.2 μm and 0.
It may be 5 μm and 1 μm, with upper limits of 100 μm, 35 μm and 25, respectively.
It may be μm, and the embodiment may be a range in which these lower limit and upper limit are combined. The average particle size can be measured, for example, by a light scattering technique known to those of skill in the art.

In certain embodiments of the invention, cosmetically acceptable oils are not soluble in solvents and have some benefit to the consumer, such as feel, protection, healing, UV protection, occlusion, slippage, hydration, or radical capture. Is the oil that brings about. Cosmetically acceptable oils can be selected from hydrocarbon-based oils and natural oils. Non-limiting examples of cosmetically acceptable oils are palm oil, mineral oil, petroleum jelly, petrolatum, silicone, dimethicone, emu oil, castor oil, squaline, avocado oil, almonds. Oil, coconut oil, cocoa butter, grape seed oil, lanolin, peanut oil, sesame oil, jojoba oil, olive oil, silicone oil, sunflower oil, safflower oil, shea butter, and wheat germ oil.

In certain embodiments of the invention, the cosmetically acceptable oil may be an aerosol propellant.

In one embodiment of the present invention, the concentration of the emulsion stabilizer used in the final product, for example, a skin care product or a hair care product, may be about 1% by weight to about 5% by weight. The concentration of emulsion stabilizer used may be selected in part based on the weight average molecular weight of the cellulose ether component of the blend. In certain embodiments, the cellulose ether is a hydrophobically modified cellulose ether having a molecular weight of about 900,000 or more, the concentration of the emulsion stabilizer used is preferably about 1 with respect to the total weight of the emulsion formulation. From% by weight to about 3% by weight, more preferably from about 1.5% by weight in yet another embodiment.
It is about 2.5% by weight, and in yet another embodiment about 2% by weight. In certain embodiments, where the cellulose ether is a hydrophobically modified cellulose ether having a molecular weight of less than 900,000, the concentration of the emulsion stabilizer used is preferably about 3 weight by weight relative to the total weight of the emulsion formulation. % To about 6% by weight, more preferably from about 4% to about 5.5% by weight in yet another embodiment, and about 5% by weight in yet another embodiment.

Preservatives are often used in personal care formulations to provide long-term storage stability, especially microbiological storage stability. Suitable preservatives include, for example, methylparaben, propylparaben, butylparaben, DMDM hydantin, imidazolidinyl urea, gluteraldehyde, phenoxyethanol, benzalconium chloride, methaneammonium chloride, benzethonium chloride, benzyl alcohol, chlorobenzyl alcohol. , Methylchloroisothiazolinone, methylisothiazolinone, sodium benzoate, chloracetamide, triclosan, iodopropynylbutylcarbamate, sodium pyrithione, pyrithione zinc, and other cosmetically acceptable preservatives known to those of skill in the art. can give.

Various other additives, as well as active and functional ingredients, may be included in the cosmetic composition as set forth herein. Not limited to these, palliatives, wetting agents, thickeners, surfactants, UV light blocking agents, fixing polymers, pigments, dyes, colorants, α-hydroxy acids,
Esthetic enhancers such as starch, perfumes and fragrances, coating film forming agents (waterproofing agents), preservatives, antifungal agents, antimicrobial agents, and other pharmaceuticals, as well as solvents.

Examples of the surfactant useful in the present invention include nonionic surfactants and amphoteric surfactants. Nonionic surfactants that can be used include polyoxyethyleneylated alcohols, polyoxypropyleneylated alcohols, or polyglycerolylated alcohols, 8
Alkylphenols and fatty acids with linear fatty chains containing ~ 22 carbon atoms and usually 2-30 mol of ethylene oxide, fatty acid amides, alkoxylated fatty alcohol alcohol amines, fatty acid esters, glycerol esters, alkoxylated fatty acid esters, sorbitan esters, Examples thereof include alkoxylated sorbitan esters, alkylphenol alkoxylates, aromatic alkoxylates, and alcohol alkoxylates. Similarly, copolymers of ethylene oxide and propylene oxide, condensates of ethylene oxide and propylene oxide with fatty alcohols, polyoxyethylated fatty amides or amines, ethanolamides, fatty acid esters of glycols, oxyethylated or non-oxyethylated sorbitan. Fatty acid esters, fatty acid esters of sucrose, fatty acid esters of polyethylene glycol, phosphate triesters and fatty acid esters of glucose derivatives are also useful.

In addition to the personal care formulation, the emulsion stabilizer of the present invention can also be used for various industries and applications. Such industries include, for example, auxiliaries in petroleum mining, such as laundry applications, crop protection, agricultural formulations, asphalt stabilizers, or coating auxiliaries.

Next, the present invention will be described by the following non-limiting examples. In the examples, the cellulose ether used is a hydrophobically modified ethyl hydroxyethyl cellulose product, but it is not intended to limit the present invention to it, and those skilled in the art will use these methods from the teachings of the present specification. You will understand how to adapt to the preparation of solutions and emulsions with other hydrophobically modified cellulose ethers in this way.

Emulsion Preparation Procedures Emulsions have been prepared according to the exemplary preparation procedures below, but one of ordinary skill in the art will understand how to adjust the amount of each reagent to other concentrations and amounts that may be desirable. Will.

a. Preparation of HM-EHEC mother liquor (4% by weight)
Hydrophobically modified ethyl hydroxyethyl cellulose ether (HM-EHEC) 2 g
Weigh and slowly disperse in 48 g of water at ambient temperature using an overhead mixer and stirring at 400 rpm using a flat blade.
After adding HM-EHEC, heating of the aqueous mixture is started. At a temperature of 75 ° C, set the timer to 15 minutes and run once. When the solution thickens, rotate 250-300 rp
Drop to m.
Make up for lost water and add preservatives.
Stir for a few more minutes at ambient temperature.

b. Preparation of cross-linked modified starch mother liquor (6% by weight)
3 g of modified starch is weighed and the modified starch is slowly dispersed in 47 g of water at ambient temperature using an overhead mixer and stirring at 400 rpm using a flat blade.
After adding the modified starch, heating of the aqueous mixture is started. At a temperature of 90 ° C, set the timer to 15 minutes and run once. When the polymer solution thickens, rotate 250-30
Drop to 0 rpm. Make up for lost water and add preservatives. Stir for a few more minutes at ambient temperature.

c. Emulsion (0.75% HM-EHEC and 1.25% modified starch and 30%
Oil example)
0.5449 g of SPAN® 80 surfactant, in a 4 oz glass jar,
0.2496g TWEEN® 40 Surfactant, 0.49655g Glyd
Weigh in sequence an ant® preservative, 28.9159 g of deionized water, and 29.7931 g of oil.
The mixture was mixed with IKA with a mixing head S25N-25F (dispersion element).
Using WRKE's Ultra Turrax® T25, 13,500 rm
Homogeneize at p for 120 seconds. Leave 30.2083 g of the homogenized mixture in the jar.
At the top of the jar containing the homogenized mixture, a mixing process using a flat-blade stirrer is placed on the emulsion and stirred using an overhead mixer at about 300 rpm.
9.3750 g (4% by weight) of the HM-EHEC stock solution and 10.4167 g (6% by weight) of the modified starch stock solution prepared in a and b are added. Mix at 300 rpm for an additional 10 minutes.
The emulsion for further evaluation weighs about 50 g in total.

Emulsion Stability For the present invention, emulsion stability was quantitatively measured using a TURBISCAN® LAB Stability Analyzer. This analyzer was used to obtain the first backscatter signal for each sample emulsion formulation. The emulsion product was then stored at 45 ° C. and scanned regularly for about 1 month. The backscatter signal measured over time was compared to the signal of the first sample. More specifically, if the maximum difference between the subsequent backscatter signals relative to the first backscatter signal is greater than 5%, the number of days until the backscatter signal reaches this 5% difference is stable. Degree, or "Turbiscan (
Recorded as "Registered Trademark) Time". The longer this time, the more stable the emulsion. This technique makes it possible to detect potential instability long before the instability becomes visually observable.

The rheological stability of the aqueous phase was also confirmed by monitoring the rheological behavior of the aqueous phase, which is an indicator of the potential retrogradation of the polysaccharide blend. The sample aqueous solution was aged at room temperature (about 20 ° C.) because the retro-gradation is more intense at low temperatures. Aqueous rheology was measured over a month to monitor potential retro-gradation. The rheological and microscopic structures of the aqueous phase, these properties are believed to reflect important roles and effects in emulsion stability (Russel, WB,
Saville, DA, and Schowalter, WR (1989), "Colloidal Dispersions" (Cambridge Mo)
nographs on Mechanics), Cambridge University Press, Cambridge, UK)
..

Two types of rheology tests were performed. Vibration rheology measurements were performed at 20 ° C. and 5% strain. The frequency was varied from 0.1 rad / sec to 100 rad / sec. 0
.. Modulus and complex viscosity values at 2 rad / sec were recorded. Shear viscosity measurement
Shear rate at 20 ° C. from about 0.1 rad / sec or about 0.2 rad / sec to about 10
It was carried out by changing to 0 rad / sec. As a rheometer, a Rheometers rheometer (Rheometers Scientific, model number SR-5000) was used.

Determination of molecular weight of modified cellulose ether a. MEHEC
Equipment: GPCm equipped with TeleDirector Array (TDA502)
ax (both made by Malvern)
Mobile phase: 0.05M sodium acetate, 0.02% by weight sodium azide, pH 6 (acetic acid)
Column: 2 x TSK GMPWXL 7.8 x 300 mm + pre-column (Tosoh)
Bioscience)
Flow rate: 0.5 ml / min Injection amount: 100 μl
Column temperature: 35 ° C
Detection: Refractive index, light scattering (7 ° and 90 °), and viscosity applied dn / dc: 0.148

All samples were dissolved in the mobile phase, shaken overnight and 0.45 μm prior to SEC analysis.
Filtration was performed with an m syringe filter (regenerated cellulose membrane, GE Healthcare).
Typical concentrations were 0.5-1 mg / ml.

Pullulan standard sample with narrow molecular weight distribution (Mn = 100,000, Mw = 112000, IV
= 0.458 dl / g, dn / dc = 0.144, Shodex) was used to calibrate the detector. The dn / dc (coefficient required for calibration of the molecular weight distribution) was set to 0.148, which is a typical value for cellulose ethers.

b. HM-EHEC
The mobile phase is 0.5% by weight RAMEA, 0.05M sodium acetate, 0.02% by weight.
Same as for EHEC, except that it is added to sodium azide and pH 6 (acetic acid). RAMEA represents a randomly methylated cyclodextrin α (Cyclolab).

Example 1 Effect of molecular weight on emulsion stability Ethyl hydroxyethyl cellulose modified to be hydrophobic on emulsion stability (H)
Experiments were performed to determine the effect of the molecular weight of M-EHEC). 1.5% cross-linked hydroxylpropyl modified waxy potato starch, also known as type "A" starch, is shown in Table 1.
0 for each of the three different types of hydrophobic EHEC samples, as shown in
.. Blended at a concentration of 5%. The three different types of hydrophobic EHEC samples had MS _EO of 2.4 or higher and DS _ethyl of 0.8 or higher, respectively. Each formulation is 0.25% Tween® 40 (nonionic ethoxylated (20) sorbitan ester surfactant, available from Croda Inc. (Edison, New Jersey)), and 0.55%. It also contained Span® 80 (a nonionic sorbitan oleate surfactant, available from Croda Inc. (Edison, New Jersey)). 30% triglyceride-based oil in the form of safflower oil, and 0
.. 5% Glydant® (preservative, available from Lonza, Inc. (Allendale, NJ)), residual water. The data in Table 1 is 1,000,000.
It is shown that HM-EHEC with a super molecular weight results in higher emulsion stability performance.

Example 2
Effect of starch modification-miscibility with water EHE modified to hydrophobicity named HM-EHEC1 as used in the preparation 1.
A sample of C was blended with each of the four different types of starch, and the blend was blended with 0.2% Tween 80, 30% tetradecane, 0.5% Glydant® preservative, and residual water as well. Used to prepare the emulsion containing. The data in Table 2 show that cross-linked modified starch provides better long-term emulsion stability compared to unmodified non-cross-linked starch.

Example 3
Effect of starch modification-crosslinking EHE modified to hydrophobicity named HM-EHEC1 as used in the preparation 1.
Samples of C were blended with different types of starch in different proportions, as shown in Table 3, and the blends were blended with 0.2% Tween 80, 30% tetradecane, 0.5% Gl.
It was used to prepare an emulsion containing a ydant® preservative and residual water. The pharmaceutical product 8 is the composition of the present invention, and the pharmaceutical products 9 to 11 are comparative examples. The data in Table 3 is
It is shown that a biopolymer blend of highly viscous hydrophobically modified cellulose ether and crosslinked starch, wherein the total amount of cellulose ether in the biopolymer blend is 50% by weight or less, provides good long-term stability. On the other hand, a biopolymer blend of the same hydrophobically modified cellulose ether and the same crosslinked starch, wherein the total amount of the cellulose ether in the biopolymer blend is more than 50% by weight is sufficient. It did not provide long-term stability. Similarly, a biopolymer blend of the same hydrophobically modified cellulose ether with uncrosslinked and unmodified starch did not provide sufficient long-term stability.

The composition corresponding to each aqueous phase of the pharmaceutical products 8 to 11 was prepared. These aqueous compositions,
They are named Formulations 8A to 11A, respectively, and are shown in Table 3A.

The rheology of the aqueous formulations 8A to 11A was measured according to the above procedure when the formulations were first prepared and then stored at a temperature of 22 ° C. for 1 month. FIG. 1 shows the formulations shown in Table 3A.
The change in elastic modulus is shown. The frequency was 0.2 rad / sec. FIG. 2 shows the change in complex viscosity of the pharmaceutical products shown in Table 3A. The frequency was 0.2 rad / sec. These figures show that when HM-EHEC1 is blended with crosslinked modified starch, as in formulations 8A and 9A, the change in rheological properties over time is very small. The changes in rheological properties exhibited by the product 10A and the product 11A using the starch which has not been modified or crosslinked are as follows.
It was extremely large.

Example 4
Stability of Triglyceride-Based Emulsion EHE modified to be hydrophobic, named HM-EHEC1 as used in Formula 1.
The sample of C was blended with the crosslinked starch in three different proportions, and the blend was blended.
0.25% Tween® 40 (nonionic ethoxylated (20) sorbitan ester surfactant, available from Croda Inc. (Edison, New Jersey)), 0.55% SSpan® 80 (Nonionic Sorbitan Oleate Surfactant, available from Croda Inc. (Edison, New Jersey)), 30% triglyceride-based oil in the form of safflower oil, 0.5% Glydant®. ) Used to prepare an emulsion containing preservatives and residual water. In each preparation, the weight ratio of the hydrophobically modified cellulose ether to the modified crosslinked starch was about 1: 1 or less. The data in Table 4 show that the blend of HM-EHEC1 and crosslinked starch A provides excellent emulsion stability for triglyceride-based (ie, safflower oil) emulsions.

Example 5
Salt Sensitivity of Emulsions Containing Modified Polysaccharide Blends Determines whether the presence of cosmetically acceptable salts commonly used in personal care formulations affects the rheological properties of aqueous emulsion stabilizers of the invention. In order to do so, an experiment was carried out. 3 and 4 show HM-EH in the pharmaceutical product 8A of Table 3A, respectively.
The salt sensitivity of the polymer blend aqueous solution of EC1 and starch A is shown. In the solution composition, 0.
Add 2% EDTA disodium. As shown in these charts, the rheology of this polymer solution is insensitive to the addition of salts, in this particular case to the addition of EDTA disodium. FIG. 3 shows the change in elastic modulus for the pharmaceutical product 8A with and without EDTA disodium. FIG. 4 shows the change in complex viscosity for the pharmaceutical product 8A with and without EDTA disodium. The data in FIGS. 3 and 4 are advantageously 0.2.
It is shown that the presence of% EDTA disodium has no significant effect on either the modulus of elasticity or the complex viscosity of the formulation.

Further experiments were performed to determine if other concentration levels of salt affect the rheological properties of aqueous solutions containing the emulsion stabilizers of the invention. Table 3 above, except that the sample of the product 8A had a NaCl concentration of 0%, 1%, 5%, 10%, and 15%.
Rheology was measured in the form of shear viscosities of 0.2 rad / sec to 100 rad / sec. The data in FIG. 5 are still remarkable for the shear viscosity of the aqueous composition containing the emulsion stabilizer of the present invention, as compared to the composition having a NaCl content of 0%, even when the salt concentration is as high as 15%. It shows that it does not have any effect. Due to this lack of salt sensitivity, there is no need to worry that the presence of salt will disrupt the rheological behavior of the final product, so when the emulsion stabilizer of the present invention is used, the composition, eg personal It is possible to increase the degree of freedom in determining the final composition of the care product.

Example 6
Tactile Characteristics In the examples in Table 5 below, more desirable tactile characteristics are realized when HM-EHEC1 is blended with crosslinked modified starch, that is, starch A, as compared with the case where HM-EHEC1 is used alone. Show that.

The hydrophobically modified cellulose ether generally has a higher viscosity and modulus than crosslinked starch and can theoretically be used alone as an emulsion stabilizer. However, in practice, the hydrophobically modified cellulose ethers have undesired tactile quality when used in personal care formulations. Provided is an emulsion stabilizer containing a cellulose ether modified to be hydrophobic enough to achieve the desired emulsion stability, but not so hydrophobic that the final product is not acceptable to consumers in terms of tactile quality. Is an issue. In addition, cross-linked modified starch not only overcomes the unwanted tactile properties associated with hydrophobically modified cellulose ethers, but also cream-separates or cineresis (
It must also be present in sufficient quantity to increase the gel strength (G') to overcome the gravitational effect).

Five formulations containing various amounts of hydrophobically modified cellulose ether and modified cross-linked starch were prepared and evaluated for tactile properties. Each formulation is 0.25% Tween® 4
0 (nonionic ethoxylated (20) sorbitan ester surfactant, Croda In
c. , (Available from Edison, NJ), 0.55% Span® 80 (Nonionic Sorbitan Oleate Surfactant, available from Croda Inc. (Edison, NJ)). Was. 30 in the form of safflower oil
% Triglyceride-based oil, 0.5% Glydant preservative, and residual water. Each composition is shown in Table 6. According to this study, the total polymer concentration was 2%, and in the total polymer,
Biopolymer blends with modified starch of 50% and about 75% give the desired texture.

Five panelists were asked to rank each of the two formulations according to the plans shown in Table 6. 30 μL of a sample of each formulation was applied to the inside of each panelist's pre-washed forearm. The panelists rubbed the formulation into the skin for 20 seconds and chose which of the two samples was tactilely preferred. For example, when the panelist is given two formulations, namely X and Y, if the panelist thinks that Y is superior to X, the formulation Y is given a score of 2 and the formulation X is given a score of 1. rice field. The overall ranking of each pharmaceutical product is the total of each test by each panelist, which is shown as the overall ranking in Table 6 and is shown in FIG. The difference in ranking over 2.9 is
It was judged to be a statistically significant difference. Differences of 2.9 or less indicated that there was no statistical difference.

The above results indicate that the pharmaceutical product 16 is the highest in terms of tactile quality. The result is
It is surprising that a formulation containing a hydrophobically modified cellulose ether in addition to starch would not have been expected to have at least comparable tactile quality, if not better than a starch-only formulation. It should be. It was not expected that replacing some of the starch with hydrophobically modified cellulose ethers would lead to improved tactile properties. The pharmaceutical product 15 provides good tactile quality, but would not be expected to function as an emulsion stabilizer that provides long-term stability in the absence of any hydrophobically modified cellulose ether.

Example 7
Stability of Triglyceride-based Emulsion Containing High Concentrations of Low Molecular Weight, Hydrophobic Modified EHEC Samples of low molecular weight, but highly hydrophobic modified EHEC samples are similarly crosslinked at high concentrations. Blended with starch to produce an emulsion formulation based on safflower oil, as shown in Table 7. Both Formulation 20 and Formulation 21 are 0.25% Tween® 40 (nonionic ethoxylated (20) sorbitan ester surfactant, Croda.
Inc. (Available from Edison, NJ), 0.55% Span (
Registered Trademark) 80 (Nonionic Sorbitan Oleate Surfactant, Croda Inc. (
(Available from Edison, NJ)), in the form of safflower oil, contained 30% triglyceride-based oil, 0.5% Glydant® preservative, and residual water. 2.4% HM-EHEC (see Table 1) and 2.6% for each formulation.
Starch A is used. The data in Table 7 are triglyceride-based (ie, triglyceride-based (i.e.,) when blends of either HM-EHEC, which has a lower molecular weight than HM-EHEC1, and crosslinked modified starch A, are used in appropriate additions to the emulsion composition. Safflower oil) Shows that it provides excellent emulsion stability to emulsions.

All documents cited in the form for carrying out the invention are incorporated herein by reference with respect to the relevant parts, and any citation of any document should be construed as an admission that it is prior art to the invention. No.

Although specific embodiments of the invention have been shown and described herein, it is not intended to limit the invention to the details shown. Rather, various modifications may be made to the above details within the scope of the claims and their equivalents without departing from the spirit and scope of the present invention.

Although specific embodiments of the invention have been shown and described herein, it is not intended to limit the invention to the details shown. Rather, various modifications may be made to the above details within the scope of the claims and their equivalents without departing from the spirit and scope of the present invention.
The present invention includes the following aspects.
Item 1.
Emulsion stabilizer
A blend of one or more cellulose ethers and one or more crosslinked starches, wherein the one or more cellulose ethers are hydrophobically modified and the cellulose ethers in the blend. Emulsion stabilizer having a total amount of 50% by weight or less.
Item 2.
Item 2. The emulsion stabilizer according to Item 1, wherein the one or more cellulose ethers are hydrophobically modified nonionic cellulose ethers.
Item 3.
The nonionic cellulose ether is methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, methyl ethyl hydroxyethyl cellulose, propyl hydroxyethyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl ethyl cellulose, hydroxypropyl propyl cellulose. Item 2. The emulsion stabilizer according to Item 2, selected from the group consisting of hydroxypropyl hydroxyethyl cellulose, methyl hydroxypropyl hydroxyethyl cellulose, hydroxypropyl cellulose, and mixtures thereof.
Item 4.
Item 3. The emulsion stabilizer according to any one of Items 1 to 3, wherein the cellulose ether modified to be one or more hydrophobic has a weight average molecular weight of 900,000 or more.
Item 5.
Item 6. The emulsion stabilizer according to any one of Items 1 to 4, wherein the cellulose ether of one or more is derived from hardwood pulp, softwood pulp, cotton raw material including cotton linter, bacterial cellulose, or regenerated cellulose. ..
Item 6.
Item 6. The emulsion stabilizer according to any one of Items 1 to 5, wherein the crosslinked starch is hydrophilic.
Item 7.
Item 6. The emulsion stabilizer according to any one of Items 1 to 6, wherein the crosslinked modified starch is soluble in water.
Item 8.
Item 6. The emulsion stabilizer according to any one of Items 1 to 7, wherein the crosslinked starch is derived from corn, wheat, rice, great millet, pea, potato, tapioca (cassava), sweet potato, and sago.
Item 9.
Item 6. The emulsion stabilizer according to any one of Items 1 to 8, wherein the crosslinked starch has an amylopectin content of more than 90%.
Item 10.
A personal care preparation containing an oil-in-water emulsion and the emulsion stabilizer according to any one of Items 1 to 9, wherein the emulsion stabilizer is about 1% by weight based on the total weight of the preparation. ~ A personal care product that is present in an amount of about 6% by weight.
Item 11.
The one or more hydrophobically modified cellulose ethers have a weight average molecular weight of 900,000 or more, and the emulsion stabilizer is about 1% by weight to about 1% by weight based on the total weight of the pharmaceutical product. Item 2. The personal care preparation according to Item 10, which is present in an amount of 3% by weight.
Item 12.
The one or more hydrophobically modified cellulose ethers have a weight average molecular weight of less than 900,000, and the emulsion stabilizer is about 3% by weight to about 3% by weight based on the total weight of the pharmaceutical product. Item 10. The personal care preparation according to Item 10, which is present in an amount of 6% by weight.
Item 13.
Item 6. The personal care preparation according to any one of Items 10 to 12, wherein the personal care preparation is a hair styling composition.
Item 14.
Item 6. The personal care preparation according to any one of Items 10 to 13, wherein the oil is selected from a hydrocarbon-based oil and a natural oil.
Item 15.
Item 6. The personal care preparation according to any one of Items 10 to 14, wherein the oil is about 10 to 50% by weight of the emulsion.

Claims (15)

Emulsion stabilizer
A blend of one or more cellulose ethers and one or more crosslinked starches, wherein the one or more cellulose ethers are hydrophobically modified and the cellulose ethers in the blend. Emulsion stabilizer having a total amount of 50% by weight or less. The emulsion stabilizer according to claim 1, wherein the one or more cellulose ethers are hydrophobically modified nonionic cellulose ethers. The nonionic cellulose ether includes methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, methyl ethyl hydroxyethyl cellulose, propyl hydroxyethyl cellulose, hydroxypropyl methyl cellulose, and the like.
The emulsion stabilizer according to claim 2, which is selected from the group consisting of hydroxypropylethyl cellulose, hydroxypropylpropyl cellulose, hydroxypropyl hydroxyethyl cellulose, methyl hydroxypropyl hydroxyethyl cellulose, hydroxypropyl cellulose, and a mixture thereof. The above-mentioned one or more hydrophobically modified cellulose ethers are 900,000.
The emulsion stabilizer according to any one of claims 1 to 3, which has the above weight average molecular weight. The emulsion stabilization according to any one of claims 1 to 4, wherein the cellulose ether of one or more is derived from hardwood pulp, softwood pulp, cotton raw material including cotton linter, bacterial cellulose, or regenerated cellulose. Agent. The emulsion stabilizer according to any one of claims 1 to 5, wherein the crosslinked starch is hydrophilic. The emulsion stabilizer according to any one of claims 1 to 6, wherein the crosslinked modified starch is soluble in water. The emulsion stabilizer according to any one of claims 1 to 7, wherein the crosslinked starch is derived from corn, wheat, rice, great millet, pea, potato, tapioca (cassava), sweet potato, and sago. The emulsion stabilizer according to any one of claims 1 to 8, wherein the crosslinked starch has an amylopectin content of more than 90%. A personal care preparation containing an oil-in-water emulsion and the emulsion stabilizer according to any one of claims 1 to 9, wherein the emulsion stabilizer is about 1 weight based on the total weight of the preparation. A personal care product that is present in an amount of% to about 6% by weight. The above-mentioned one or more hydrophobically modified cellulose ethers are 900,000.
The personal care preparation according to claim 10, wherein the emulsion stabilizer has the above weight average molecular weight and is present in an amount of about 1% by weight to about 3% by weight based on the total weight of the preparation. The above-mentioned one or more hydrophobically modified cellulose ethers are 900,000.
The personal care preparation according to claim 10, wherein the emulsion stabilizer has a weight average molecular weight of less than about 3% by weight to about 6% by weight based on the total weight of the preparation. The personal care preparation according to any one of claims 10 to 12, wherein the personal care preparation is a hair styling composition. The personal care preparation according to any one of claims 10 to 13, wherein the oil is selected from a hydrocarbon-based oil and a natural oil. The personal care preparation according to any one of claims 10 to 14, wherein the oil is about 10 to 50% by weight of the emulsion.

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