Cosmetic composition containing biodegradable cellulose ester microparticles

Abstract

The present invention provides a cosmetic composition containing biodegradable microparticles prepared from a biodegradable mixed cellulose ester. More specifically, it provides a cosmetic composition containing environmentally friendly cellulose-based microparticles that can be used in a wide range of cosmetic and personal care applications and that can provide high cosmetic properties.

Description

[Background technology]

[0001] Particulate matter refers to particles with a diameter of less than 1 millimeter (mm). Such particles may be found in consumer products such as personal care products and cosmetics. Many products containing such particulate matter are designed to be washed off the user's body after application. When particulate matter-containing products are washed off the user's body, the particles are discharged into drainpipes and collected by local water treatment facilities. To date, many known particulate matter has been formed from plastic or polymer materials, such as polyethylene, polypropylene, polymethyl methacrylate, nylon, and polyurethane. These materials generally have limited biodegradability. Furthermore, due to their small size, the likelihood of them being captured by water treatment facilities is limited, and as a result, the particles may be released from the facilities into larger bodies of water (e.g., rivers, seas, and oceans). Once in these larger bodies of water, plastic or polymer particulate matter can be taken up by wildlife or cause other environmental concerns. Therefore, recent research is being conducted to see if particulate matter can be produced from more environmentally friendly materials. On the other hand, consumers tend to have high expectations regarding the personal care products and / or cosmetics they use, and some of these products contain microparticles.

[0002] Therefore, it is desirable to develop a commercially desirable cosmetic composition containing biodegradable microparticles that meets the high expectations of everyday consumers. [Overview of the project]

[0003] In one embodiment, the present technology relates to a cosmetic composition comprising biodegradable microparticles, wherein the biodegradable microparticles comprise a mixed cellulose ester. The biodegradable microparticles exhibit at least 50% biodegradation in 60 days according to at least one of the OECD301B, OECD301C, or OECD301F test methods. Furthermore, the mixed cellulose ester comprises (a) an average degree of substitution of acetyl substituents in the range of 0.1 to 2.3 ("DS").Ac (b) The average degree of substitution for the propionyl substituent is in the range of 0.1 to 1.5 ("DS Pr ) or the average degree of substitution for butyryl substituents in the range of 0.1 to 1.5 ("DS Bu (c) For hydroxyl substituents, the average degree of substitution is in the range of 0.6 to 2.8 ("DS OH It has ''.

[0004] In one embodiment, the technology relates to a cosmetic composition comprising 0.5 to 15% by weight of biodegradable microparticles, wherein the biodegradable microparticles comprise a mixed cellulose ester. In the embodiment, the biodegradable microparticles also exhibit at least 50% biodegradation in 60 days according to at least one of the OECD 301B, OECD 301C, or OECD 301F test methods, and have a particle size of 0.1 to 100 or 1 to 20 m 2 It has an average BET surface area within the range of / g. Furthermore, in embodiments, the mixed cellulose ester has an average degree of substitution (DS) of acetyl substituents within the range of 0.1 to 2.3 or 1.5 to 2.3. Ac (b) The butyryl substituent has an average degree of substitution in the range of 0.1 to 1.5 or 0.1 to 0.3 ("DS Bu (c) The hydroxyl substituent has an average degree of substitution in the range of 0.6 to 2.8 or 0.6 to 1.0 ("DS OH It has ''.

[0005] In one aspect, the present technology relates to a method for preparing a cosmetic composition comprising biodegradable microparticles. Generally, the method includes (a) providing a plurality of biodegradable microparticles comprising a mixed cellulose ester, wherein the biodegradable microparticles exhibit a biodegradation degree of at least 50% in 60 days according to at least one of the OECD 301B test method, the OECD 301C test method, or the OECD 301F test method, and the method further includes (b) preparing a preliminary cosmetic mixture by mixing the biodegradable microparticles with one or more cosmetic additives, and (c) preparing a cosmetic composition from the preliminary cosmetic mixture. Further, the mixed cellulose ester has (a) an average degree of substitution ( "DS Ac ") in the range of 0.1 to 2.3 for acetyl substituents, (b) an average degree of substitution ( "DS Pr ") in the range of 0.1 to 1.5 for propionyl substituents or an average degree of substitution ( "DS Bu ") in the range of 0.1 to 1.5 for butyryl substituents, and (c) an average degree of substitution ( "DS OH ") in the range of 0.6 to 2.8 for hydroxyl substituents. BRIEF DESCRIPTION OF THE DRAWINGS

[0006] [Figure 1] It is a schematic diagram showing an exemplary process for manufacturing cellulose ester microparticles. [Figure 2] It is a more detailed schematic diagram showing an exemplary process for manufacturing cellulose ester microparticles. [Figure 3] It is a schematic diagram showing another process for manufacturing cellulose ester microparticles by continuous particle formation. [Figure 4] It is a schematic diagram showing another process for manufacturing cellulose ester microparticles by preparing a dope and an aqueous mixture respectively, and performing the preparation of an emulsion / dispersion and particle hardening together. [Figure 5] It is a schematic diagram showing another process for manufacturing cellulose ester microparticles by preparing a composite emulsion / dispersion. [Figure 6]This is a schematic diagram illustrating another process for producing cellulose ester nanoparticles by combining emulsion / dispersion preparation and particle curing. [Figure 7] This is a schematic diagram illustrating another process for producing cellulose ester nanoparticles by removing the solvent before particle hardening. [Modes for carrying out the invention]

[0007] This disclosure relates to cosmetic compositions prepared using biodegradable cellulose ester microparticles that exhibit superior properties compared to conventional microparticles. The process disclosed herein allows for control of the solidity of the microparticles to be produced so that microparticles with desired properties can be obtained. Alternatively, microparticles produced by mechanically micronizing or reducing the size of bulk cellulose ester (immediately after production) can also yield CE microparticles with desirable properties. Because CE is biodegradable along with these qualities, the CE microparticles produced herein are desirable for use in cosmetic compositions.

[0008] The present invention can be more readily understood by referring to the following detailed description and examples provided herein. Naturally, this disclosure is not limited to the specific methods, formulations, and conditions described, and therefore may vary. Furthermore, naturally, the terms used herein are solely for the purpose of describing specific aspects of the disclosed embodiments and are not intended to limit them.

[0009] Values ​​may be expressed as "about" or "approximately" a given number. Similarly, ranges may be expressed herein as "about" one particular value to and / or "about" another particular value. Where such ranges are expressed, another aspect includes that one particular value to and / or other particular values. Similarly, where "about" is used before a value and the value is expressed as an approximation, as is clear, that particular value takes on another aspect.

[0010] As used herein, the terms "a," "an," and "the" mean one or more.

[0011] As used herein, the term "and / or" means that when listing two or more things, any one of the listed things may be taken alone, or any combination of two or more of the listed things may be taken. For example, if a composition is described as containing components A, B, and / or C, the composition may contain only A, only B, only C, a combination of A and B, a combination of A and C, a combination of B and C, or a combination of A, B, and C.

[0012] As used herein, the terms “comprising,” “comprises,” and “comprise” are non-restrictive transitional clauses used to connect a subject (listed before the term) with one or more constituent elements (listed after the term), and the subject is not necessarily composed solely of the one or more constituent elements listed after the transitional clause.

[0013] As used herein, the terms “having,” “has,” and “have” have a non-restrictive meaning, similar to “comprising,” “comprises,” and “comprise.”

[0014] As used herein, the terms “including,” “includes,” and “include” have a non-restrictive meaning, similar to “comprising,” “comprises,” and “comprise.”

[0015] As used herein, “mixed cellulose ester” refers to a cellulose ester having at least two different ester substituents on a single cellulose ester polymer chain.

[0016] The term "degree of substitution" is used to describe the average degree of substitution of substituents per anhydrous glucose unit ("AGU"). Generally, ordinary cellulose contains three hydroxyl groups in each substituteable AGU. Therefore, the DS can have a value between 0 and 3. However, low molecular weight mixed cellulose esters may have a total degree of substitution slightly greater than 3 due to the contribution of terminal groups. Low molecular weight mixed cellulose esters will be described in more detail later in this disclosure. Since DS is a statistical mean, a value of 1 does not guarantee that all AGUs have one substituent. In some cases, unsubstituted anhydrous glucose units may exist, some with two substituents, some with three, and often the value is a non-integer. The total DS is defined as the average number of substituents in total per anhydrous glucose unit. The degree of substitution per AGU can also refer to specific substituents, such as hydroxyl, acetyl, butyryl, or propionyl. Furthermore, the degree of substitution can identify a given hydroxyl group based on the carbon atoms of the anhydrous glucose unit.

[0017] Degree of substitution is hydroxyl (i.e., DS) OH When referring to ), the criterion is the average hydroxyl group per unsubstituted anhydrous glucose. As a result, DS OH This is not used in the calculation of the total degree of substitution.

[0018] The description of this invention uses numerical ranges to quantify specific parameters relating to the invention. Naturally, when a numerical range is given, such a range should be understood as literal support for claims that specify only the lower limit of that range, and further, for claims that specify only the upper limit of that range. For example, if the disclosed numerical range is 10 to 100, it serves as literal support for claims that specify "greater than 10" (no upper limit) and claims that specify "less than 100" (no lower limit).

[0019] This specification uses specific numerical values ​​to quantify certain parameters related to the present invention, and these specific numerical values ​​may not be an explicit part of a numerical range. Naturally, each specific numerical value presented herein should be understood as providing literal support for a broad range, an intermediate range, and a narrow range. The broad range associated with each specific numerical value is +60% to -60% of that value, rounded to two significant figures. The intermediate range associated with each specific numerical value is +30% to -30% of that value, rounded to two significant figures. The narrow range associated with each specific numerical value is +15% to -15% of that value, rounded to two significant figures. For example, if a specific temperature of 62°F is stated in the specification, such a statement provides literal support for a broad numerical range of 25°F to 99°F (62°F ± 37°F), an intermediate numerical range of 43°F to 81°F (62°F ± 19°F), and a narrow numerical range of 53°F to 71°F (62°F ± 9°F). These broad, intermediate, and narrow numerical ranges should apply not only to specific values ​​but also to the differences between such specific values. Therefore, if the specification states a first pressure of 110 psia (absolute pressure) and a second pressure of 48 psia (absolute pressure) (a difference of 62 psi), the broad, intermediate, and narrow ranges for the pressure difference between these two flows are 25 to 99 psi, 43 to 81 psi, and 53 to 71 psi, respectively.

[0020] Throughout this application, where any patent or publication is referenced, the entirety of the disclosures of the references is intended to be incorporated by reference to this application in order to more fully illustrate the state of the art to which the present invention relates, to the extent that such references do not conflict with the present invention.

[0021] In certain embodiments, CE microparticles can be produced by a solvent process or an emulsion process. Referring here to Figure 1, CE microparticles 112 can be produced by mixing cellulose ester (CE) 100, solvent 102, water 104, hydrophilic colloid 106, and surfactant 108 in one or more units. In the illustrated example, CE 100, solvent 102, water 104, hydrophilic colloid 106, and surfactant 108 are mixed in unit 110 to prepare an initial emulsion. The initial emulsion comprises a dispersed phase and a continuous phase. The dispersed phase comprises at least a portion of CE 100 and at least a portion of solvent 102. The continuous phase comprises at least a portion of water 104, at least a portion of hydrophilic colloid 106, and at least a portion of surfactant 108.

[0022] Once mixed, the initial emulsion can be stirred in unit 110 to prepare a pre-cured dispersion containing a solid phase and a liquid phase. The solid phase contains initial particles, which contain at least a portion of CE 100 and at least a portion of solvent 102. The liquid phase contains at least a portion of water 104, at least a portion of hydrophilic colloid 106, and at least a portion of surfactant 108. Additional water 104 (i.e., drowning liquid / extractant) can be added to the pre-cured dispersion to increase the water concentration around the initial particles. An initial cured dispersion containing the initial particles and drowning liquid is prepared therefrom. The initial cured dispersion can be stirred in unit 110 to facilitate the transfer of solvent from the initial particles to the drowning liquid. This solvent transfer facilitates the curing of the initial particles, producing cured CE particles 112. The cured CE particles 112 are incorporated into the drowning liquid containing the solvent.

[0023] The CE particles 112 can be recovered from the dispersion 114 by first processing them in the solid / liquid separation unit 116. The solid material flow 118 containing the CE particles 112 can be led to the solid material processing unit 120. In the solid material processing unit 120, the CE particles 112 are washed with water 122 and then dried to recover them. This will be explained in more detail below. The liquid flow 124 resulting from the sedimentation liquid containing the solvent can be led to the liquid processing unit 126. If necessary, the excess liquid flow 128 led from unit 110 and the washing water flow 130 from unit 120 can also be received and processed in unit 126.

[0024] In unit 126, the liquid received therein can be separated into at least a water-rich flow 132 and a solvent-rich flow 134. In some embodiments, the water-rich flow 132 can be recovered, and at least a portion of it can be used, for example, in unit 110. Furthermore, the solvent-rich flow 134 can be recycled and used as at least a portion of the solvent for forming CE microparticles 112 in unit 110. The reuse of recovered water and / or solvent facilitates improving the economics of the CE microparticle formation process described herein.

[0025] In certain embodiments, CE fine particles can be produced from a mixed cellulose ester (e.g., cellulose acetate butyrate CAB) by subjecting the bulk cellulose ester (CE) to a mechanical particle or size reduction process. In embodiments, the mechanical particle or size reduction process is a grinding process. The grinding process grinds the bulk CE material and reduces its size using one or more high-speed gas jets or liquid jets. In embodiments, the grinding process is a jet mill grinding process. The jet mill grinding process reduces the size of the bulk CE material using one or more high-speed gas jets (e.g., air or inert gas). In embodiments, the jet mill grinding process utilizes a fluidized bed counter-jet mill. In embodiments, the mechanical grinding process yields CE fine particles having an average sphericity of less than 60%, less than 50%, less than 40%, or less than 30%. In embodiments, the mechanical grinding process yields CE fine particles having a D[4,3] average particle size of less than 40 microns, less than 30 microns, or less than 20 microns.

[0026] Mixed cellulose esters In one embodiment, or in combination with any embodiment referenced herein, CE100 can be a mixed cellulose ester.

[0027] In general, the cellulose esters described herein, such as CE100, can be produced by any method known in the art. An example of a process for producing cellulose esters is taught in Kirk-Othmer, Encyclopedia of Chemical Technology, 5th Edition, Vol. 5, Wiley-Interscience, New York (2004), pp. 394-444, the entire disclosure of which is incorporated by reference. Cellulose, the starting material for producing cellulose esters, can be obtained from various sources in different grades. Sources include, for example, lignocellulose sources (e.g., coniferous pulp, hardwood pulp), cotton linters, corn fiber and other agricultural sources, and bacterial cellulose.

[0028] One method for producing cellulose esters is by esterification. In such a method, cellulose is mixed with a suitable organic acid, acid anhydride, and / or catalyst, and then converted to cellulose triester. Next, a water-acid mixture is added to the cellulose triester to carry out ester hydrolysis. The mixture can be filtered to remove gel particles or fibers. Water is added to the mixture to precipitate the cellulose ester. The cellulose ester can then be washed with water to remove reaction by-products, and then dehydrated and dried.

[0029] Suitable acylation reagents for use herein include, but are not limited to, alkyl carboxylic acid anhydrides or aryl carboxylic acid anhydrides, carboxylic acid halides, and / or carboxylic acid esters, which contain the alkyl or aryl groups described herein as suitable for the acyl substituents of the substituted cellulose esters. Suitable carboxylic acid anhydrides include, but are not limited to, acetic anhydride, propionic anhydride, butyric anhydride, pivaloyl anhydride, benzoic acid anhydride, and naphthoyl anhydride. Suitable carboxylic acid halides include, but are not limited to, acetyl chloride or acetyl bromide, propionyl chloride or propionyl bromide, butyrill chloride or butyryl bromide, pivaloyl chloride or pivaloyl bromide, benzoyl chloride or benzoyl bromide, and naphthoyl chloride or naphthoyl bromide. Suitable carboxylic acid esters include, but are not limited to, acetyl esters, propionyl esters, butyryl esters, pivaloyl esters, benzoyl esters, and naphthoyl methyl esters. In one or more embodiments, the acylation reagent can be one or more carboxylic acid anhydrides selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, pivaloyl anhydride, benzoyl anhydride, and naphthoyl anhydride.

[0030] In various embodiments, the hydrolyzed cellulose triesters may have three substituents independently selected from alkanoyls having 2 to 12 carbon atoms. Examples of cellulose triesters include cellulose triacetate, cellulose trippropionate, cellulose triptylate, or mixed triesters of cellulose, such as cellulose acetate propionate and cellulose acetate butylate. These cellulose triesters can be prepared by several methods known to those skilled in the art. For example, cellulose triesters can be prepared by heterogeneous acylation of cellulose in a mixture of carboxylic acid and anhydride in the presence of a catalyst such as H2SO4. Cellulose triesters can also be prepared by homogeneous acylation of cellulose dissolved in a suitable solvent such as LiCl / DMAc or LiCl / NMP.

[0031] After esterification of cellulose to triester, some of the acyl substituents may be removed by hydrolysis or alcohol decomposition to obtain a secondary cellulose ester. Alternatively, the secondary cellulose ester may be prepared directly without hydrolysis by using a limited amount of acylation reagent. This process is particularly useful when the reaction is carried out in a solvent that dissolves cellulose.

[0032] The cellulose esters prepared in this manner generally have the following structure. [ka] In the formula, R 2 , R 3 , and R 6 This refers to hydrogen atoms bonded to cellulose via ester bonds (however, R 2 , R 3 , and R 6 These are alkyl-acyl groups and / or aryl-acyl groups (for example, those listed above), which are not hydrogen at the same time.

[0033] The degree of polymerization ("DP") of the cellulose esters prepared by these methods can be at least 10. In other embodiments, the DP of the cellulose ester can be at least 50, at least 100, or at least 250. In other embodiments, the DP of the cellulose ester can be in the range of about 5 to about 100, or in the range of about 10 to about 50.

[0034] Suitable acylation reagents for use herein include, but are not limited to, alkyl carboxylic acid anhydrides or aryl carboxylic acid anhydrides, carboxylic acid halides, and / or carboxylic acid esters, which contain the alkyl or aryl groups described herein as suitable for the acyl substituents of the substituted cellulose esters. Suitable carboxylic acid anhydrides include, but are not limited to, acetic anhydride, propionic anhydride, butyric anhydride, pivaloyl anhydride, benzoic acid anhydride, and naphthoyl anhydride. Suitable carboxylic acid halides include, but are not limited to, acetyl chloride or acetyl bromide, propionyl chloride or propionyl bromide, butyrill chloride or butyryl bromide, pivaloyl chloride or pivaloyl bromide, benzoyl chloride or benzoyl bromide, and naphthoyl chloride or naphthoyl bromide. Suitable carboxylic acid esters include, but are not limited to, acetyl esters, propionyl esters, butyryl esters, pivaloyl esters, benzoyl esters, and naphthoyl methyl esters. In one or more embodiments, the acylation reagent can be one or more carboxylic acid anhydrides selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, pivaloyl anhydride, benzoyl anhydride, and naphthoyl anhydride.

[0035] In a first aspect, this application discloses a mixed cellulose ester ("MCE") comprising (1) a plurality of acetyl substituents, (2) a plurality of propionyl substituents, and (3) a plurality of hydroxyl substituents, wherein the MCE has an average degree of substitution of 0.1 to 2.3 for the acetyl substituents ("DS"). AcThe MCE has an average degree of substitution of 0.1 to 1.5 for the propionyl substituent ("DS Pr ) has, and MCE has an average degree of substitution of 0.6 to 2.8 for hydroxyl substituents ("DS OH It has ''.

[0036] In one embodiment, or in combination with any other embodiment, class, or subclass of this first embodiment, DS Ac is at least 0.1, at least 0.2, at least 0.3, at least 0.4, at least 0.5, at least 0.6, at least 0.7, at least 0.8, at least 0.9, at least 1.0, at least 1.1, at least 1.2, at least 1.3, at least 1.4, at least 1.5, at least 1.6, at least 1.7, at least 1.8, at least 1.9, or at least 2.0. Additionally or alternatively, DS Ac This is less than 2.3, less than 2.2, less than 2.1, less than 2.0, less than 1.9, less than 1.8, less than 1.7, less than 1.6, less than 1.5, less than 1.4, less than 1.3, less than 1.2, less than 1.1, less than 1.0, less than 0.9, less than 0.8, less than 0.7, less than 0.5, less than 0.4, or less than 0.3.

[0037] In one embodiment, or in combination with any other embodiment, class, or subclass of this first embodiment, DS AcThis refers to 0.6~2.2, or 0.6~2.1, or 0.6~2.0, or 0.6~1.9, or 0.6~1.8, or 0.7~2.3, or 0.7~2.2, or 0.7~2.1, or 0.7~2.0, or 0.7~1.9, or 0.8~2.3, or 0.8~2.2, or 0.8~2.1, or 0.8~2.0, or 0.8~1.9, or 0.9~2.3, or 0.9~2.2, or 0.9~2.1, or 0.9~2.0, or 0.9~1.9, or 1.0~2.3, or 1.0~ 2.2, or 1.0-2.1, or 1.0-2.0, or 1.0-1.9, or 1.1-2.3, or 1.1-2.2, or 1.1-2.1, or 1.1-2.0, or 1.1-1.9, or 1.2-2.3, or 1.2-2.2, or 1.2-2.1, or 1.2-2.0, or 1.2-1.9, or 0.6-1.5, or 0.6-1.3, or 0.6-1.1, or 0.6-0.9, or 0.7-1.5, or 0.7-1.3, or 0.7-1.1, or 0.7-0.9.

[0038] In one embodiment, or in combination with any other embodiment, class, or subclass of this first embodiment, DS Pr is at least 0.05, at least 0.1, at least 0.15, at least 0.2, at least 0.3, at least 0.4, at least 0.5, at least 0.6, at least 0.7, at least 0.8, at least 0.9, at least 1.0, at least 1.1, at least 1.2, at least 1.3, or at least 1.4. Additionally or alternatively, DS Pr This is less than 1.5, less than 1.4, less than 1.3, less than 1.2, less than 1.1, less than 1.0, less than 0.9, less than 0.8, less than 0.7, less than 0.5, less than 0.4, less than 0.35, less than 0.3, or less than 0.25.

[0039] In one embodiment, or in combination with any other embodiment, class, or subclass of this first embodiment, DS PrThis includes 0.05~0.9, or 0.05~0.85, or 0.05~0.8, or 0.05~0.75, or 0.05~0.7, or 0.05~0.6, or 0.05~0.5, or 0.05~0.4, or 0.05~0.35, or 0.05~0.3, or 0.05~0.25, or 0.1~0.9, or 0.1~0.85, or 0.1~0.8, or 0.1~0.75, or 0.1~0.7, or 0.1~0.6, and 0.1~0.5, or 0.1~0.4, or 0.1~0.35, or 0.1~0.3, or 0.1~0.25, or 0.15~0.95, or 0.15~0.9, or 0.15~0.85, or 0.15~0.8, or 0.15~0.75, or 0.15~0.7, or 0.15~0.65, or 0.15~0.6, or 0.15~0.5, or 0.15~0.4, or 0.15~0.35, or 0.15~0.3, or 0.15~0.25, or 0.2~0.95, or 0.2~0.9, or 0.2~0.85, or 0.2~0.8, or 0.2~0.75, or 0.2~0.7, or 0.2~0.65, 0.25~0.95, or 0.25~0.9, or 0.25~0.85, or 0.25~0.8, or 0.25~0.75, or 0.25~0.7, or 0.25~0.65, or 0.3~0.95, or 0.3~0.9, or 0 0.3~0.85, or 0.3~0.8, or 0.3~0.75, or 0.3~0.7, or 0.3~0.65, or 0.35~0.95, or 0.35~0.9, or 0.35~0.85, or 0.35~0.8, or 0.35~0.75, or 0.35~0.7, or 0.35~0.65, or 0.4~0.95, or 0.4~0.9, or 0.4~0.85, or 0.4~0.8, or 0.4~0.75, and 0.4 ~0.7, or 0.4~0.65, or 0.45~0.95, or 0.45~0.9, or 0.45~0.85, or 0.45~0.8, or 0.45~0.75, or 0.45~0.7, or 0.45~0.65, or 0.5~0.95, or 0.5~0.9, or 0.5~0.85, or 0.5~0.8, or 0.5~0.75, or 0.5~0.7, or 0.The ranges are 5-0.65, or 0.1-0.9, or 0.1-0.85, or 0.1-0.8.

[0040] In one embodiment, or in combination with any other embodiment, class, or subclass of this first embodiment, DS OH is at least 0.5, at least 0.55, at least 0.6, at least 0.65, at least 0.7, at least 0.75, at least 0.8, at least 0.85, at least 0.9, at least 1.0, at least 1.1, at least 1.2, at least 1.3, at least 1.4, at least 1.5, at least 1.6, at least 1.7, at least 1.8, at least 1.9, at least 2.0, at least 2.1, at least 2.2, at least 2.3, at least 2.4, at least 2.5, or at least 2.6. Additionally or alternatively, DS OH This is less than 2.8, less than 2.7, less than 2.6, less than 2.5, less than 2.4, less than 2.3, less than 2.2, less than 2.1, less than 2.0, less than 1.9, less than 1.8, less than 1.7, less than 1.6, less than 1.5, less than 1.4, less than 1.3, less than 1.2, less than 1.15, less than 1.1, less than 1.05, less than 1.0, less than 0.95, less than 0.9, less than 0.85, or less than 0.8.

[0041] In one embodiment, or in combination with any other embodiment, class, or subclass of this first embodiment, DS OHThese ranges are 0.5-1.5, or 0.5-1.45, or 0.5-1.40, or 0.5-1.35, or 0.5-1.30, or 0.5-1.25, or 0.5-1.2, or 0.5-1.15, or 0.5-1.1, or 0.5-1.05, or 0.5-1.0, or 0.5-0.95, or 0.5-0.9, or 0.5-0.85, or 0.5-0.8, or 0.55-1.5, or 0.55-1.45, or 0.55-1.40, or 0.55-1.35, or 0.55-1.30, or 0.55-1.25 , or 0.55~1.2, or 0.55~1.15, or 0.55~1.1, or 0.55~1.05, or 0.55~1.0, or 0.55~0.95, or 0.55~0.9, or 0.55~0.85, or 0.55~0.8, or 0.6~1.5, or 0.6~1.45, or 0.6~1.40, or 0.6~1.35, or 0.6~1.30, or 0.6~1.25, or 0.6~1.2, or 0.6~1.15, or 0.6~1.1, or 0.6~1.05, or 0.6~1.0, or 0.6~0. 95, or 0.6~0.9, or 0.6~0.85, or 0.6~0.8, or 0.65~1.5, or 0.65~1.45, or 0.65~1.40, or 0.65~1.35, or 0.65~1.30, or 0.65~1.25, or 0.65~1.2, or 0.65~1.15, or 0.65~1.1, or 0.65~1.05, or 0.65~1.0, or 0.65~0.95, or 0.65~0.9, or 0.65~0.85, or 0.65~0.8, or 0.7~1.5, or 0.7~1.45, or 0.7~1.40, or 0.7~1.35, or 0.7~1.30, or 0.7~1.25, or 0.7~1.2, or 0.7~1.15, or 0.7~1.1, or 0.7~1.05, or 0.7~1.0, or 0.7~0.95, or 0.7~0.9, or 0.7~0.85, or 0.7~0.8, or 0.75~1.5, or 0.75~1.45, or 0.75~1.40, or 0.75~1.35, or 0.75~1.30, or 0.75~1.25, or 0.75~1.2, or 0.75~1.15, or 0.75~1.1, or 0.75~1.05, or 0.75~1.0, or 0.75~0.95, or 0.75~0.9, or 0.8~1.5, or 0.8~1.45, or 0.8~1.40, or 0.8~1.35, or 0.8~1.30, or 0.8~1.25, or 0.8~1.2, or 0.8~1.15, or 0.8~1.1, or 0.8~1.05, or 0.8~1. The values ​​are 0, or 0.8-0.95, or 0.8-0.9, or 0.85-1.5, or 0.85-1.45, or 0.85-1.40, or 0.85-1.35, or 0.85-1.30, or 0.85-1.25, or 0.85-1.2, or 0.85-1.15, or 0.85-1.1, or 0.85-1.05, or 0.85-1.0, or 0.85-0.95, or 0.85-0.9.

[0042] In one embodiment, or in combination with any other embodiment, class, or subclass of this first embodiment, DS Pr and DS Ac The sum of these values ​​is 1.9-2.44, or 1.9-2.0, or 1.9-2.1, or 1.9-2.2, or 1.9-2.3, or 2.0-2.44, or 2.0-2.1, or 2.0-2.2, or 2.0-2.3, or 2.1-2.44, or 2.1-2.2, or 2.1-2.3, or 2.2-2.44, or 2.2-2.3.

[0043] In one embodiment, or in combination with any other embodiment, class, or subclass of this first embodiment, the ratio of hydroxyl substituents to acetyl substituents (hydroxyl substituent:acetyl substituent) in the mixed cellulose ester is at least 0.4:1, at least 0.45:1, at least 0.5:1, at least 0.6:1, at least 0.7:1, at least 0.8:1, at least 0.9:1, at least 1:1, at least 1.1:1, at least 1.2:1, at least 1.3:1, at least 1.4:1, at least 1.5:1, at least 1.6:1, at least 1.7:1, at least 1.8:1, at least 1.9:2, or at least 2:1. Additionally or alternatively, the ratio of hydroxyl substituents to acetyl substituents (hydroxyl substituent:acetyl substituent) in the mixed cellulose ester is less than 2:1, less than 1.9:1, less than 1.8:1, less than 1.7:1, less than 1.6:1, less than 1.5:1, less than 1.4:1, less than 1.3:1, less than 1.2:1, less than 1.1:1, or less than 1:1.

[0044] In one embodiment, or in combination with any other embodiment, class, or subclass of this first embodiment, the ratio of hydroxyl substituents to propionyl substituents in the MCE (hydroxyl substituent:propionyl substituent) is at least 0.4:1, at least 0.45:1, at least 0.5:1, at least 0.6:1, at least 0.7:1, at least 0.8:1, at least 0.9:1, at least 1:1, at least 1.1:1, at least 1.2:1, at least 1.3:1, at least 1.4:1, at least 1.5:1, at least 1.6:1, at least 1.7:1, at least 1.8:1, at least 1.9:2, or at least 2:1. Additionally or alternatively, the ratio of hydroxyl substituents to propionyl substituents in the MCE (hydroxyl substituent:propionyl substituent) is less than 2:1, less than 1.9:1, less than 1.8:1, less than 1.7:1, less than 1.6:1, less than 1.5:1, less than 1.4:1, less than 1.3:1, less than 1.2:1, less than 1.1:1, or less than 1:1, or less than 0.9:1, or less than 0.8:1, or less than 0.7:1, or less than 0.6:1, or less than 0.5:1.

[0045] In one embodiment, or in combination with any other embodiment, class, or subclass of this first embodiment, the MCE exhibits at least 40% biodegradability, at least 45% biodegradability, or at least 50% biodegradability, or at least 55% biodegradability, at least 60% biodegradability, or at least 65% biodegradability, or at least 70% biodegradability, or at least 75% biodegradability, or at least 80% biodegradability, or at least 85% biodegradability in 56 days, according to at least one of the OECD301B test method, OECD301C test method, or OECD301F test method.

[0046] In one embodiment, or in combination with any other embodiment, class, or subclass of this first embodiment, the MCE exhibits at least 40% biodegradability, at least 45% biodegradability, or at least 50% biodegradability, or at least 55% biodegradability, at least 60% biodegradability, or at least 65% biodegradability, or at least 70% biodegradability, or at least 75% biodegradability, or at least 80% biodegradability, or at least 85% biodegradability in 60 days, according to at least one of the OECD301B test method, OECD301C test method, or OECD301F test method.

[0047] In one embodiment, or in combination with any other embodiment, class, or subclass of this first embodiment, the weight-average molecular weight of MCE is in the range of 5,000 to 100,000 Da, or 5,000 to 50,000 Da, or 5,000 to 25,000 Da, or 15,000 to 100,000 Da, or 15,000 to 50,000 Da, or 15,000 to 25,000 Da, or 50,000 to 100,000 Da, or 75,000 to 100,000 Da, or 15,000 to 250,000 Da.

[0048] In a second aspect, this application discloses a mixed cellulose ester ("MCE") comprising (1) a plurality of acetyl substituents, (2) a plurality of propionyl substituents, and (3) a plurality of hydroxyl substituents, wherein the MCE has an average degree of substitution of the acetyl substituents of 0.1 to 2.3, or 0.1 to 1.9, or 1.5 to 2.3 ("DS"). Ac The MCE has an average degree of substitution of 0.1 to 1.5, or 0.1 to 0.6, or 0.1 to 0.3 for the propionyl substituent ("DS Pr ) has, and MCE has an average degree of substitution of 0.7 to 2.8 or 0.7 to 1.2 for the hydroxyl substituent ("DS OH It has ''.

[0049] In one embodiment, or in combination with any other embodiment, class, or subclass of this second embodiment, DS Ac is at least 0.1, at least 0.2, at least 0.3, at least 0.4, at least 0.5, at least 0.6, at least 0.7, at least 0.8, at least 0.9, at least 1.0, at least 1.1, at least 1.2, at least 1.3, at least 1.4, at least 1.5, at least 1.6, at least 1.7, at least 1.8, at least 1.9, or at least 2.0. Additionally or alternatively, DS Ac This is less than 2.3, less than 2.2, less than 2.1, less than 2.0, less than 1.9, less than 1.8, less than 1.7, less than 1.6, less than 1.5, less than 1.4, less than 1.3, less than 1.2, less than 1.1, less than 1.0, less than 0.9, less than 0.8, less than 0.7, less than 0.5, less than 0.4, or less than 0.3.

[0050] In one embodiment, or in combination with any other embodiment, class, or subclass of this second embodiment, DS AcThis refers to 0.6~0.7, or 0.6~0.8, or 0.6~0.9, or 0.6~1.0, or 0.6~1.1, or 0.6~1.2, or 0.6~1.3, or 0.6~1.4, or 0.6~1.5, or 0.6~1.6, or 0.6~1.7, or 0.6~1.8, or 0.6~1.9, or 0.6~2.0, or 0.6~2.1, or 0.7~0.9, or 0.7~1.0, or 0.7~1.1, or 0.7~ 1.2, or 0.7~1.3, or 0.7~1.4, or 0.7~1.5, or 0.7~1.6, or 0.7~1.7, or 0.7~1.8, or 0.7~1.9, or 0.7~2.0, or 0.7~2.1, or 0.8~0.9, or 0.8~1.0, or 0.8~1.1, or 0.8~1.2, or 0.8~1.3, or 0.8~1.4, or 0.8~1.5, or 0.8~1.6, or 0.8~1.7, also 0.8~1.8, or 0.8~1.9, or 0.8~2.0, or 0.8~2.1, or 0.9~1.0, or 0.9~1.1, or 0.9~1.2, or 0.9~1.3, or 0.9~1.4, or 0.9~1.5, or 0.9~1.6, or 0.9~1.7, or 0.9~1.8, or 0.9~1.9, or 0.9~2.0, or 0.9~2.1, or 1.0~1.1, or 1.0~1.2, or 1.0~1 0.3, or 1.0-1.4, or 1.0-1.5, or 1.0-1.6, or 1.0-1.7, or 1.0-1.8, or 1.0-1.9, or 1.0-2.0, or 1.0-2.1, or 1.1-1.2, or 1.1-1.3, or 1.1-1.4, or 1.1-1.5, or 1.1-1.6, or 1.1-1.7, or 1.1-1.8, or 1.1-1.9, or 1.1-2.0, or 1.1-2.1.

[0051] In one embodiment, or in combination with any other embodiment, class, or subclass of this second embodiment, DS Pris at least 0.1, at least 0.2, at least 0.3, at least 0.4, at least 0.5, at least 0.6, at least 0.7, at least 0.8, at least 0.9, at least 1.0, at least 1.1, at least 1.2, at least 1.3, or at least 1.4. Additionally or alternatively, DS Pr This is less than 1.5, less than 1.4, less than 1.3, less than 1.2, less than 1.1, less than 1.0, less than 0.9, less than 0.8, less than 0.7, less than 0.5, less than 0.4, or less than 0.3.

[0052] In one embodiment, or in combination with any other embodiment, class, or subclass of this second embodiment, DS Pr This includes 1.05-1.35, or 1.05-1.3, or 1.05-1.25, or 1.05-1.2, or 1.05-1.15, or 1.05-1.1, or 1.1-1.4, or 1.1-1.35, or 1.1-1.3, or 1.1-1.25, or 1.1-1.2, or 1.1-1.15, or 1.15-1.4, and The values ​​are 1.15-1.35, or 1.15-1.3, or 1.15-1.25, or 1.15-1.2, or 1.2-1.4, or 1.2-1.35, or 1.2-1.3, or 1.2-1.25, or 1.25-1.4, or 1.25-1.35, or 1.25-1.3, or 1.3-1.4, or 1.3-1.35.

[0053] In one embodiment, or in combination with any other embodiment, class, or subclass of this second embodiment, DS OH is at least 0.6, at least 0.7, at least 0.8, at least 0.9, at least 1.0, at least 1.1, at least 1.2, at least 1.3, at least 1.4, at least 1.5, at least 1.6, at least 1.7, at least 1.8, at least 1.9, at least 2.0, at least 2.1, at least 2.2, at least 2.3, at least 2.4, at least 2.5, or at least 2.6. Additionally or alternatively, DS OHThis is less than 2.8, less than 2.7, less than 2.6, less than 2.5, less than 2.4, less than 2.3, less than 2.2, less than 2.1, less than 2.0, less than 1.9, less than 1.8, less than 1.7, less than 1.6, less than 1.5, less than 1.4, less than 1.3, less than 1.2, less than 1.1, less than 1.0, less than 0.9, or less than 0.8.

[0054] In one embodiment, or in combination with any other embodiment, class, or subclass of this second embodiment, DS OH This refers to 0.7~1.35, or 0.7~1.3, or 0.7~1.25, or 0.7~1.2, or 0.7~1.15, or 0.7~1.1, or 0.7~1.05, or 0.7~1.0, or 0.7~0.95, or 0.7~0.9, or 0.7~0.85, or 0.7~0.8, or 0.7~0.75, or 0.75~1.4, or 0.75~1.35, or 0.75~1.3, or 0.75~1.25, or 0.75~1.2, or 0.75~1.15, or 0.75~1.1, or 0.75~1.05, or 0.75~1.0, or 0.75~0.95, or 0.8 ~1.4, or 0.8~1.35, or 0.8~1.3, or 0.8~1.25, or 0.8~1.2, or 0.8~1.15, or 0.8~1.1, or 0.8~1.05, or 0.85~1.4, or 0.85~1.35, or 0.85~1.3, or 0.85~1.25, or 0.85~1.2, or 0.85~1.15, or 0.85~1.1, or 0.85~1.05, or 0.9~1.4, or 0.9~1.35, or 0.9~1.3, or 0.9~1.25, or 0.9~1.2, or 0.9~1.15, or 0.9~1.1, or 0.9~1.05.

[0055] In one embodiment, or in combination with any other embodiment, class, or subclass of this second embodiment, DS Pr and DS AcThe sum of these is 1.65~2.3, or 1.65~2.2, or 1.65~2.1, or 1.65~2.0, or 1.65~1.9, or 1.65~1.8, or 1.7~2.3, or 1.7~2.2, or 1.7~2.1, or 1.7~2.0, or 1.7~1.9, or 1.7~1.8, or 1.75~2.3, or 1.75~2.2, or The ranges are 1.75-2.1, or 1.75-2.0, or 1.75-1.9, or 1.8-2.3, or 1.8-2.2, or 1.8-2.1, or 1.8-2.0, or 1.8-1.9, or 1.9-2.3, or 1.9-2.2, or 1.9-2.1, or 1.9-2.0, or 2.0-2.3, or 2.0-2.2, or 2.0-2.1.

[0056] In one embodiment, or in combination with any other embodiment, class, or subclass of this second embodiment, DS OHThese ranges from 0.6 to 0.7, or 0.7 to 1.35, or 0.7 to 1.3, or 0.7 to 1.25, or 0.7 to 1.2, or 0.7 to 1.15, or 0.7 to 1.1, or 0.7 to 1.05, or 0.7 to 1.0, or 0.7 to 0.95, or 0.7 to 0.9, or 0.7 to 0.85, or 0.7 to 0.8, or 0.7 to 0.75, or 0.75 to 1.4, or 0.75 to 1.35, or 0.75 to 1.3, or 0.75 to 1.25, or 0.75 to 1.2, or 0.75 to 1.15, or 0.75 to 1.1, or 0.75 to 1.05, or 0.75 to 1.0, or 0.75 to 0.95, or 0.8~1.4, or 0.8~1.35, or 0.8~1.3, or 0.8~1.25, or 0.8~1.2, or 0.8~1.15, or 0.8~1.1, or 0.8~1.05, or 0.85~1.4, or 0.85~1.35, or 0.85~1.3, or 0.85~1.25, or 0.85~1.2, or 0.85~1.15, or 0.85~1.1, or 0.85~1.05, or 0.9~1.4, or 0.9~1.35, or 0.9~1.3, or 0.9~1.25, or 0.9~1.2, or 0.9~1.15, or 0.9~1.1, or 0.9~1.05.

[0057] In one embodiment, or in combination with any other embodiment, class, or subclass of this second embodiment, the ratio of hydroxyl substituents to acetyl substituents (hydroxyl substituent:acetyl substituent) in the mixed cellulose ester is at least 0.4:1, at least 0.5:1, at least 0.6:1, at least 0.7:1, at least 0.8:1, at least 0.9:1, at least 1:1, at least 1.1:1, at least 1.2:1, at least 1.3:1, at least 1.4:1, at least 1.5:1, at least 1.6:1, at least 1.7:1, at least 1.8:1, at least 1.9:2, or at least 2:1. Additionally or alternatively, the ratio of hydroxyl substituents to acetyl substituents (hydroxyl substituent:acetyl substituent) in the mixed cellulose ester is less than 2:1, less than 1.9:1, less than 1.8:1, less than 1.7:1, less than 1.6:1, less than 1.5:1, less than 1.4:1, less than 1.3:1, less than 1.2:1, less than 1.1:1, or less than 1:1.

[0058] In one embodiment, or in combination with any other embodiment, class, or subclass of this second embodiment, the ratio of hydroxyl substituents to propionyl substituents in the MCE (hydroxyl substituent:propionyl substituent) is at least 0.4:1, at least 0.5:1, at least 0.6:1, at least 0.7:1, at least 0.8:1, at least 0.9:1, at least 1:1, at least 1.1:1, at least 1.2:1, at least 1.3:1, at least 1.4:1, at least 1.5:1, at least 1.6:1, at least 1.7:1, at least 1.8:1, at least 1.9:2, or at least 2:1, or at least 3:1, or at least 4:1. Additionally or alternatively, the ratio of hydroxyl substituents to propionyl substituents in the MCE (hydroxyl substituent:propionyl substituent) is less than 6:1, less than 5:1, less than 4:1, less than 3:1, less than 2:1, less than 1.9:1, less than 1.8:1, less than 1.7:1, less than 1.6:1, less than 1.5:1, less than 1.4:1, less than 1.3:1, less than 1.2:1, less than 1.1:1, or less than 1:1.

[0059] In one embodiment, or in combination with any other embodiment, class, or subclass of this second embodiment, the MCE exhibits at least 40% biodegradability, at least 45% biodegradability, or at least 50% biodegradability, or at least 55% biodegradability, at least 60% biodegradability, or at least 65% biodegradability, or at least 70% biodegradability, or at least 75% biodegradability, or at least 80% biodegradability, or at least 85% biodegradability in 56 days, according to at least one of the OECD301B test method, OECD301C test method, or OECD301F test method.

[0060] In one embodiment, or in combination with any other embodiment, class, or subclass of this second embodiment, the MCE exhibits at least 40% biodegradability, at least 45% biodegradability, or at least 50% biodegradability, or at least 55% biodegradability, at least 60% biodegradability, or at least 65% biodegradability, or at least 70% biodegradability, or at least 75% biodegradability, or at least 80% biodegradability, or at least 85% biodegradability in 60 days, according to at least one of the OECD301B test method, OECD301C test method, or OECD301F test method.

[0061] In one embodiment, or in combination with any other embodiment, class, or subclass of this second embodiment, the weight-average molecular weight of MCE is in the range of 5,000 to 100,000 Da, or 5,000 to 50,000 Da, or 5,000 to 25,000 Da, or 15,000 to 100,000 Da, or 15,000 to 50,000 Da, or 15,000 to 25,000 Da, or 50,000 to 100,000 Da, or 75,000 to 100,000 Da, or 15,000 to 250,000 Da.

[0062] Furthermore, in a third aspect, this application discloses a mixed ester cellulose ester ("MCE") comprising (1) a plurality of acetyl substituents, (2) a plurality of butyryl substituents, and (3) a plurality of hydroxyl substituents, wherein the MCE has an average degree of substitution of 0.1 to 2.4, or 0.1 to 2.4, or 1.5 to 2.4 ("DS") for the acetyl substituents. Ac The MCE has an average degree of substitution of 0.1 to 1.5, or 0.1 to 0.6, or 0.1 to 0.3 for the butyryl substituent ("DS Bu The MCE has an average degree of substitution of 0.6-2.8, 0.6-1.5, or 0.6-1.2 for the hydroxyl substituent ("DS OH It has ''.

[0063] In one embodiment, or in combination with any other embodiment, class, or subclass of this first embodiment, DS Ac is at least 0.1, at least 0.2, at least 0.3, at least 0.4, at least 0.5, at least 0.6, at least 0.7, at least 0.8, at least 0.9, at least 1.0, at least 1.1, at least 1.2, at least 1.3, at least 1.4, at least 1.5, at least 1.6, at least 1.7, at least 1.8, at least 1.9, or at least 2.0. Additionally or alternatively, DS Ac This is less than 2.3, less than 2.2, less than 2.1, less than 2.0, less than 1.9, less than 1.8, less than 1.7, less than 1.6, less than 1.5, less than 1.4, less than 1.3, less than 1.2, less than 1.1, less than 1.0, less than 0.9, less than 0.8, less than 0.7, less than 0.5, less than 0.4, or less than 0.3.

[0064] In one embodiment, or in combination with any other embodiment, class, or subclass of this third embodiment, DS AcThese ranges are 0.9~2.4, 0.9~2.3, or 0.9~2.2, or 0.9~2.1, or 0.9~2.0, or 0.9~1.9, or 0.9~1.8, or 0.9~1.7, or 0.9~1.6, or 0.9~1.4, 0.9~1.3, or 0.9~1.2, or 0.9~1.1, or 0.9~1.0, or 0.92~2.4, 0.92~2.3, or 0.92~2.2, or 0.92~2.1, or 0.92~2.0, or 0.92~1.9, or 0.92~1.8, or 0.92~1.7, or 0.92~1. 6, or 0.92~1.4, 0.92~1.3, or 0.92~1.2, or 0.92~1.1, or 0.92~1.0, or 0.94~2.4, 0.94~2.3, or 0.94~2.2, or 0.94~2.1, or 0.94~2.0, or 0.94~1.9, or 0.94~1.8, or 0.94~1.7, or 0.94~1.6, or 0.94~1.4, 0.94~1.3, or 0.94~1.2, or 0.94~1.1, or 0.94~1.0, or 0.96~2.4, 0.96~2.3, or 0.96~ 2.2, or 0.96~2.1, or 0.96~2.0, or 0.96~1.9, or 0.96~1.8, or 0.96~1.7, or 0.96~1.6, or 0.96~1.4, 0.96~1.3, or 0.96~1.2, or 0.96~1.1, or 0.96~1.0, or 0.98~2.4, 0.98~2.3, or 0.98~2.2, or 0.98~2.1, or 0.98~2.0, or 0.98~1.9, or 0.98~1.8, or 0.98~1.7, or 0.98~1.6, 0.98~1.4, 0.9 8~1.3, or 0.98~1.2, or 0.98~1.1, or 0.98~1.0, or 1.0~2.4, 1.0~2.3, or 1.0~2.2, or 1.0~2.1, or 1.0~2.0, or 1.0~1.9, or 1.0~1.8, or 1.0~1.7, or 1.0~1.6, or 1.0~1.4, or 1.0~1.3, 1.0~1.2, or 1.0~1.1, or 1.1~2.4, or 1.1~2.3, or 1.1~2.2, or 1.1~2.1, or 1.1~2.0, or 1.1~1.9, or 1.1-1.8, or 1.1-1.7, or 1.1-1.6, 1.1-1.4, or 1.1-1.3, or 1.1-1.2, or 1.2-2.4, or 1.2-2.3, or 1.2-2.2, or 1.2-2.1, or 1.2-2.0, or 1.2-1.9, or 1.2-1.8, or 1.2-1.7, or 1.2-1.6, or 1.2-1.4, or 1.2-1.3, or 1.3-2.4, or 1.3-2.3, or 1.3 ~2.2, or 1.3~2.1, or 1.3~2.0, or 1.3~1.9, or 1.3~1.8, or 1.3~1.7, or 1.3~1.6, or 1.3~1.4, or 1.4~2.4, or 1.4~2.3, or 1.4~2.2, or 1.4~2.1, or 1.4~2.0, or 1.4~1.9, or 1.4~1.8, or 1.4~1.7, or 1.4~1.6, or 1.5~2.4, or 1.5~2.3, or 1. 5-2.2, or 1.5-2.1, or 1.5-2.0, or 1.5-1.9, or 1.5-1.8, or 1.5-1.7, or 1.5-1.6, or 1.6-2.4, or 1.6-2.3, or 1.6-2.2, or 1.6-2.1, or 1.6-2.0, or 1.6-1.9, or 1.6-1.8, or 1.6-1.7, or 1.7-2.4, or 1.7-2.3, or 1.7-2.2, or 1.7-2.1, or 1 The ranges are 0.7-2.0, or 1.7-1.9, or 1.7-1.8, or 1.8-2.3, or 1.8-2.1, or 1.8-2.0, or 1.8-1.9, or 1.9-2.3, or 1.9-2.2, or 1.9-2.1, or 1.9-2.0, or 2.0-2.4, or 2.0-2.3, or 2.0-2.2, or 2.0-2.1, or 2.1-2.4, or 2.1-2.3, or 2.1-2.2, or 2.2-2.3.

[0065] In one embodiment, or in combination with any other embodiment, class, or subclass of this third embodiment, DS Buis at least 0.05, at least 0.1, at least 0.15, at least 0.2, at least 0.3, at least 0.4, at least 0.5, at least 0.6, at least 0.7, at least 0.8, at least 0.9, at least 1.0, at least 1.1, at least 1.2, at least 1.3, or at least 1.4. Additionally or alternatively, DS Bu This is less than 1.5, less than 1.4, less than 1.3, less than 1.2, less than 1.1, less than 1.0, less than 0.9, less than 0.8, less than 0.7, less than 0.5, less than 0.4, less than 0.35, less than 0.3, or less than 0.25.

[0066] In one embodiment, or in combination with any other embodiment, class, or subclass of this third embodiment, DS BuThis includes 0.1~1.35, or 0.1~1.3, or 0.1~1.25, or 0.1~1.2, or 0.1~1.15, or 0.1~1.1, or 0.1~1.0, or 0.1~0.8, or 0.1~0.6, or 0.1~0.5, or 0.1~0.4, or 0.1~0.3, or 0.1~0.25, or 0.15~1.35, or 0.15~1.3, or 0.15~1.25, or 0.15~1.2, or 0.15~1.15, or 0.15~1.1, or 0.15~1.0, or 0.15~0.8, or 0 0.15~0.6, or 0.15~0.5, or 0.15~0.4, or 0.15~0.3, or 0.15~0.25, or 0.2~1.35, or 0.2~1.3, or 0.2~1.25, or 0.2~1.2, or 0.2~1.15, or 0.2~1.1, or 0.2~1.0, or 0.2~0.8, or 0.2~0.6, or 0.2~0.4, or 0.3~1.35, or 0.3~1.3, or 0.3~1.25, or 0.3~1.2, or 0.3~1.15, or 0.3~1.1, or 0.3~1.0 , or 0.3~0.8, or 0.3~0.6, or 0.3~0.5, or 0.4~1.35, or 0.4~1.3, or 0.4~1.25, or 0.4~1.2, or 0.4~1.15, or 0.4~1.1, or 0.4~1.0, or 0.4~0.8, or 0.4~0.6, or 0.5~1.35, or 0.5~1.3, or 0.5~1.25, or 0.5~1.2, or 0.5~1.15, or 0.5~1.1, or 0.5~1.0, or 0.5~0.8, or 0.5~0.7, or 0.6~1.35 , or 0.6~1.3, or 0.6~1.25, or 0.6~1.2, or 0.6~1.15, or 0.6~1.1, or 0.6~1.0, or 0.6~0.8, or 0.7~1.35, or 0.7~1.3, or 0.7~1.25, or 0.7~1.2, or 0.7~1.15, or 0.7~1.1, or 0.7~1.0, or 0.8~1.35, or 0.8~1.3, or 0.8~1.25, or 0.8~1.2, or 0.8~1.15, or 0.8~1.1, or 0.8~1.0, or 0.9~1.35, or 0.9~1.3, or 0.9~1.25, or 0.9~1.2, or 0.9~1.15, or 0.9~1.1, or 1.0~1.35, or 1.0~1.3, or 1.0~1.25, or 1.0~1.2, or 1.0~1.15, or 1.0~1.1, or 1.05~1.35, or 1.05~1.3, or 1.05~1.25, or 1.05~1.2, or 1.05~1.15, or 1.05~1.1, or 1.1~1.4, or 1.1~ The values ​​are 1.35, or 1.1-1.3, or 1.1-1.25, or 1.1-1.2, or 1.1-1.15, or 1.15-1.4, or 1.15-1.35, or 1.15-1.3, or 1.15-1.25, or 1.15-1.2, or 1.2-1.4, or 1.2-1.35, or 1.2-1.3, or 1.2-1.25, or 1.25-1.4, or 1.25-1.35, or 1.25-1.3, or 1.3-1.4, or 1.3-1.35.

[0067] In one embodiment, or in combination with any other embodiment, class, or subclass of this third embodiment, DS OH is at least 0.5, at least 0.55, at least 0.6, at least 0.7, at least 0.8, at least 0.9, at least 1.0, at least 1.1, at least 1.2, at least 1.3, at least 1.4, at least 1.5, at least 1.6, at least 1.7, at least 1.8, at least 1.9, at least 2.0, at least 2.1, at least 2.2, at least 2.3, at least 2.4, at least 2.5, or at least 2.6. Additionally or alternatively, DS OH This is less than 2.8, less than 2.7, less than 2.6, less than 2.5, less than 2.4, less than 2.3, less than 2.2, less than 2.1, less than 2.0, less than 1.9, less than 1.8, less than 1.7, less than 1.6, less than 1.5, less than 1.4, less than 1.3, less than 1.2, less than 1.1, less than 1.0, less than 0.9, less than 0.85, or less than 0.8.

[0068] In one embodiment, or in combination with any other embodiment, class, or subclass of this third embodiment, DS OH This includes 0.5~1.3, 0.5~1.2, 0.5~1.1, 0.5~1.0, or 0.5~0.95, or 0.5~0.9, or 0.5~0.85, or 0.5~0.8, or 0.5~0.75, or 0.5~0.7, or 0.5~0.65, or 0.5~0.6, or 0.5~0.55, or 0.55~1.0, or 0.55~0.95, or 0.55~0.9, or 0.55~0.85, or 0.55~0.8, or 0.55~0.75, or 0 The ranges are 0.55-0.7, or 0.55 or 0.65, or 0.55-0.6, or 0.6-0.65, or 0.6-0.7, or 0.6-0.75, or 0.6-0.8, or 0.6-0.85, or 0.6-0.9, or 0.6-0.95, or 0.6-1.0, or 0.65-0.7, or 0.65-0.75, or 0.65-0.8, or 0.65-0.85, or 0.65-0.9, or 0.65-0.95, or 0.65-1.0.

[0069] In one embodiment, or in combination with any other embodiment, class, or subclass of this third embodiment, DS Bu and DS Ac The sum is 1.65-2.3, or 1.65-2.2, or 1.65-2.1, or 1.65-2.0, or 1.65-1.9, or 1.65-1.8, or 1.7-2.3, or 1.7-2.2, or 1.7-2.1, or 1.7-2.0, or 1.7-1.9, or 1.7-1.8, or 1.75-2.3, or 1.75-2.2, or 1.75 ~2.1, or 1.75~2.0, or 1.75~1.9, or 1.8~2.3, or 1.8~2.2, or 1.8~2.1, or 1.8~2.0, or 1.8~1.9, or 1.9~2.3, or 1.9~2.2, or 1.9~2.1, or 1.9~2.0, 2.0~2.4, or 2.0~2.3, or 2.0~2.2, or 2.0~2.1.

[0070] In one embodiment, or in combination with any other embodiment, class, or subclass of this third embodiment, the ratio of hydroxyl substituents to acetyl substituents in the mixed cellulose ester (hydroxyl substituent:acetyl substituent) is at least 0.4:1, at least 0.45:1, at least 0.5:1, at least 0.6:1, at least 0.7:1, at least 0.8:1, at least 0.9:1, at least 1:1, at least 1.1:1, at least 1.2:1, at least 1.3:1, at least 1.4:1, at least 1.5:1, at least 1.6:1, at least 1.7:1, at least 1.8:1, at least 1.9:2, or at least 2:1. Additionally or alternatively, the ratio of hydroxyl substituents to acetyl substituents (hydroxyl substituent:acetyl substituent) in the mixed cellulose ester is less than 2:1, less than 1.9:1, less than 1.8:1, less than 1.7:1, less than 1.6:1, less than 1.5:1, less than 1.4:1, less than 1.3:1, less than 1.2:1, less than 1.1:1, less than 1:1, less than 0.9:1, less than 0.8:1, less than 0.7:1, less than 0.6:1, or less than 0.5:1.

[0071] In one embodiment, or in combination with any other embodiment, class, or subclass of this third embodiment, the ratio of hydroxyl substituents to butyryl substituents (hydroxyl substituent:butyryl substituent) in the mixed cellulose ester is at least 0.4:1, at least 0.5:1, at least 0.6:1, at least 0.7:1, at least 0.8:1, at least 0.9:1, at least 1:1, at least 1.1:1, at least 1.2:1, at least 1.3:1, at least 1.4:1, at least 1.5:1, at least 1.6:1, at least 1.7:1, at least 1.8:1, at least 1.9:2, at least 2:1, at least 3:1, or at least 4:1. Additionally or alternatively, the ratio of hydroxyl substituents to butyryl substituents (hydroxyl substituent:butyryl substituent) in the mixed cellulose ester is less than 6:1, less than 5:1, less than 4:1, less than 3:1, less than 2:1, less than 1.9:1, less than 1.8:1, less than 1.7:1, less than 1.6:1, less than 1.5:1, less than 1.4:1, less than 1.3:1, less than 1.2:1, less than 1.1:1, or less than 1:1.

[0072] In one embodiment, or in combination with any other embodiment, class, or subclass of this third embodiment, the MCE exhibits at least 40% biodegradability, at least 45% biodegradability, or at least 50% biodegradability, or at least 55% biodegradability, at least 60% biodegradability, or at least 65% biodegradability, or at least 70% biodegradability, or at least 75% biodegradability, or at least 80% biodegradability, or at least 85% biodegradability in 56 days, according to at least one of the OECD301B test method, OECD301C test method, or OECD301F test method.

[0073] In one embodiment, or in combination with any other embodiment, class, or subclass of this third embodiment, the MCE exhibits at least 40% biodegradability, at least 45% biodegradability, or at least 50% biodegradability, or at least 55% biodegradability, at least 60% biodegradability, or at least 65% biodegradability, or at least 70% biodegradability, or at least 75% biodegradability, or at least 80% biodegradability, or at least 85% biodegradability in 60 days, according to at least one of the OECD301B test method, OECD301C test method, or OECD301F test method.

[0074] In one embodiment, or in combination with any other embodiment, class, or subclass of this third embodiment, the weight-average molecular weight of MCE is in the range of 5,000 to 100,000 Da, or 5,000 to 50,000 Da, or 5,000 to 25,000 Da, or 15,000 to 100,000 Da, or 15,000 to 50,000 Da, or 15,000 to 25,000 Da, or 50,000 to 100,000 Da, or 75,000 to 100,000 Da, or 15,000 to 250,000 Da.

[0075] In one embodiment, or in combination with any embodiment referenced herein, the butyric acid content of the mixed cellulose esters of the first, second, and / or third embodiment (including any class or subclass of these embodiments) is less than 500 ppm by weight, less than 400 ppm by weight, less than 300 ppm by weight, less than 200 ppm by weight, less than 100 ppm by weight, less than 50 ppm by weight, less than 20 ppm by weight, less than 10 ppm by weight, less than 7.5 ppm by weight, less than 5 ppm by weight, less than 2.5 ppm by weight, or less than 1 ppm by weight.

[0076] In one embodiment, or in combination with any embodiment referenced herein, the acetic acid content of the mixed cellulose ester of the first, second, and / or third embodiment (including any class or subclass of these embodiments) is less than 500 ppm by weight, less than 400 ppm by weight, less than 300 ppm by weight, less than 200 ppm by weight, less than 100 ppm by weight, less than 50 ppm by weight, less than 20 ppm by weight, less than 10 ppm by weight, less than 7.5 ppm by weight, less than 5 ppm by weight, less than 2.5 ppm by weight, or less than 1 ppm by weight.

[0077] In one embodiment, or in combination with any embodiment referenced herein, the propionic acid content of the mixed cellulose esters of the first, second, and / or third embodiment (including any class or subclass of these embodiments) is less than 500 ppm by weight, less than 400 ppm by weight, less than 300 ppm by weight, less than 200 ppm by weight, less than 100 ppm by weight, less than 50 ppm by weight, less than 20 ppm by weight, less than 10 ppm by weight, less than 7.5 ppm by weight, less than 5 ppm by weight, less than 2.5 ppm by weight, or less than 1 ppm by weight.

[0078] In one embodiment, or in combination with any embodiment referenced herein, the sulfuric acid content of the mixed cellulose esters of the first, second, and / or third embodiment (including any class or subclass of these embodiments) is less than 500 ppm by weight, less than 400 ppm by weight, less than 300 ppm by weight, less than 200 ppm by weight, less than 100 ppm by weight, less than 50 ppm by weight, less than 20 ppm by weight, less than 10 ppm by weight, less than 7.5 ppm by weight, less than 5 ppm by weight, less than 2.5 ppm by weight, or less than 1 ppm by weight.

[0079] In one embodiment, or in combination with any embodiment referenced herein, CE100 may be a mixed cellulose ester of the first, second, and / or third embodiment (including any class or subclass of these embodiments).

[0080] Solvent system A solvent system such as solvent 102 can typically solubilize CE to produce the dispersed phase / solid phase of the emulsion / dispersion described herein. In one embodiment, or in combination with any embodiment referred to herein, solvent 102 may consist of a single solvent component or may be a solvent system comprising multiple solvent components. The multiple solvent components may comprise at least two solvent components, at least three solvent components, or a total of three solvent components.

[0081] In one embodiment, or in combination with any embodiment referenced herein, solvent 102 comprises at least one, at least two, or all three of the following: C1-C4 alkyl acetates, C1-C4 alcohols, and water. Examples of C1-C4 alkyl acetates include one or more of methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, and sec-butyl acetate. Examples of C1-C4 alcohols include one or more of methanol, ethanol, propanols (e.g., isopropanol, n-propanol, and isopropyl alcohol), and butanols (e.g., n-butanol, isobutanol, sec-butanol, and tert-butanol).

[0082] In one embodiment, or in combination with any embodiment referenced herein, if solvent 102 contains a plurality of solvent components, C1-C4 alkyl acetate may be present in one or more of the following amounts: (1) at least 10, 25, 50, 60, or 70% by weight; (2) 99% or less by weight, 95% or less by weight, 90% or less by weight, 85% or less by weight, or 80% or less by weight; and (3) within the range of 10-99, 25-95, 50-90, or 70-85% by weight.

[0083] In one embodiment, or in combination with any embodiment referenced herein, if the solvent 102 contains a plurality of solvent components, the C1-C4 alcohols are present in (1) an amount of at least 1, 2, 4, 6, 8, or 10% by weight, (2) an amount of 80% by weight or less, 60% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, or 15% by weight or less, and (3) one or more amounts within the range of 1-80, 2-60, 4-40, 6-30, 8-20, or 10-15% by weight.

[0084] In one embodiment, or in combination with any embodiment referenced herein, if the solvent 102 contains a plurality of solvent components, water is present in one or more of the following amounts: (1) at least 1, 2, 4, 6, or 8 by weight; (2) 50% or less by weight, 25% or less by weight, 20% or less by weight, or 15% or less by weight; and (3) within the range of 1-50, 2-25, 4-30, 6-20, or 8-15% by weight.

[0085] In one embodiment, or in combination with any embodiment referenced herein, solvent 102 comprises at least one, at least two, or all three of ethyl acetate, n-propanol, and water. In such embodiments, ethyl acetate is present in amounts ranging from 50 to 90, 55 to 90, 60 to 90, 65 to 90, 65 to 85, 70 to 85, or 75 to 85% by weight; n-propanol is present in amounts ranging from 4 to 40, 5 to 35, 6 to 30, 7 to 25, 8 to 20, 10 to 20, or 10 to 15% by weight; and water is present in amounts ranging from 4 to 30, 5 to 25, 6 to 20, 7 to 15, 8 to 12, or 9 to 12% by weight.

[0086] Surprisingly, it has been found that water contributes to and / or enables the solubilization of certain mixed cellulose esters. In particular, water is beneficial for mixed cellulose esters with high biodegradability (e.g., DS above a certain threshold). OH It was found that it contributes to the solubilization of (those with a value) and / or enables the solubilization of such mixed cellulose esters. These findings are disclosed in the "Experiments" section below.

[0087] Hydrophilic colloid Hydrophilic colloids described herein, such as hydrophilic colloid 106, are used as colloidal protectants and / or viscosity improvers. In one embodiment, or in combination with any embodiment referred to herein, hydrophilic colloid 106 is a hydrophilic colloid. For example, hydrophilic colloid 106 may include at least one of gelatin, natural rubber, protein, or cellulose derivatives. Examples of cellulose derivatives include methylcellulose and carboxymethylcellulose, or one or both.

[0088] Hydrophilic colloids such as carboxymethylcellulose can be selected based on the desired viscosity of the resulting aqueous mixture. In one embodiment, or in combination with any embodiment referred to herein, a "low" viscosity hydrophilic colloid has a viscosity in the range of 10 to 50 cps, a "medium" viscosity hydrophilic colloid has a viscosity in the range of 400 to 800 cps, and a "high" viscosity hydrophilic colloid has a viscosity in the range of 1500 to 3000 cps.

[0089] Surfactant-based In one embodiment, or in combination with any embodiment referenced herein, the surfactant 108 comprises two or more individual emulsifiers. The individual emulsifiers can be distinguished from one another based on their hydrophilic-lipophilic balance (HLB) values. For example, if the surfactant 108 comprises two individual emulsifiers, such emulsifiers may include a low-HLB emulsifier and a high-HLB emulsifier.

[0090] In one embodiment, or in combination with any embodiment referenced herein, the HLB value of the high-HLB emulsifier is at least 6, 8, 10, 12, 14, 16, or 18, and the HLB value of the low-HLB emulsifier is 12 or less, 10 or less, 8 or less, 6 or less, or 4 or less.

[0091] In one embodiment, or in combination with any embodiment referenced herein, the HLB value of the high-HLB emulsifier is greater than the HLB value of the low-HLB emulsifier by at least one of the following: (1) at least 2, 4, 8, 10, 12, or 14 greater; (2) at least 25 greater, at least 20 greater, or at least 15 greater; or (3) at least 2-25 greater, at least 8-20 greater, or at least 12-15 greater.

[0092] In one embodiment, or in combination with any embodiment referenced herein, the low-HLB emulsifier is a glycerol ester of stearic acid. In one embodiment, or in combination with any embodiment referenced herein, the high-HLB emulsifier is a secondary alcohol ethoxylate.

[0093] In one embodiment, or in combination with any embodiment referenced herein, the surfactant 108 further comprises a third emulsifier. The third emulsifier has an HLB value greater than that of the low HLB emulsifier. In one embodiment, or in combination with any embodiment referenced herein, the third emulsifier is polyethylene glycol ester of stearic acid.

[0094] When surfactant 108 is composed of all three emulsifiers, the low HLB emulsifier and the third emulsifier can be present in ratios of at least 0.25:1, 0.5:1, 0.75:1, 1:1, 1.25:1, 1.5:1, 1.75:1, or 2:1, and / or ratios of 5:1 or less, 4:1 or less, 3:1 or less, 2:1 or less, 1.75:1 or less, 1.5:1 or less, or 1.25:1 or less. The low HLB emulsifier and the third emulsifier can constitute a composite emulsifier. Furthermore, the high HLB emulsifier and the combined emulsifier may be present in surfactant 108 in ratios of at least 0.25:1, 0.5:1, 0.75:1, 1:1, 1.25:1, 1.5:1, 1.75:1, or 2:1, and / or ratios of 5:1 or less, 4:1 or less, 3:1 or less, 2:1 or less, 1.75:1 or less, 1.5:1 or less, or 1.25:1 or less.

[0095] Referring here to Figure 2, the illustrated process for producing CE fine particles 112 includes separately preparing a CE dope 136 and an aqueous mixture 138. Next, the CE dope 136 and the aqueous mixture 138 are mixed to form the CE fine particles 112. For example, the CE dope 136 can be prepared in unit 140, and the aqueous mixture 138 can be prepared in unit 142. Then, the CE dope 136 and the aqueous mixture 138 can be mixed in unit 144 to prepare an emulsion and / or dispersion. This will be explained in more detail below.

[0096] In one embodiment, or in combination with any embodiment referenced herein, CE dope 136 is prepared from CE 100, solvent 102, water 104, and, in some embodiments, recycled solvent 146 obtained from a solvent-rich flow 134.

[0097] In one embodiment, or in combination with any embodiment referenced herein, CE100 is present in the CE dope in (1) at least 1, 2, 4, 6, 8, or 10% by weight, (2) 80% or less by weight, 60% or less by weight, 40% or less by weight, 30% or less by weight, 20% or less by weight, or 15% or less by weight, and (3) one or more within the ranges of 1-80, 2-60, 4-40, 6-30, 8-20, or 10-15% by weight.

[0098] In one embodiment, or in combination with any embodiment referenced herein, if the solvent 102 contains C1-C4 alkyl acetate, the C1-C4 alkyl acetate is present in the CE dope 136 in one or more of the following amounts: (1) at least 10, 25, 50, 60, or 65% by weight; (2) 95% or less by weight, 90% or less by weight, 85% or less by weight, 80% or less by weight, or 75% or less by weight; and (3) within the range of 10-95, 25-90, 50-85, or 65-75% by weight.

[0099] In one embodiment, or in combination with any embodiment referenced herein, if the solvent 102 contains C1-C4 alcohols, the C1-C4 alcohols are present in the CE dope 136 in one or more of the following amounts: (1) at least 1, 2, 4, 6, or 8 by weight; (2) 50% or less by weight, 25% or less by weight, 20% or less by weight, or 15% or less by weight; and (3) within the range of 1-50, 2-25, 4-30, 6-20, or 8-15% by weight.

[0100] In one embodiment, or in combination with any other embodiment, the ratio of solvent to CE used for dissolving and preparing CE-doped 136 (solvent:CE) is at least 1:1, 2:1, 3:1, 4:1, or 5:1, and / or 100:1 or less, 50:1 or less, 25:1 or less, or 10:1 or less.

[0101] In one embodiment, or in combination with any embodiment referenced herein, if the solvent 102 contains water, water is present in the CE dope 136 in one or more of the following amounts: (1) at least 0.5, 1, 2, 4, or 6% by weight; (2) 40% or less by weight, 25% or less by weight, 15% or less by weight, or 10% or less by weight; and (3) within the range of 0.5 to 40, 1 to 25, 2 to 15, 4 to 20, or 6 to 10% by weight.

[0102] In one particular embodiment, CE dope 136 is prepared from CE 100, solvent 102 containing ethyl acetate and n-propanol, and water 104. In such embodiment, CE is present in CE dope 136 in amounts ranging from 6 to 30, 7 to 25, 8 to 20, 9 to 20, 10 to 15, or 12 to 15% by weight; ethyl acetate is present in CE dope 136 in amounts ranging from 50 to 85, 55 to 85, 60 to 85, 65 to 85, 70 to 85, or 75 to 85% by weight; n-propanol is present in CE dope 136 in amounts ranging from 4 to 30, 6 to 25, 8 to 20, 10 to 20, or 12 to 15% by weight; and water is present in CE dope 136 in amounts ranging from 4 to 20, 5 to 18, 6 to 16, 7 to 14, or 8 to 12% by weight.

[0103] In one embodiment, or in combination with any embodiment referenced herein, CE100, solvent 102, and water 104 are mixed in unit 140 until substantially homogeneous to produce CE dope 136. In one embodiment, or in combination with any embodiment referenced herein, these components are mixed at room temperature (e.g., at least 15, 20, 25, or 30°C and / or 45°C or below, 40°C or below, 35°C or below, 30°C or below, 25°C or below, or 20°C) for at least 1, 2, 5, 10, 15, 20, 25, 30, 45, 60, 120, or 240 minutes and / or for the length of time required to produce a substantially homogeneous mixture.

[0104] In one embodiment, or in combination with any embodiment referenced herein, an aqueous mixture 138 is prepared from water 104, a hydrophilic colloid 106, a surfactant 108, and, in some embodiments, a recycled solvent 146 obtained from a solvent-rich stream 134. Optionally, additional solvent 148 may be added to units 140 and / or 142 as needed to maintain the concentration(s) of the solvent components at a suitable level.

[0105] In one embodiment, or in combination with any embodiment referenced herein, the ratio of the recycled solvent portion to the new solvent portion used in units 140 and / or 142 (recycled solvent portion:new solvent portion) is at least 2.5:1, 10:1, 25:1, 50:1, 75:1, 90:1, 95:1, or 99:1 by weight, and / or 1000:1 or less, 500:1 or less, 200:1 or less, or 100:1 or less by weight.

[0106] In one embodiment, or in combination with any embodiment referenced herein, the difference between the composition of the recycled solvent and the composition of the new solvent is 10% by weight or less, 5% by weight or less, 2% by weight or less, or 1% by weight or less in total.

[0107] In one embodiment, or in combination with any embodiment referenced herein, the new solvent and the recycled solvent portion have substantially the same composition.

[0108] In one embodiment, or in combination with any embodiment referenced herein, water is present in the aqueous mixture 138 in one or more of the following amounts: (1) at least 40, 60, 70, 80, or 85% by weight; (2) 99% or less by weight, 97% or less by weight, 95% or less by weight, 94% or less by weight, or 92% or less by weight; and (3) 40-99, 70-95, or 85-92% by weight.

[0109] In one embodiment, or in combination with any embodiment referenced herein, the hydrophilic colloid is present in the aqueous mixture 138 in one or more of the following amounts: (1) at least 0.001, 0.005, 0.01, 0.05, or 0.1% by weight; (2) 15% by weight or less, 10% by weight or less, 5% by weight or less, 2% by weight or less, or 1% by weight or less; and (3) 0.001 to 15, 0.01 to 5, or 0.1 to 2% by weight.

[0110] In one embodiment, or in combination with any embodiment referenced herein, the surfactant is present in the aqueous mixture 138 in one or more of the following amounts: (1) at least 0.005, 0.01, 0.05, 0.1, or 0.5% by weight; (2) 15% or less by weight, 10% or less by weight, 5% or less by weight, 2% or less by weight, or 1.5% or less by weight; and (3) within the range of 0.005 to 15, 0.05 to 5, or 0.5 to 1.5% by weight.

[0111] As described above, examples of surfactants described herein include high-HLB emulsifiers and low-HLB emulsifiers. In such embodiments, the high-HLB emulsifier and the low-HLB emulsifier are present in the aqueous mixture 138 in a ratio of high-HLB emulsifier to low-HLB emulsifier within the range of at least 0.25:1, 0.5:1, 1:1, 1.5:1, or 1.75:1, and / or a ratio of high-HLB emulsifier to low-HLB emulsifier within the range of 10:1 or less, 5:1 or less, 3:1 or less, or 2.5:1 or less, and / or a ratio of high-HLB emulsifier to low-HLB emulsifier within the range of 0.25:1 to 10:1, 0.5:1 to 5:1, or 1:1 to 3:1.

[0112] Referring again to Figure 2, in some embodiments, an additional solvent 148 and / or recycled solvent 146 are introduced into unit 142. In such embodiments, the solvent used to prepare the CE-doped 136 and aqueous mixture 138 is a common C1-C4 alkyl acetate. By using at least one common component in the solvent systems introduced into units 140 and 142, the simplification of solvent separation, recovery, and reuse as described herein is facilitated.

[0113] In one embodiment, or in combination with any embodiment referenced herein, if the aqueous mixture 138 contains C1-C4 alkyl acetate, the C1-C4 alkyl acetate is present in the aqueous mixture 138 in one or more of the following amounts: (1) at least 1, 2, 4, 6, or 8% by weight; (2) 50% or less by weight, 40% or less by weight, 30% or less by weight, 20% or less by weight, or 15% or less by weight; and (3) within the range of 1-50, 2-40, or 6-20% by weight.

[0114] In one embodiment, or in combination with any embodiment referred to herein, C1-C4 alkyl acetates are present in the aqueous mixture 138 in amounts of 25, 20, 15, 10, 5, or 2% by weight of C1-C4 alkyl acetates in water at 20°C, with solubility not exceeding 2% by weight.

[0115] The C1-C4 alkyl acetate may be either methyl acetate or ethyl acetate, or both. In one embodiment, or in combination with any embodiment referenced herein, if the C1-C4 alkyl acetate is ethyl acetate, ethyl acetate is present in the aqueous mixture in an amount ranging from 2 to 25, 4 to 20, 6 to 15, or 8 to 10% by weight. In one embodiment, or in combination with any embodiment referenced herein, if the C1-C4 alkyl acetate is methyl acetate, methyl acetate is present in the aqueous mixture in an amount ranging from 5 to 50, 10 to 40, 15 to 35, or 20 to 30% by weight.

[0116] In one particular embodiment, the aqueous mixture 138 is prepared from water 104, hydrophilic colloid 106, surfactant 108, and C1-C4 alkyl acetate. In such embodiments, water is present in the aqueous mixture 138 in an amount ranging from 70 to 95, 75 to 95, 80 to 95, 85 to 95, or 87.5 to 92.5% by weight; hydrophilic colloids are present in the aqueous mixture 138 in an amount ranging from 0.01 to 5, 0.1 to 4, 0.5 to 3, 0.6 to 2, 0.7 to 1, or 0.8 to 0.9% by weight; surfactants are present in the aqueous mixture 138 in an amount ranging from 0.05 to 5, 0.1 to 5, 0.1 to 4, 0.5 to 3, 0.6 to 2, 0.7 to 1, or 0.8 to 1% by weight; and C1-C4 alkyl acetates are present in the aqueous mixture 138 in an amount ranging from 2 to 40, 3 to 35, 4 to 30, 5 to 25, 5 to 20, 5 to 15, 5 to 10, or 6 to 10% by weight.

[0117] In one embodiment, or in combination with any embodiment referenced herein, water 104, hydrophilic colloid 106, surfactant 108, and optionally C1-C4 alkyl acetate are mixed in unit 142 to produce an aqueous mixture 138. In one embodiment, or in combination with any embodiment referenced herein, these components are mixed at a temperature of at least 15, 20, 25, 30, 35, 40, 45, or 50°C and / or below 100°C, 75°C, 50°C, 40°C, 35°C, 30°C, 25°C, or 20°C for at least 1, 2, 5, 10, 15, 20, 25, 30, 45, 60, 120, or 240 minutes and / or for a length of time necessary to produce a substantially homogeneous mixture, depending on the viscosity of the hydrophilic colloid used.

[0118] Preparation of emulsions / dispersions Once prepared, the CE dope 136 and aqueous mixture 138 can be mixed in unit 144 to produce the emulsion and / or dispersion described above.

[0119] In one embodiment, or in combination with any embodiment referenced herein, the ratio of CE dope 136 to aqueous mixture 138 mixed in unit 144 to prepare the initial emulsion (CE dope 136: aqueous mixture 138) is at least 0.05:1 to 10:1, 0.1:1 to 5:1, 0.2:1 to 2:1, or 0.4:1 to 0.8:1.

[0120] In one embodiment, or in combination with any embodiment referenced herein, the initial emulsion contains water in an amount of at least 10, 20, 30, 40, 50, or 60% by weight, and / or 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, or 40% by weight or less.

[0121] Once mixed, the initial emulsion is converted into a pre-cured dispersion containing solid and liquid phases. This conversion can be carried out by at least one of shearing, spraying (ultrasonic or electrostatic), and film emulsification.

[0122] In one embodiment, or in combination with any embodiment referenced herein, a mixture of CE dope and aqueous mixture is passed through a high-shear mixer and recirculated to disperse the solid phase into the liquid phase, accelerate the hardening of the solid phase, and generate initial fine particles. This shearing can be performed while supplying the CE dope 136 and aqueous mixture 138 to unit 144, and / or after a predetermined amount of CE dope 136 and aqueous mixture 138 has been placed in unit 144.

[0123] In one embodiment, or in combination with any embodiment referenced herein, a mixture of CE dope and aqueous mixture is passed through a high shear mixer for at least 1, 2, 3, 4, or 5 residence cycles, and / or 20, 15, 10, 9, or 8 residence cycles, based on the total volume of the high shear mixer used, and recirculated. High shear mixing is also performed for at least 1, 2, 5, 10, 15, 20, 25, 30, 45, 60, 120, or 240 minutes, and / or for the length of time required to recirculate the volume of the mixture according to the predetermined number of residence cycles.

[0124] To generate initial particles that form the CE particles described herein, the mixture of CE dope and aqueous mixture is stirred in unit 144. The stirring performed in unit 144 can be quantified by at least one of (1) the impeller tip velocity, (2) the impeller Reynolds number, and (3) the power-to-mass ratio (power:mass ratio). In one embodiment, or in combination with any embodiment referred to herein, high-shear mixing is performed with an impeller tip velocity of at least 25, 50, 75, 100, 150, 200, 250, or 300 cm / sec, and / or an impeller tip velocity of 1000 cm / sec or less, 500 cm / sec or less, 400 cm / sec or less, 300 cm / sec or less, 200 cm / sec or less, or 100 cm / sec or less. In one embodiment, or in combination with any embodiment referenced herein, high-shear mixing is performed at impeller Reynolds numbers of at least 500, 1000, 1500, 2000, 3000, 4000, 5000, or 6000, and / or impeller Reynolds numbers of 15000 or less, 10000 or less, 8000 or less, 6000 or less, 5000 or less, 4000 or less, or 3000 or less. In one embodiment, or in combination with any embodiment referenced herein, high shear mixing is performed at an output:mass ratio of at least 0.01, 0.02, 0.03, 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, or 3.0, and / or an output:mass ratio of 10.0 or less, 7.5 or less, 5.0 or less, 4.0 or less, 3.0 or less, 2.5 or less, 2.0 or less, 1.5 or less, 1.0 or less, 0.5 or less, or 0.1 or less.

[0125] As used herein, terms such as “solid,” “solid phase,” “particle,” and “fine particles” refer to semi-solid materials that retain their respective properties (i.e., the property of flowing together) when the surrounding aqueous / continuous phase is removed.

[0126] Hardening by extractant A pre-cured dispersion 150 prepared in unit 144, containing initial particles (i.e., solid phase), can be introduced into a curing unit 152 to convert the initial particles into cured CE particles 112. In unit 152, the initial particles contained in the pre-cured dispersion 150 are brought into contact with an extractant 154 (i.e., a precipitate) to produce a cured dispersion 156. That is, this contact step facilitates the desolvation of the initial particles and their curing into CE particles. In one embodiment, or in combination with any embodiment referred to herein, the extractant is water. Alternatively, the extractant may be methanol, ethanol, or a combination thereof.

[0127] In one embodiment, or in combination with any embodiment referenced herein, the pre-cured dispersion and the extractant are mixed in unit 152 in a weight ratio of extractant to dispersion of at least 0.5:1, 1:1, 1.5:1, 2:1, or 1.5:1 and / or 10:1 or less, 8:1 or less, 6:1 or less, 4:1 or less, or 3:1 or less (extractant:dispersion).

[0128] In one embodiment, or in combination with any embodiment referenced herein, the weight ratio of the extractant to the pre-cured particles used in the contact step (extractant:pre-cured particles) is at least 2:1, 5:1, 10:1, 20:1, 30:1, or 40:1, and / or 200:1 or less, 100:1 or less, 80:1 or less, 60:1 or less, or 50:1 or less.

[0129] As a result, in one embodiment, or in combination with any embodiment referred to herein, the cured dispersion 156 contains water in one or more of the following amounts: (1) at least 25, 50, 60, 70, 80, 85, or 90% by weight; (2) 99% or less by weight, 97.5% or less by weight, 95% or less by weight, 92.5% or less by weight, 90% or less by weight, 80% or less by weight, 70% or less by weight, 60% or less by weight; and (3) 50-99%, 70-95%, or 80-92.5% by weight.

[0130] In one embodiment, or in combination with any embodiment referenced herein, the cured dispersion 156 contains water at a weight concentration at least 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or 5 times higher than the weight concentration of water in the initial emulsion, and / or at a weight concentration of 100 times or less, 70 times or less, 50 times or less, 25 times or less, 15 times or less, 10 times or less, 5 times or less, or 2.5 times or less.

[0131] In one embodiment, or in combination with any embodiment referenced herein, the curing of the fine particles is performed under stirring. The stirring performed in unit 152 can be quantified by at least one of (1) the impeller tip velocity, (2) the impeller Reynolds number, and (3) the ratio of output to mass (output:mass). In one embodiment, or in combination with any embodiment referenced herein, conversion / curing is performed at an impeller tip velocity of at least 25, 50, 75, 100, 150, 200, 250, or 300 cm / sec, and / or an impeller tip velocity of 1000 cm / sec or less, 500 cm / sec or less, 400 cm / sec or less, 300 cm / sec or less, 200 cm / sec or less, or 100 cm / sec or less. In one embodiment, or in combination with any embodiment referenced herein, conversion / curing is performed at an impeller Reynolds number of at least 500, 1000, 1500, 2000, 3000, 4000, 5000, or 6000, and / or an impeller Reynolds number of 15000 or less, 10000 or less, 8000 or less, 6000 or less, 5000 or less, 4000 or less, or 3000 or less. In one embodiment, or in combination with any embodiment referenced herein, conversion / curing is performed at an output:mass ratio of at least 0.01, 0.02, 0.03, 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, or 3.0, and / or at an output:mass ratio of 10.0 or less, 7.5 or less, 5.0 or less, 4.0 or less, 3.0 or less, 2.5 or less, 2.0 or less, 1.5 or less, 1.0 or less, 0.5 or less, or 0.1 or less.

[0132] Furthermore, the conversion / curing is performed for a time of at least 0.1, 0.5, 1, 2, 4, 6, 8, 10, or 20 minutes and / or for a time of 12 hours or less, 8 hours or less, 6 hours or less, 4 hours or less, or 2 hours or less at a temperature of at least 0, 5, or 10°C and / or a temperature of 100°C or less, 75°C or less, 50°C or less, or 25°C or less.

[0133] In one embodiment, or in combination with any embodiment referenced herein, the conversion / curing is performed in a single container or in multiple containers. Depending on the amount of CE microparticles to be produced and the volume of containers available for curing, multiple containers may be required. In embodiments using multiple containers, a first portion of the pre-cured dispersion 150 can be received into a first curing unit, and a second portion of the pre-cured dispersion can be received into a second curing unit. Flow may then be carried out between the separate curing units to facilitate the transfer of material so as to accelerate the desolvation of the initial microparticles.

[0134] In one embodiment, or in combination with any embodiment referenced herein, the pre-cured dispersion 150 has a solid content of at least 0.5, 1, 2, 3, or 4% by weight, and / or a solid content of 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, or 6% by weight or less.

[0135] As a result of curing, in one embodiment, or in combination with any embodiment referenced herein, the cured dispersion 156 has a solid content of at least 0.05, 0.1, 0.5, or 1% by weight, and / or a solid content of 20% by weight or less, 10% by weight or less, 5% by weight or less, 2% by weight or less, or 1% by weight or less.

[0136] In one embodiment, or in combination with any embodiment referenced herein, the solid content of the pre-cured dispersion is at least 1.5, 2, 3, or 4 times the solid content of the cured dispersion, and / or 20 times or less, 10 times or less, 8 times or less, or 6 times or less. In other words, in unit 152, the solvent is extracted from the initial fine particles to produce the cured dispersion 156. The cured dispersion 156 comprises cured CE fine particles 112 and a precipitate containing the solvent.

[0137] Isolation / Separation of CE Microparticles The CE particles 112 can be isolated and recovered from the cured dispersion 156 using any suitable technique in unit 158. In one embodiment, or in combination with any embodiment referenced herein, isolation can be performed by at least one, at least two, or all three of the following: (1) flotation of one or more liquid components from the cured CE particles; (2) separation of the cured CE particles from one or more liquid components by filtration; and (3) centrifugation, redispersion, and drying of the cured particles.

[0138] The processing of solids and / or the isolation of CE particles may be carried out in a single unit, as shown in Figure 1, or in multiple units, as shown in Figure 2. Referring to Figure 2, the wet solids flow 160 and the separated mother liquor flow 162 are discharged from unit 158. The wet solids flow 160 contains cured CE particles and residual liquid. In one embodiment, or in combination with any embodiment referred to herein, the wet solids flow 160 has a solid content of at least 10, 20, 25, 30, 35, 40, or 45% by weight, and / or 60% by weight or less, 65% by weight or less, 50% by weight or less, 45% by weight or less, or 40% by weight or less. This allows the wet solids flow 160 to be sent to downstream units with fewer clogging and processing problems.

[0139] Next, the wet solid material 160 may be processed in a washing unit 164 and a second solid / liquid separation unit 166, if applicable. In unit 164, the cured CE particles are washed with water 122 to produce a washed solid material 168. Next, the washed solid material 168 is processed in unit 166 by at least one, at least two, or all three of the following: (1) draining one or more liquid components from the cured CE particles, (2) separating the cured CE particles from one or more liquid components by filtration, and (3) centrifuging, redispersing, and drying the cured particles. This second solid / liquid separation step facilitates a reduction in the solvent content in the liquid surrounding the cured CE particles.

[0140] The washing liquid 130 can be recovered from the second solid / liquid separation step and then recycled for use as at least part of the aqueous mixture in unit 142 and / or for use as at least part of the sediment in unit 152.

[0141] In one embodiment, or in combination with any embodiment referenced herein, at least 1, 5, or 10% by weight and / or 90% by weight or less, 50% by weight or less, 20% by weight or less, or 10% by weight or less of the aqueous mixture 138 is used as the recirculated washing solution.

[0142] In one embodiment, or in combination with any embodiment referenced herein, at least 1, 5, or 10% by weight, and / or 90% by weight or less, 50% by weight or less, 20% by weight or less, or 10% by weight or less of the sedimentation liquid 154 used in unit 152 is a recirculated washing liquid.

[0143] The wet solid material 172 discharged from unit 166 is then received into drying unit 170. In one embodiment, or in combination with any embodiment referred to herein, drying is carried out in unit 170 by applying heat while stirring. Such stirring smoothly suppresses aggregation of the recovered CE particles 112. The properties of the recovered CE particles 112 are described in further detail below.

[0144] In one embodiment, or in combination with any embodiment referred to herein, the drying unit 170 is a rotary cone dryer.

[0145] Liquid treatment and recycling The separated mother liquor stream 162 discharged from unit 164 can be processed to recover water and / or solvent. The recovered water and / or solvent can then be recycled to one or more of the units shown in Figure 2 in order to improve the economic efficiency of the particulate formation process described herein.

[0146] The liquid processing may be carried out in a single unit, as shown in Figure 1, or in multiple units, as shown in Figure 2. Referring to Figure 2, the mother liquor flow 162 includes, for example, at least a portion of the water and at least a portion of the solvent introduced in units 140 and / or 142. The mother liquor flow 162 may also contain residual amounts of hydrophilic colloid, surfactant, and any components used to produce the mixed cellulose ester.

[0147] The mother liquor flow 162 can be heated (174) and then separated in unit 176 into at least two separate flows (for example, a solvent-heavy flow 134 and a water-heavy (solvent-low) flow 132). The mother liquor flow 162 can be separated in unit 176 using any suitable method. In one embodiment, or in combination with any embodiment described herein, the separation of liquids can be carried out by distillation or the like.

[0148] In one embodiment, or in combination with any embodiment referenced herein, the water-rich stream 132 comprises (1) water, (2) a surfactant, (3) a hydrophilic colloid, and (4) one or more C1-C4 alkyl acetates.

[0149] Thus, the water-rich flow 132 can be cooled 181 and then recirculated to one or more units as shown in Figure 2. For example, the composition of the water-rich flow 132 can be recirculated to at least one of the units 142 as a flow 178 for use in the preparation of an aqueous mixture 138, and / or recirculated to unit 152 as a flow 180 for use in the desolvation of initial fine particles, thereby reducing the amount of water required for such processes. Any excess material not needed in these processes can be discharged from the system and, for example, used in wastewater treatment.

[0150] In one embodiment, or in combination with any embodiment referenced herein, the ratio of recycled water in stream 180 used in the curing process to recycled water in stream 178 used in the preparation of the aqueous mixture 138 is at least 1:1, 1.5:1, 2:1, 3:1, 4:1, and / or 20:1 or less, 10:1 or less, 8:1 or less, or 6:1 or less.

[0151] In one embodiment, or in combination with any embodiment referenced herein, the ratio of recycled water in the flow 180 used in the curing process to discharged water is at least 1:1, 1.5:1, 2:1, 3:1, 4:1, and / or 20:1 or less, 10:1 or less, 8:1 or less, or 6:1 or less.

[0152] In one embodiment, or in combination with any embodiment referenced herein, at least 75, 90, 95, 98, 99, or 100% by weight of the extractant used in unit 152 is recycled water recovered downstream of unit 152 (for example, water contained in flow 132 which contains a large amount of water to be recycled back into unit 152).

[0153] In one embodiment, or in combination with any embodiment referenced herein, fresh water 154 is added to unit 152 for use in the curing process.

[0154] In one embodiment, or in combination with any embodiment described herein, the ratio of the total amount of new water added to the wastewater is at least 0.25:1, 0.5:1, 0.75:1, or 0.9:1, and / or 4:1 or less, 2:1 or less, 1.5:1 or less, 1.25:1 or less, or 1.1:1 or less.

[0155] In one embodiment, or in combination with any embodiment referenced herein, the solvent-rich stream 134 comprises one or more of (1) C1-C4 alkyl acetates, (2) C1-C4 alcohols, and (3) water.

[0156] Therefore, the solvent-rich flow 134 can be recycled to one or more units as shown in Figure 2. For example, the composition of the solvent-rich flow 134 can be recycled to at least one of the units 140 for use as part of the solvent in the preparation of the CE dope 136, and / or recycled to unit 142 for use in the preparation of the aqueous mixture 138. Any excess material not needed for these processes can be discharged from the system.

[0157] In one embodiment, or in combination with any embodiment referenced herein, at least 75, 90, 95, 98, 99, or 100% by weight of the solvent used in the unit 140 for preparing the CE-doped 136 is recycled solvent 146.

[0158] In one embodiment, or in combination with any embodiment referenced herein, fresh water 104 is added to unit 142 for use in preparing the aqueous mixture 138.

[0159] In one embodiment, or in combination with any embodiment referenced herein, the ratio of the total amount of water in flows 178 and 180 to the total amount of new water 104 added in unit 142 is at least 2:1, 4:1, 6:1, or 8:1.

[0160] In one embodiment, or in combination with any embodiment referenced herein, the aqueous mixture 138 comprises an azeotropic mixture of water and C1-C4 alkyl acetates, and / or an azeotropic mixture of water and C1-C4 alcohols, derived from a water-rich stream 132.

[0161] Hydroxyl is typically a strong hydrogen bonding group. Therefore, the DS of a given substance OH As carbon number increases, the opportunities for hydrogen bonding increase. The cosolvent alcohols in the solvent systems described herein are also strong hydrogen bonding agents. However, surprisingly, it has been found that the ability of cosolvent alcohols to form hydrogen bonds decreases as the number of carbon atoms (i.e., C1-C4) increases. Thus, a low-carbon binary solvent system without water has a higher DS threshold than the biodegradation threshold. OH (For example, DS with a value greater than 0.8) OH It was found that cellulose esters having ) could be dissolved. In contrast, a water-free binary solvent system with a high carbon number showed a higher DS threshold than the same. OH It was found that cellulose esters having [certain properties] could not be dissolved. Thus, it was found that the presence of a substantially sterically hindrance-free strong hydrogen bonding agent (i.e., water) in a solvent system containing a high-carbon alcohol promoted the dissolution of the mixed CE described herein into the solvent system.

[0162] In one embodiment, or in combination with any embodiment referenced herein, the recycling solvent 146 contains water in an amount of at least 1, 2, 4, 6, or 8% by weight, and / or 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, or 10% by weight or less.

[0163] In one embodiment, or in combination with any embodiment referenced herein, the recycled solvent 146 contains at least one azeotropic mixture, the azeotropic mixture comprising water and another component.

[0164] In one embodiment, or in combination with any embodiment referenced herein, the azeotrope may be present in the recycled solvent 146, and may be a water / alcohol azeotrope, a water / alkyl acetate azeotrope, or both a water / alcohol azeotrope and a water / alkyl acetate azeotrope.

[0165] In one embodiment, or in combination with any embodiment referenced herein, the recycled solvent 146 contains multiple azeotropes. In one embodiment, or in combination with any embodiment referenced herein, the multiple azeotropes contain multiple binary azeotropes. In one embodiment, or in combination with any embodiment referenced herein, the components of the solvent system are selected such that the recycled solvent 146 does not contain any ternary azeotropes, thereby simplifying the recovery and recycling of the solvent.

[0166] In one embodiment, or in combination with any embodiment referenced herein, the content of the ternary azeotrope mixture in the solvent-rich stream 134 is less than 10% by weight, less than 1% by weight, less than 0.1% by weight, or 0.0% by weight.

[0167] In one embodiment, or in combination with any embodiment referenced herein, the recycled solvent 146 contains a total of three binary azeotropes, such as a water / alcohol azeotrope, a water / alkyl acetate azeotrope, and an alcohol / alkyl acetate azeotrope.

[0168] Additional Embodiments Referring here to Figure 3, CE fine particles 112 are generated by continuous particle formation. In an exemplary embodiment, particle formation is initiated in unit 142, in which water 104, hydrophilic colloid 106, surfactant 108, and, in some embodiments, recycled solvent 146 derived from a solvent-rich stream 134 are mixed to prepare an aqueous mixture 138.

[0169] The aqueous mixture 138 is discharged from unit 142 and received into dispersion preparation unit 182. In unit 182, the aqueous mixture 138 is mixed with CE 100, solvent 102, and optionally, recycled solvent 146 derived from solvent-rich flow 134. Thus, rather than preparing the CE dope 136 and aqueous mixture 138 in separate units, the aqueous mixture 138, CE 100, and solvent 102 are mixed in a common unit to prepare the initial emulsion.

[0170] In one embodiment, or in combination with any embodiment referenced herein, the aqueous mixture 138, CE 100, and solvent 102 are stirred in unit 182, and the mixture of CE dope and aqueous mixture is passed through a high-shear mixer and recirculated to disperse the solid phase in the liquid phase of the initial emulsion, thereby accelerating the hardening of the solid phase and generating initial fine particles.

[0171] To generate initial fine particles, a mixture of aqueous mixture 138, CE100, and solvent 102 is stirred in unit 182. The stirring performed in unit 182 can be quantified by at least one of (1) impeller tip velocity, (2) impeller Reynolds number, and (3) power-to-mass ratio (power:mass). In one embodiment, or in combination with any embodiment referred to herein, high-shear mixing is performed with an impeller tip velocity of at least 25, 50, 75, 100, 150, 200, 250, or 300 cm / sec, and / or an impeller tip velocity of 1000 cm / sec or less, 500 cm / sec or less, 400 cm / sec or less, 300 cm / sec or less, 200 cm / sec or less, or 100 cm / sec or less. In one embodiment, or in combination with any embodiment referenced herein, high-shear mixing is performed at impeller Reynolds numbers of at least 500, 1000, 1500, 2000, 3000, 4000, 5000, or 6000, and / or impeller Reynolds numbers of 15000 or less, 10000 or less, 8000 or less, 6000 or less, 5000 or less, 4000 or less, or 3000 or less. In one embodiment, or in combination with any embodiment referenced herein, high shear mixing is performed at an output:mass ratio of at least 0.01, 0.02, 0.03, 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, or 3.0, and / or an output:mass ratio of 10.0 or less, 7.5 or less, 5.0 or less, 4.0 or less, 3.0 or less, 2.5 or less, 2.0 or less, 1.5 or less, 1.0 or less, 0.5 or less, or 0.1 or less.

[0172] Next, the pre-cured dispersion 150 is discharged from unit 182, and the cured CE fine particles 112 are recovered from there as described above.

[0173] Referring to Figure 4, CE fine particles 112 are produced by preparing the dope and aqueous mixture separately, and by combining the preparation of the emulsion / dispersion with particle curing. In an exemplary embodiment, particle formation is initiated as shown in Figure 2, at which time the CE dope 136 and aqueous mixture 138 are prepared in separate units.

[0174] In Figure 4, however, the CE dope 136 and aqueous mixture 138 are supplied to a common emulsion / dispersion preparation and particle curing unit 184. In unit 184, the CE dope 136 and aqueous mixture 138 are mixed and stirred to prepare an initial emulsion as described herein. Once the initial emulsion is prepared, the extractant 154 is supplied directly to unit 184 to desolvent the initial particles.

[0175] Referring to Figure 5, CE particles 112 are produced by the preparation of a complex emulsion / dispersion. In an exemplary embodiment, particle formation is initiated by mixing CE 100, solvent 102, water 104, hydrophilic colloid 106, surfactant 108, and optionally recycled solvent 146 and recycled water 178 in a common unit 186. This mixture is stirred as described herein to produce a pre-cured dispersion 150 containing initial particles. The pre-cured dispersion is received into unit 152 and the initial particles are desolvented as described herein.

[0176] Referring to Figure 6, CE fine particles 112 are produced by combining the preparation of an emulsion / dispersion and particle curing. In an exemplary embodiment, particle formation is initiated by mixing CE 100, solvent 102, water 104, hydrophilic colloid 106, surfactant 108, and optionally recycled solvent 146 and recycled water 178 in a common unit 188. These components are mixed and stirred in unit 188 to prepare an initial emulsion as described herein. Once the initial emulsion is prepared, the solvent is removed from the initial fine particles by supplying extractant 154 directly to unit 188.

[0177] Referring to Figure 7, CE fine particles 112 are generated by solvent removal before particle curing. In an exemplary embodiment, the pre-cured dispersion 150 discharged from unit 144 is received in the removal unit 190, not in the particle curing unit 152. In unit 190, a low-solvent dispersion 192 with reduced solvent content is prepared by removing at least a portion of the solvent of the pre-cured dispersion 150 from its liquid phase. The low-solvent dispersion 192 is received in unit 152, and the pre-cured fine particles contained therein are cured as described above. The removal solvent stream 194 discharged from unit 190 can be led to unit 176 for liquid processing and recirculation.

[0178] In one embodiment, or in combination with any embodiment referenced herein, removal in unit 190 is performed by bar vaporization, cross-flow membrane filtration (ultrafiltration or nanofiltration), flashpot, spraypot, or wiped film evaporation.

[0179] In one embodiment, or in combination with any embodiment referenced herein, the removal in unit 190 reduces the solvent in the dispersion by at least 30% by weight, at least 50% by weight, at least 75% by weight, at least 90% by weight, 30-90% by weight, or 50-75% by weight.

[0180] In one embodiment, or in combination with any embodiment referenced herein, the low solvent dispersion 192 has at least 3, 4, 5, or 6% by weight and / or 40% by weight or less, 30% by weight or less, 20% by weight or less, or 10% by weight or less of solids.

[0181] In one embodiment, or in combination with any embodiment referenced herein, the volume ratio of the settling liquid to the dispersion (settling liquid:dispersion) used in unit 152 is less than 2.5:1, less than 2:1, less than 1.75:1, less than 1.5:1, less than 1.25:1, or less than 1:1.

[0182] Hardened CE fine particles The cured CE microparticles produced by the processes disclosed herein exhibit desirable tactile and / or optical qualities, making them desirable for use in, for example, personal care products, cosmetics, and the like. The terms “beads,” “microparticles,” or “CE microparticles” as used herein may be used interchangeably with the term “cured CE microparticles.” However, while “cured CE microparticles” are produced by a wet solvent / emulsion process, microbeads can also be produced by mechanical milling processes (e.g., jet milling) from larger forms of CE, including dry milling or size reduction processes (as described herein).

[0183] In one embodiment, or in combination with any embodiment referenced herein, CE fine particles are produced at rates of at least 50, 100, 250, 500, 1000, 2500, 5000, or 10000 kg / day, and / or at rates of 100000 kg / day or less, 75000 kg / day or less, or 50000 kg / day or less. To achieve these production rates, CE, solvent, and / or water are supplied into the system at one or more of the following corresponding rates.

[0184] In one embodiment, or in combination with any embodiment referenced herein, CE is supplied to unit 140 at a rate of at least 50, 100, 250, 500, 1000, 2500, 5000, or 10000 kg / day, and / or at a rate of 100000 kg / day or less, 75000 kg / day or less, or 50000 kg / day or less.

[0185] In one embodiment, or in combination with any embodiment referenced herein, the solvent is supplied to unit 140 at a rate of at least 50, 100, 250, 500, 1000, 2500, 5000, or 10000 kg / day, and / or at a rate of 100000 kg / day or less, 75000 kg / day or less, or 50000 kg / day or less.

[0186] In one embodiment, or in combination with any embodiment referenced herein, water is supplied to unit 152 at a rate of at least 500, 1000, 2500, 5000, 10000, 25000, 50000, or 100000 kg / day, and / or 1,000,000 kg / day or less, 750,000 kg / day or less, or 500,000 kg / day or less.

[0187] In one embodiment, or in combination with any embodiment referenced herein, the hardness of the cured CE fine particles at 20°C is higher than the hardness of the initial fine particles contained in the pre-cured dispersion 150 and / or the initial fine particles formed in any process described herein.

[0188] In one embodiment, or in combination with any embodiment referenced herein, the hardness of the cured CE particles is at least 1.1, 1.25, 1.5, 1.75, or twice as high as the hardness of the initial particles.

[0189] In one embodiment, or in combination with any embodiment referenced herein, the solvent content of the cured CE fine particles is less than 100 ppm, less than 50 ppm, less than 25 ppm, or less than 10 ppm.

[0190] In one embodiment, or in combination with any embodiment referred to herein, the cured CE fine particles have a solvent content lower than that of the initial fine particles.

[0191] In one embodiment, or in combination with any embodiment referenced herein, the solvent content of the cured CE fine particles is less than 0.99, less than 0.95, less than 0.9, less than 0.8, less than 0.7, less than 0.6, or less than 0.5 of the solvent content of the initial fine particles.

[0192] In one embodiment, or in combination with any embodiment referenced herein, the volume-based D50 particle size of the CE particles is within 50, 25, 15, 10, 5, or 2% of the D50 particle size of the initial particles.

[0193] In one embodiment, or in combination with any embodiment referenced herein, the volume-based D50 particle size of the CE particles is less than 0.99, less than 0.95, less than 0.9, less than 0.8, less than 0.7, less than 0.6, or less than 0.5 of the volume-based D50 particle size of the initial particles.

[0194] In one embodiment, or in combination with any embodiment referenced herein, the volume-based D50 particle size of the CE particles is 1-100, 1-80, 1-70, 1-60, 1-50, 1-40, 1-35, 1-30, 1-25, 1-20, 1-15, 1-10, 2-100, 2-80, 2-70, 2-60, 2-50, 2-40, 2-35, 2-30, 2-25, 2-20, 2-15, 2-10, 3-100, 3-80, 3-70, 3-60, 3-50, 3-40, 3-35, 3-30, 3-25, 3-20, 3-15, 3-10, 5-100, 5-80, 5-70, 5-60, 5-50, 5-40, 5-35, 5-30, 5-25, 5-20, 5-1 5, 5-10, 10-100, 10-80, 10-70, 10-60, 10-50, 10-40, 10-35, 10-30, 10-25, 10-20, 10-15, 15-100, 15-80, 15-70, 15-60, 15-50, 15-40, 15-35, 15-30, 15-25, 15-20, 20-100, 20- The range is 80, 20-70, 20-60, 20-50, 20-40, 20-35, 20-30, 25-100, 25-80, 25-70, 25-60, 25-50, 25-40, 25-35, 25-30, 30-100, 30-80, 30-70, 30-60, 30-50, 30-40, or within the range of 30-35 microns. For example, CE particles can have a volume-based D50 particle size of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100 microns.

[0195] Where used herein, the term “volume-based D50” means that, based on volume, 50% of the beads / microparticles have a maximum dimension of less than or equal to a specified value (e.g., 10 microns). The D50 value may also be treated as the median particle size. To ensure a representative D50 value is obtained, the sample amount of beads / microparticles should be at least 0.5 grams. The sample amount of microparticles is then dispersed and mixed in 1.5 ounces of isopropanol. The D50 test is performed by a computer algorithm using laser diffraction and Mie theory to generate the particle size distribution. One suitable particle size analyzer for determining the D50 value is the Malvern Mastersizer 3000 from Malvern Panalytical. When using the Malvern Mastersizer, the light shielding rate can be set to 2% to 5%, and the sample measurement time is set to 3 seconds for both red and blue light measurements. The dispersed sample is added until the desired light shielding rate (approximately 4%) is achieved, and then the measurement is performed. After the first measurement, the sample is sonicated at 50% power for 120 seconds. Next, after ultrasonic treatment, once the light energy has stabilized (usually less than 1 minute), the dispersed sample is measured again.

[0196] In one embodiment, or in combination with any embodiment referenced herein, the volume-based D10 particle size of the CE particles is 0.5-20, 0.5-15, 0.5-12, 0.5-10, 0.5-5, 0.5-4, 0.5-3, 0.5-2, 0.5-1, 1-20, 1-15, 1-12, 1-5, 1-3, 2-20, 2-10, 2-5, 3-20, 3-15, 3-10, 4-20, 4-15, 4-10, 5-20, 5-15, 5-10, 10-20, or 10-15 microns. For example, CE particles can have a volume-based D10 particle size of 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 microns.

[0197] As used herein, the term “volume-based D10” means that, based on volume, 10% of the beads / microparticles have a maximum dimension of no more than a specified value (e.g., 10 microns). To ensure a representative D10 value is obtained, the sample amount of beads / microparticles should be at least 0.5 grams. The sample amount of microparticles is then dispersed and mixed in 1.5 ounces of isopropanol. The D10 test is performed by a computer algorithm using laser diffraction and Mie theory to generate the particle size distribution. One suitable particle size analyzer for determining the D10 value is the Malvern Mastersizer 3000 from Malvern Panalytical. When using the Malvern Mastersizer, the light shielding rate can be set to 2% to 5%, and the sample measurement time is set to 3 seconds for both red and blue light measurements. The dispersed sample is added until the desired light shielding rate (approximately 4%) is achieved, and then the measurement is performed. After the first measurement, the sample is sonicated at 50% power for 120 seconds. Next, after ultrasonic treatment, once the light energy has stabilized (usually less than 1 minute), the dispersed sample is measured again.

[0198] In one embodiment, or in combination with any embodiment referenced herein, the volume-based D90 particle size of CE particles is 1-100, 1-80, 1-70, 1-60, 1-50, 1-40, 1-35, 1-30, 1-25, 1-20, 1-15, 1-10, 5-100, 5-80, 5-70, 5-60, 5-50, 5-40, 5-35, 5-30, 5-25, 5-20, 5-15, 5-10, 10-100, 10-80, 10-70, 10-60, 10-50, 10-40, 10-35, 10-30, 10-25 The ranges are 10-20, 10-15, 15-100, 15-80, 15-70, 15-60, 15-50, 15-40, 15-35, 15-30, 15-25, 15-20, 20-100, 20-80, 20-70, 20-60, 20-50, 20-40, 20-35, 20-30, 25-100, 25-80, 25-70, 25-60, 25-50, 25-40, 25-35, 25-30, 30-100, 30-80, 30-70, 30-60, 30-50, 30-40, or 30-35 microns. For example, CE particles can have a volume-based D90 particle size of 100, 90, 80, 70, 60, 50, 49, 48, 47, 46, 45, 44, 43, 42, 41, 40, 39, 38, 37, 36, 35, 34, 33, 32, 31, 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, or 20 microns.

[0199] As used herein, the term “volume-based D90” means that, based on volume, 90% of the beads / microparticles have a maximum dimension of no more than a specified value (e.g., 10 microns). To ensure a representative D90 value is obtained, the sample amount of beads / microparticles should be at least 0.5 grams. The sample amount of microparticles is then dispersed and mixed in 1.5 ounces of isopropanol. The D90 test is performed by a computer algorithm using laser diffraction and Mie theory to generate the particle size distribution. One suitable particle size analyzer for determining the D90 value is the Malvern Mastersizer 3000 from Malvern Panalytical. When using the Malvern Mastersizer, the light shielding rate can be set to 2% to 5%, and the sample measurement time is set to 3 seconds for both red and blue light measurements. The dispersed sample is added until the desired light shielding rate (approximately 4%) is achieved, and then the measurement is performed. After the first measurement, the sample is sonicated at 50% power for 120 seconds. Next, after ultrasonic treatment, once the light energy has stabilized (usually less than 1 minute), the dispersed sample is measured again.

[0200] In one embodiment, or in combination with any embodiment referenced herein, the volume-based D100 particle size of CE particles is 1-100, 1-80, 1-70, 1-60, 1-50, 1-40, 1-35, 1-30, 1-25, 1-20, 1-15, 1-10, 5-100, 5-80, 5-70, 5-60, 5-50, 5-40, 5-35, 5-30, 5-25, 5-20, 5-15, 5-10, 10-100, 10-80, 10-70, 10-60, 10-50, 10-40, 10-35, 10-30, 10-25 The ranges are 10-20, 10-15, 15-100, 15-80, 15-70, 15-60, 15-50, 15-40, 15-35, 15-30, 15-25, 15-20, 20-100, 20-80, 20-70, 20-60, 20-50, 20-40, 20-35, 20-30, 25-100, 25-80, 25-70, 25-60, 25-50, 25-40, 25-35, 25-30, 30-100, 30-80, 30-70, 30-60, 30-50, 30-40, or 30-35 microns. For example, CE particles can have a volume-based D100 particle size of 100, 90, 80, 70, 60, 50, 49, 48, 47, 46, 45, 44, 43, 42, 41, 40, 39, 38, 37, 36, 35, 34, 33, 32, 31, 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, or 20 microns.

[0201] As used herein, the term “volume-based D100” means that, based on volume, 100% of the beads / microparticles have a maximum dimension of no more than a specified value (e.g., 10 microns). To ensure a representative D100 value is obtained, the sample amount of beads / microparticles should be at least 0.5 grams. The sample amount of microparticles is then dispersed and mixed in 1.5 ounces of isopropanol. The D100 test is performed by a computer algorithm using laser diffraction and Mie theory to generate a particle size distribution. One suitable particle size analyzer for determining the D100 value is the Malvern Mastersizer 3000 from Malvern Panalytical. When using the Malvern Mastersizer, the light shielding rate can be set to 2% to 5%, and the sample measurement time is set to 3 seconds for both red and blue light measurements. The dispersed sample is added until the desired light shielding rate (approximately 4%) is achieved, and then the measurement is performed. After the first measurement, the sample is sonicated at 50% power for 120 seconds. Next, after ultrasonic treatment, once the light energy has stabilized (usually less than 1 minute), the dispersed sample is measured again.

[0202] In one embodiment, or in combination with any embodiment referenced herein, the D[4.3] average particle size of the CE particles is 1-100, 1-80, 1-70, 1-60, 1-50, 1-40, 1-35, 1-30, 1-25, 1-20, 1-15, 1-10, 1-8, 1-6, 1-5, 2-40, 2-35, 2-30, 2-25, 2-20, 2-15, 2-10, 2-8, 2-6, 2-5, 3-40, 3-35, 3-30, 3-25, 3-20, 3-15, 3-10, 3-8, 3-6, 3-5, 4-40, 4-35, 4-30, 4-25, 4-20, 4-15, 4-10, 4-8, 4-6, 5-100, 5-80, 5-70, 5-60, 5-50, 5-40, 5-35, 5-30 5-25, 5-20, 5-15, 5-10, 10-100, 10-80, 10-70, 10-60, 10-50, 10-40, 10-35, 10-30, 10-25, 10-20, 10-15, 15-100, 15-80, 15-70, 15-60, 15-50, 15-40, 15-35, 15-30, 15-25, 15-20, 20- The range is 100, 20-80, 20-70, 20-60, 20-50, 20-40, 20-35, 20-30, 25-100, 25-80, 25-70, 25-60, 25-50, 25-40, 25-35, 25-30, 30-100, 30-80, 30-70, 30-60, 30-50, 30-40, or within the range of 30-35 microns. For example, CE particles can have a volume-based D100 particle size of 100, 90, 80, 70, 60, 50, 49, 48, 47, 46, 45, 44, 43, 42, 41, 40, 39, 38, 37, 36, 35, 34, 33, 32, 31, 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, or 20 microns.

[0203] As used herein, the term “D[4,3] mean particle size” refers to the D[4,3] mean, as defined in ASTM E 799 and also known as the De Brouckere mean. This is calculated by dividing the sum of the fourth-power Di* percentages by the sum of the cubes of the same Di* percentages. To ensure a representative D[4,3] value is obtained, the sample amount of beads / microparticles should be at least 0.5 grams. The sample amount of microparticles is then dispersed and mixed in 1.5 ounces of isopropanol. One suitable particle size analyzer for determining the D100 value is the Malvern Mastersizer 3000 from Malvern Panalytical. When using the Malvern Mastersizer, the light shielding rate can be set to 2% to 5%, and the sample measurement time is set to 3 seconds for both red and blue light measurements. The dispersed sample is added until the desired light shielding rate (approximately 4%) is achieved, and then the measurement is performed. After the first measurement, the sample is sonicated at 50% power for 120 seconds. Next, after ultrasonic treatment, once the light energy has stabilized (usually less than 1 minute), the dispersed sample is measured again.

[0204] In one embodiment, or in combination with any embodiment referenced herein, the CE particles have an average sphericity of at least 10, 20, 30, 40, 50, 60, 70, 80, 90, 95, 95, 97, 98, or 99%. Additionally or alternatively, the CE particles may have an average sphericity of 99% or less, 95% or less, 90% or less, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, or 30% or less. In a particular embodiment, the CE particles have an average sphericity in the range of 5 to 60, or 5 to 50, or 5 to 40, or 5 to 30, or 5 to 25, or 5 to 20, or 10 to 60, or 10 to 50, or 10 to 40, or 10 to 30, or 10 to 25, or 10 to 20%. In the embodiment, the CE particles are produced by a mechanical grinding process (as described herein), such as jet mill grinding, and have an average sphericity within the range of 5-40, 5-30, 5-25, 5-20, 10-40, 10-30, 10-25, or 10-20%.

[0205] In certain embodiments, the CE particles have an average sphericity in the range of 70-100, or 70-90, or 70-80, or 75-100, or 75-90, or 75-80, or 80-100, or 80-90%. In embodiments, the CE particles are produced by a solvent process or emulsion process (as described herein) and have an average sphericity in the range of 70-100, or 70-90, or 70-80%.

[0206] The average sphericity is determined by (1) obtaining a secondary emission / ETD detector scanning electron microscope (SEM) image of a representative sample of at least 40 particles; (2) selecting a square sample area centered on the SEM center containing exactly 30 particles whose entire circumference is clearly visible (i.e., not flattened) on this SEM image; (3) measuring the maximum and minimum diameters of the 30 clearly visible particles within this sample area (each extending through the center of gravity of the particle, but not necessarily perpendicular to each other); (4) obtaining the sphericity of each of the 30 individual particles by dividing the minimum diameter by the maximum diameter and multiplying the result by 100%; and (5) obtaining the average sphericity by averaging the sphericities of the 30 individual particles. As used herein, the term “spherical” when describing the shape of CE particles means that the CE particles have an average sphericity of at least 70%. As used herein, the term “spherical elliptic” when describing the shape of CE particles means that the CE particles have an average sphericity of less than 70%.

[0207] In one embodiment, or in combination with any embodiment referenced herein, the CE particles exhibit a unimodal particle size distribution having spans of at least 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, or 1.4 and / or spans of less than 3.0, less than 2.9, less than 2.8, less than 2.7, less than 2.6, less than 2.5, less than 2.4, less than 2.3, less than 2.2, less than 2.1, less than 2.0, less than 1.9, less than 1.8, less than 1.7, less than 1.6, or less than 1.5. In certain embodiments, CE particles exhibit a unimodal particle size distribution having spans of 1.0–3.0, 1.0–2.5, 1.0–2.0, 1.0–1.8, 1.0–1.6, 1.2–3.0, 1.2–2.5, 1.2–2.0, 1.2–1.8, 1.2–1.6, 1.3–3.0, 1.3–2.5, 1.3–2.0, 1.3–1.8, or 1.3–1.6. As used herein, “unimodal particle size distribution” refers to a particle size distribution of a material having only a single prominent peak size distribution. This is in contrast to a multimodal particle size distribution having two or more peaks. The “span” of a unimodal peak can be determined using the following formula with the D10, D50, and D90 values ​​of the particle. (D x (90)-D x (10)) / D x (50) In the formula, "x" is the specified particle size.

[0208] In one embodiment, or in combination with any embodiment referenced herein, the CE particles have an average smoothness of at least 10, 20, 30, 40, 50, 60, 70, 80, 90, 95, 95, 97, 98, or 99%. Additionally or alternatively, the CE particles may have an average smoothness of 99% or less, 95% or less, 90% or less, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, or 30% or less.

[0209] The average smoothness is determined by (1) acquiring a secondary emission / EDT detector scanning electron microscope (SEM) image of a representative sample of at least 20 microparticles; (2) selecting a square sample region centered on the SEM containing exactly 10 microparticles whose entire circumference is clearly visible (i.e., not crushed); (3) binarizing the sample region by manual binarization using upper and lower thresholds selected to match the exact shape of the dark region of the particles; (4) for each of the 10 microparticles, selecting a square region at or near the center of the particle, with a length and width of approximately 1 / 3 of the particle diameter (before binarization); (5) obtaining the smoothness of the 10 individual particles by dividing the area of ​​the dark region in the square region by the total area of ​​the square region and multiplying the result by 100%; and (6) obtaining the average smoothness by averaging the smoothness of these 10 individual particles.

[0210] In one embodiment, or in combination with any embodiment referenced herein, CE particles, when measured according to ISO9277 using a Micromeritics ASAP 2020 apparatus and krypton gas, have a density of at least 0.1, 0.5, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4 0.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, or 8.0 m² / g average BET surface area, and / or 100 m² / g or less, 95 m² / g or less, 90 m² / g or less, 85 m² / g or less, 80 m² / g or less, 75 m² / g or less, 70 m² / g or less Bottom, 65m2 / g or less, 60m2 / g or less, 55m2 / g or less, 50m2 / g or less, 45m2 / g or less, 40m2 / g or less, 35m2 / g or less, 30m2 / g or less, 29m2 / g or less, 28m2 / g or less, 27m2 / g or less, 26 m2 / g or less, 25m2 / g or less, 24m2 / g or less, 23m2 / g or less, 22m2 / g or less, 21m2 / g or less, 20m2 / g or less, 19m2 / g or less, 18m2 / g or less, 17m2 / g or less, 16m2 / g or less, 15m2 / g or less Bottom, 14m2 / g or less, 13m2 / g or less, 12m2 / g or less, 11m2 / g or less, 10m2 / g or less, 9m2 / g or less, 8m2 / g or less, 7m2 / g or less, 6m2 / g or less, 5m2 / g or less, 4m2 / g or less, 3m2 / g or less, 2 Have an average BET surface area of ​​.5m2 / g or less, 2m2 / g or less, 1.9m2 / g or less, 1.8m2 / g or less, 1.7m2 / g or less, 1.6m2 / g or less, 1.5m2 / g or less, 1.4m2 / g or less, or 1.3m2 / g or less.

[0211] In one embodiment, or in combination with any embodiment referenced herein, CE particles have a BET mean pore diameter of at least 25, 30, 35, 40, 45, 50, 55, 56, 57, 58, or 59 angstroms, and / or a BET mean pore diameter of less than 75 angstroms, less than 70 angstroms, less than 65 angstroms, or less than 60 angstroms, when measured according to ISO9277 and ISO15901-02 using a Micromeritics ASAP 2020 apparatus and nitrogen gas.

[0212] In one embodiment, or in combination with any embodiment referenced herein, CE particles have a BJH mean pore diameter of at least 50, 60, 70, 80, 90, 100, 110, 120, 125, or 130 angstroms, and / or a BJH mean pore diameter of less than 200 angstroms, less than 190 angstroms, less than 180 angstroms, less than 170 angstroms, less than 160 angstroms, less than 150 angstroms, less than 140 angstroms, or less than 130 angstroms, when measured in accordance with ISO 15901-02 using a Micromeritics ASAP 2020 apparatus and nitrogen gas.

[0213] In one embodiment, or in combination with any embodiment referred to herein, the BJH surface area of ​​pores in CE particles ranging from 17 to 3,000 angstroms is at least 0.5, 1.0, 1.1, 1.2, 1.3, 1.4, or 1.5 m² when measured according to ISO 15901-02 using a Micromerics ASAP 2020 apparatus and nitrogen gas. 2 / g, and / or 2.5m 2 Less than / g, 2.0m 2 Less than / g, 1.9m 2 Less than / g, 1.8m 2 Less than / g, 1.7m 2 Less than / g, 1.6m 2 Less than / g, 1.5m 2 Less than / g, 1.4m 2 Less than / g, or 1.3m 2It is less than / g.

[0214] In one embodiment, or in combination with any embodiment referenced herein, the BJH volume of pores in CE particles ranging from 17 to 3,000 angstroms is at least 0.001, 0.002, 0.003, or 0.004 mL / g and / or less than 0.1 mL / g, less than 0.05 mL / g, or 0.01 mL / g, when measured according to ISO 15901-02 using a Micromeretics ASAP 2020 apparatus and nitrogen gas.

[0215] In one embodiment, or in combination with any embodiment referenced herein, the true specific gravity of the CE particles is at least 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9 and / or 1.5 or less, 1.4 or less, 1.3 or less, 1.2 or less, 1.1 or less, 1.0 or less, 0.9 or less, 0.8 or less, 0.7 or less, or 0.6 or less, as measured according to JIS Z8807-1976.

[0216] In one embodiment, or in combination with any embodiment referenced herein, the bulk density of CE particles is at least 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, or 0.8, and / or 1.4 or less, 1.3 or less, 1.2 or less, 1.1 or less, 1.0 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, or 0.5 or less, as measured according to JIS 1201-1.

[0217] In one embodiment, or in combination with any embodiment referenced herein, the polydispersity index of the CE particles is less than 0.8, less than 0.7, less than 0.6, less than 0.5, less than 0.4, or less than 0.3.

[0218] In one embodiment, or in combination with any embodiment referenced herein, the surfactant content of the CE fine particles is less than 200 ppm by weight, less than 150 ppm by weight, less than 100 ppm by weight, less than 50 ppm by weight, less than 20 ppm by weight, less than 10 ppm by weight, less than 7.5 ppm by weight, less than 5 ppm by weight, less than 2.5 ppm by weight, or less than 1 ppm by weight.

[0219] In one embodiment, or in combination with any embodiment referenced herein, the plasticizer content of the CE fine particles is less than 200 ppm by weight, less than 150 ppm by weight, less than 100 ppm by weight, less than 50 ppm by weight, less than 20 ppm by weight, less than 10 ppm by weight, less than 7.5 ppm by weight, less than 5 ppm by weight, less than 2.5 ppm by weight, or less than 1 ppm by weight.

[0220] In one embodiment, or in combination with any embodiment referenced herein, the butyric acid content of the CE fine particles is less than 500 ppm by weight, less than 400 ppm by weight, less than 300 ppm by weight, less than 200 ppm by weight, less than 100 ppm by weight, less than 50 ppm by weight, less than 20 ppm by weight, less than 10 ppm by weight, less than 7.5 ppm by weight, less than 5 ppm by weight, less than 2.5 ppm by weight, or less than 1 ppm by weight.

[0221] In one embodiment, or in combination with any embodiment referenced herein, the acetic acid content of the CE fine particles is less than 500 ppm by weight, less than 400 ppm by weight, less than 300 ppm by weight, less than 200 ppm by weight, less than 100 ppm by weight, less than 50 ppm by weight, less than 20 ppm by weight, less than 10 ppm by weight, less than 7.5 ppm by weight, less than 5 ppm by weight, less than 2.5 ppm by weight, or less than 1 ppm by weight.

[0222] In one embodiment, or in combination with any embodiment referenced herein, the propionic acid content of the CE fine particles is less than 500 ppm by weight, less than 400 ppm by weight, less than 300 ppm by weight, less than 200 ppm by weight, less than 100 ppm by weight, less than 50 ppm by weight, less than 20 ppm by weight, less than 10 ppm by weight, less than 7.5 ppm by weight, less than 5 ppm by weight, less than 2.5 ppm by weight, or less than 1 ppm by weight.

[0223] The butyric acid, acetic acid, and propionic acid content of CE microparticles can be measured by gas chromatography ("GC"). In one GC method, the butyric acid, acetic acid, and propionic acid content can be measured by placing approximately 100 mg of CE microparticles into a weighed 4-dram vial, followed by the addition of an internal standard solution containing nonane in a 90:10 dichloromethane / methanol mixture. A magnetic stirrer is placed in the vial, and the sample is stirred for 2 hours. After stirring, 8.0 mL of n-heptane is added dropwise to precipitate the polymer, and then the sample is vortexed. Approximately 100 mg of the supernatant is transferred to a GC vial along with 100 μL of pyridine and 450 μL of BSTFA. The sample is heated at 80°C for 30 minutes, and then cooled to room temperature before injection. The sample is simultaneously chromatographed using 100% dimethylpolysiloxane and 14% cyanopropyl-phenyl-methylpolysiloxane columns with temperature programming and flame ionization detection. Alternatively, in the second GC method, approximately 30 mg of CE microparticles are placed in a weighed GC vial, followed by 200 μL of an internal standard solution containing decane in pyridine and 1.0 mL of BSTFA. The vial is heated at 80°C for 30 minutes, then cooled to room temperature before injection. The sample is then simultaneously chromatographed using 100% dimethylpolysiloxane and 6% cyanopropyl-phenyl-methylpolysiloxane columns with temperature programming and flame ionization detection.

[0224] In one embodiment, or in combination with any embodiment referred to herein, the sulfuric acid content of CE particles is less than 500 ppm by weight, less than 400 ppm by weight, less than 300 ppm by weight, less than 200 ppm by weight, less than 100 ppm by weight, less than 50 ppm by weight, less than 20 ppm by weight, less than 10 ppm by weight, less than 7.5 ppm by weight, less than 5 ppm by weight, less than 2.5 ppm by weight, or less than 1 ppm by weight. The sulfuric acid content of CE particles can be measured by the following method: First, the test sample is placed in a titration cell and dissolved in the solvent to a total volume of 70 mL. A solvent blank is also prepared for comparison. Next, the sample and the blank are titrated with 0.05 N potassium hydroxide in methanol using an automatic titrator equipped with a composite glass potentiometric electrode. The acid value is calculated based on the weight of the sample and the value obtained by subtracting the KOH consumed in the blank from the KOH consumed in the sample.

[0225] In one embodiment, or in combination with any embodiment referenced herein, the CE fine particles contain, as a CE content, at least 50, 55, 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99% by weight of a mixed cellulose ester of the first embodiment, the second embodiment, and / or the third embodiment (including any class or subclass of these embodiments). Additionally or alternatively, the CE particles may contain, as CE content, a mixed cellulose ester of the first, second, and / or third embodiment (including any class or subclass of these embodiments) in amounts less than 99.9% by weight, less than 99.5% by weight, less than 99% by weight, less than 98% by weight, less than 97% by weight, less than 96% by weight, less than 95% by weight, less than 94% by weight, less than 93% by weight, less than 92% by weight, less than 91% by weight, less than 90% by weight, less than 89% by weight, less than 88% by weight, less than 87% by weight, less than 86% by weight, or less than 85% by weight. In certain embodiments, the CE particles may essentially consist of a mixed cellulose ester of the first, second, and / or third embodiment (including any class or subclass of these embodiments).

[0226] In one embodiment, or in combination with any embodiment referenced herein, the CE fine particles may include an additional biodegradable cellulose ester different from the mixed cellulose ester of the first, second, and / or third embodiment. In such embodiments, this additional cellulose ester may be a cellulose ester that exhibits at least 40% biodegradability, at least 45% biodegradability, or at least 50% biodegradability, or at least 55% biodegradability, at least 60% biodegradability, or at least 65% biodegradability, or at least 70% biodegradability, or at least 75% biodegradability, or at least 80% biodegradability, or at least 85% biodegradability in 60 days according to at least one of the OECD 301B, OECD 301C, or OECD 301F test methods.

[0227] In one embodiment, or in combination with any embodiment referenced herein, the CE particles may contain at least 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10% by weight of an additional biodegradable cellulose ester different from the mixed cellulose ester of the first, second, and / or third embodiment. Additionally or alternatively, the CE particles may contain less than 50% by weight, less than 45% by weight, less than 40% by weight, less than 35% by weight, less than 30% by weight, less than 25% by weight, less than 20% by weight, less than 15% by weight, less than 10% by weight, or less than 5% by weight of an additional biodegradable cellulose ester different from the mixed cellulose ester of the first, second, and / or third embodiment.

[0228] In one embodiment, or in combination with any embodiment referenced herein, the CE fine particles have a moisture content in an amount of (1) more than 0% by weight, (2) 10% by weight or less, 9% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, 5% by weight or less, 4% by weight or less, 3% by weight or less, 2% by weight or less, 1% by weight or less, or 0.05% by weight or less, and (3) one or more amounts within the range of 0 to 10, 0 to 5, 0 to 4, 0 to 3, or 1.3% by weight.

[0229] In one embodiment, or in combination with any embodiment referenced herein, CE particles exhibit at least 40% biodegradability, at least 45% biodegradability, or at least 50% biodegradability, or at least 55% biodegradability, or at least 60% biodegradability, or at least 65% biodegradability, or at least 70% biodegradability, or at least 75% biodegradability, or at least 80% biodegradability, or at least 85% biodegradability in 56 days, according to at least one of the OECD301B, OECD301C, or OECD301F test methods.

[0230] In one embodiment, or in combination with any embodiment referenced herein, CE particles exhibit at least 40% biodegradability, at least 45% biodegradability, or at least 50% biodegradability, or at least 55% biodegradability, at least 60% biodegradability, or at least 65% biodegradability, or at least 70% biodegradability, or at least 75% biodegradability, or at least 80% biodegradability, or at least 85% biodegradability, according to at least one of the OECD301B, OECD301C, or OECD301F test methods, after 60 days.

[0231] In one embodiment, or in combination with any other embodiment referenced herein, CE particles exhibit an oil absorption capacity of at least 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100 mL per 100 g (or an oil absorption capacity of at least 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100 g per 100 g of particles).

[0232] In one embodiment, or in combination with any other embodiment referenced herein, the CE microparticles exhibit a zeta potential of at least -95, at least -90, at least -85, at least -80, at least -75, at least -70, at least -65, at least -60, at least -55, at least -50, or at least -45 mV. Additionally or alternatively, the CE microparticles may exhibit a zeta potential of less than -5 mV, less than -10 mV, less than -15 mV, less than -20 mV, less than -25 mV, less than -30 mV, less than -35 mV, less than -40 mV, less than -45 mV, less than -50 mV, less than -55 mV, less than -60 mV, or less than -65 mV.

[0233] The zeta potential was measured after dispersing the microparticles in water by vortex mixing for 30 seconds. The microparticle concentration was adjusted to 0.5 mg / ml. The zeta potential test was performed using a sample cell DTS1070 with a Malvern Panalytical Zetasizer Nano series model ZEN3600 instrument. Subsequently, the Smolkovsky model was used to calculate the zeta potential.

[0234] In one embodiment, or in combination with any other embodiment referenced herein, the CE particles exhibit a haze transmittance of at least 20, at least 25, at least 30, at least 35, at least 40, or at least 45%. Additionally or alternatively, the CE particles may exhibit a haze transmittance of less than 90%, less than 85%, less than 80%, less than 75%, less than 70%, less than 65%, less than 60%, less than 55%, less than 50%, less than 45%, or less than 40%. The haze transmittance can be measured by preparing an aqueous emulsion containing 5 wt% biodegradable beads / particles using a BYK gloss meter and BYK Haze Gard I.

[0235] The detailed procedure for measuring haze (turbidity) is as follows. A W / O emulsion for measuring haze % was prepared using the following procedure. Two phases were used for emulsion preparation. Phase A was prepared from water, magnesium sulfate heptahydrate (Merck), and Euxyl PE9010 (Ashland) (each at weight concentrations of 59:2:1). Phase B was prepared using caprylic / capric triglyceride (Making Cosmertics), C12-15 alkyl benzoate (Making Cosmes), Emullium Illustro (Gattefosse), Bentoline Gel ISD V (Elementis), and fine particle powder (each at weight concentrations of 12.5:12.5:5:3:5). Phase A was prepared by mixing the listed components. Phase B was prepared by overhead stirring until all components were dissolved, except for the fine particle powder. Next, add phase A to phase B while stirring at 1000 rpm until completely mixed. Then, add the fine powder to the mixture while stirring at 1000 rpm for 5 minutes. Homogenize the resulting mixture using Ultrax Turax at 10,000 rpm for 5 minutes. 50 o The haze transmittance of the drawdown film (coated film) (38 μm) after drying in C for 5 minutes is measured using BYK Haze Gard I.

[0236] In one embodiment, or in combination with any other embodiment referred to herein, CE particles exhibit a total transmittance of at least 50, at least 60, at least 70, at least 75, at least 80, at least 85, at least 86, at least 87, at least 88, or at least 89% when measured using a BYK Haze-Gard I unit.

[0237] Cosmetic formulations Cured CE microparticles produced by processes disclosed herein (e.g., emulsion processes) or by physical grinding processes (e.g., jet mill grinding) can be used to produce a variety of cosmetic compositions. Cosmetic compositions can be produced by (1) preparing a plurality of CE microparticles, (2) preparing a preliminary cosmetic mixture by mixing the CE beads / microparticles with one or more cosmetic additives, and (3) preparing a cosmetic composition from the preliminary cosmetic mixture.

[0238] In one embodiment, or in combination with any other embodiment referenced herein, the cosmetic composition may contain at least 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15% by weight of CE microparticles. Additionally or alternatively, the cosmetic composition may contain less than 99% by weight, less than 90% by weight, less than 80% by weight, less than 70% by weight, less than 60% by weight, less than 50% by weight, less than 40% by weight, less than 30% by weight, less than 25% by weight, less than 20% by weight, less than 15% by weight, less than 10% by weight, or less than 5% by weight of CE microparticles. For example, a cosmetic composition may contain CE fine particles in amounts of 0.1-90, 0.1-50, 0.1-30, 0.1-20, 0.1-15, 0.1-10, 0.1-5, 1-90, 1-50, 1-30, 1-20, 1-15, 1-10, or 1-5% by weight.

[0239] In one embodiment, or in combination with any other embodiments referenced herein, the cosmetic composition may be a foundation, sunscreen, lipstick, mascara, eyeshadow, lotion, dry shampoo, liquid shampoo, body wash, lotion, hair conditioner, skin moisturizer, face wash, tablets, foot powder, baby powder, shaving cream, or shaving gel.

[0240] In one embodiment, or in combination with any other embodiment referenced herein, the cosmetic composition may be a loose powder, compressed powder, gel, emulsion, liquid, or aerosol.

[0241] In one embodiment, or in combination with any other embodiment referenced herein, the cosmetic composition comprises at least one, two, three, four, or five cosmetic additives in an amount of at least 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99% by weight. Additionally or alternatively, the cosmetic composition may comprise at least one, two, three, four, or five cosmetic additives in an amount of less than 99% by weight, less than 95% by weight, less than 90% by weight, less than 85% by weight, less than 80% by weight, less than 75% by weight, less than 70% by weight, less than 65% by weight, less than 60% by weight, less than 55% by weight, or less than 50% by weight. For example, a cosmetic composition may contain at least one, two, three, four, or five cosmetic additives in weights of 1-99, 1-95, 1-90, 1-85, 1-80, 5-99, 5-95, 5-90, 5-85, 10-99, 10-95, 10-85, 10-80, 15-99, 15-95, 15-90, 15-85, or 15-80%.

[0242] Generally, cosmetic additives include solvents, colorants, oils, waxes, fatty acids, alcohols, esters, hydrocarbons, silicone oils, surfactants, metallic soaps, humectants, thickeners, UV absorbers, antioxidants, oil absorbers, exfoliants, water, or combinations thereof.

[0243] In one embodiment, or in combination with any other embodiment referenced herein, the colorant comprises pigments (e.g., organic pigments and / or inorganic pigments) and / or dyes.

[0244] In one embodiment, or in combination with any other embodiment referenced herein, the oil comprises triglycerin, soybean oil, cocoa butter, palm oil, palm kernel oil, hydrogenated oil, and / or hydrogenated castor oil.

[0245] In one embodiment, or in combination with any other embodiment referenced herein, the wax comprises carnauba wax, candelilla wax, lanolin, lanolin, candelilla wax, cotton wax, montan wax, kapok wax, lanolin acetate, lanolin, and / or isopropyl lanolin fatty acid.

[0246] In one embodiment, or in combination with any other embodiment referred to herein, the fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, behenic acid, oleic acid, undecylenic acid, linoleic acid, eicosapentaenoic acid (EPA), and / or docosahexaenoic acid.

[0247] In one embodiment, or in combination with any other embodiment referred to herein, the alcohol includes cetyl alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodecanol, lauryl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, and / or cetostearyl alcohol.

[0248] In one embodiment, or in combination with any other embodiment referred to herein, the esters include isopropyl myristate, 2-octyldodecyl myristate, cetyl 2-ethylhexanoate, diisostearyl malate, tripropylene glycol dieopenate, isononyl isononanoate, isotridyl isononanoate, cetyl octanoate, isocetyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyldimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, and neopentyl glycol dicaprate. This includes di-2-heptyl undecanoate glycerin, tri-2-ethylhexanoate trimethylpropane, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexanoate, glycerin tri-2-ethylhexanoate, glycerin trioctanoate, glycerin triisopalmitate, trimethylolpropane triisostearate, ethylhexyl palmitate, glycerin trimyristate, tri-2-heptyl undecanoate glyceride, castor oil fatty acid methyl ester, oleyl oleate, acetoglyceride, 2-heptyl undecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamate hexyldecyl palmitate, hexyldecyl adipate, diisopropyl sebacate, ethylhexyl succinate, and / or triethyl citrate.

[0249] In one embodiment, or in combination with any other embodiment referenced herein, the hydrocarbons include paraffin, petrolatum, and / or microcrystalline waxes.

[0250] In one embodiment, or in combination with any other embodiment referenced herein, the surfactant includes anionic surfactants, cationic surfactants, and / or nonionic surfactants.

[0251] In one embodiment, or in combination with any other embodiment referred to herein, the thickener comprises guar gum, pectin, starch, gelatin, collagen, cellulose derivatives, and / or mannan.

Examples

[0252] Experiment The following experiments include the preparation of cellulose esters, the preparation of microparticles, the preparation of cosmetic formulations containing the microparticles, and the testing of such compositions.

[0253] Preparation of Cellulose Ester Example 1-1: Cellulose acetate butyrate (CAB) was prepared as follows.

[0254] A mixture of cellulose and an acid (cellulose (4.3 parts) and AcOH (11.8 parts)) was added to a stirring reactor, immersed without heating, and then the mixture was heated to 55 o °C. An amount of sulfuric acid was added and the reactor was cooled to 30 o °C. Subsequently, a mixture of acetic anhydride (Ac2O) (8.9 parts) and butyric anhydride (Bu2O) (5.6 parts) was added, and the mixture was cooled to about 9 o °C while stirring. Additional sulfuric acid was added up to a total of 0.6 parts, and the resulting reaction mixture was warmed to 50 o °C until the acylation reaction was complete and the desired molecular weight was obtained. A mixture of butyric acid (BuOH) (18 parts) and H2O (7.4 parts) was added to this reaction mixture. Then, the mixture was stirred at 68 o °C for 1020 minutes, but after 80 minutes, a mixture of magnesium acetate (Mg(OAc)2) (0.61 parts), BuOH (6.9 parts) and H2O (2.7 parts) was added. After sufficient time had elapsed, the mixture was completely neutralized with a solution of Mg(OAc)2 (0.86 parts), BuOH (1.5 parts) and H2O (4.8 parts). Then, the mixture was precipitated into water by a conventional method, washed, and dried to recover CAB.

[0255] The substitution degree (DS) and molecular weight (Mw) of the CAB of Example 1-1 were measured. The results of DS and Mw are as follows. Example 1-1: Cellulose acetate butyrate (DS Ac = 1.87, DS Bu = 0.22, DS OH = 0.91, and M w = 90766)

[0256] General procedure for the preparation of cellulose ester (Examples 1-2 to 1-8) A cellulose mixture (cellulose and AcOH) ("cellulose mixture") and sulfuric acid, Ac2O and Bu2O ("acylation solution") were cooled to 30 o °C in a stirring reactor, and the reaction mixture was cooled to about 7 o °C while stirring. Additional sulfuric acid was added to the target amount, and the resulting reaction mixture was heated to 45 o °C to 65 o °C while stirring until the acylation reaction was completed and the desired molecular weight was obtained. The reaction mixture was treated with an aqueous solution of AcOH and BuOH ("hydrolysis solution") and stirred at 68 o °C under hydrolysis conditions. Then, the reaction mixture was quenched, neutralized, precipitated, washed, and dried by a conventional method. The relative amounts and reaction conditions of Examples 1-2 to 1-8 are described in Table 1.1 below.

Table 1

[0257] Characteristic evaluation of cellulose ester The results showing the DS and Mw of Examples 1-2 to 1-8 are described in Table 1.2 below.

[0258] DS and Mw were determined as follows.

[0259] Substitution degree The degree of substitution of substituents on the cellulose ester skeleton is determined using proton nuclear magnetic resonance spectroscopy. Gel permeation chromatography is performed on cellulose ester in stabilized tetrahydrofuran. The apparatus is an Agilent 1260, consisting of a degasser, an isocratic pump with a flow rate of 1.0 ml / min, an autosampler with an injection volume of 25 microliters, a column oven set to 28°C, and a refractive index detector at 28°C. The column set consists of Agilent PLgel 5 micron guard, Mixed-C, and Oligopore in series. This system is calibrated with monodisperse polystyrene standards in the molecular weight range of approximately 4 million to 162. The sample is prepared by weighing approximately 25 milligrams of the sample into 10 ml of solvent to which 10 microliters of toluene, used as a flow marker, and stirring with a stirring rod in an 8-dram screw-cap vial until dissolved.

[0260] molecular weight The molecular weight is determined by gel permeation chromatography. Gel permeation chromatography is performed on cellulose ester in stabilized tetrahydrofuran. The apparatus is an Agilent 1260, consisting of a degasser, an isocratic pump with a flow rate of 1.0 ml / min, an autosampler with an injection volume of 25 microliters, a column oven set to 28°C, and a refractive index detector at 28°C. The column set consists of Agilent PLgel 5 micron guard, Mixed-C, and Oligopore in series. This system is calibrated with monodisperse polystyrene standards in the molecular weight range of approximately 4 million to 162. The sample is prepared by weighing approximately 25 milligrams of the sample into 10 ml of solvent to which 10 microliters of toluene, to be used as a flow marker, and stirring with a stirring rod in an 8-dram screw-cap vial until dissolved.

[0261] Preparation of fine particles Examples 2-1 to 2-13: Fine particles were prepared from the cellulose esters of Examples 1-2 to 1-8. As described below, Examples 2-1 to 2-11 were prepared by jet milling, and Examples 2-12 and 2-13 were prepared by emulsion process.

[0262] Comparative Examples 1-3: Furthermore, as described below, fine particles were prepared from commercially available cellulose ester by jet milling.

[0263] The results for each particle size are listed in Table 1.2 below. The results include the cellulose ester used, particle size (PS), oil absorption, and surface area (SSA / BET).

[0264] Jet mill grinding There are several jet mill grinding settings that can be used to reduce particle size. Such settings are described in A. Chamayou and JADodds, Air Jet Milling, Handbook of Powder Technology, volume 12, Chapter 8, 2007 ("Chamayou"). Figure 7 of Chamayou shows an example of a fluidized bed opposing jet mill that can be used to reduce the size of cellulose ester particles, as shown in Table 1 below (for fine particles that are said to be prepared by jet mill grinding). Using the jet mill grinding process, the particle size of cellulose ester was reduced from 300-900 μm to approximately 10 μm. The operation of this basic jet mill is as follows: Cellulose ester is placed in a hopper and introduced into the top of the mill, typically via a double valve device (or via an injection device) ("FEED IN"). The cellulose ester particles fall to the bottom of the mill by gravity, where they are pushed out into one of three high-pressure airflows. The three high-pressure airflows face each other geometrically, forming the so-called "grinding zone". Within the grinding zone, cellulose ester particles are reduced in size (ground) through interparticle collisions. The ground particles are then transported upward by mass transfer in a vertical airflow (fluidized bed) and finally carried to a classifier. The classifier allows particles smaller than the desired minimum size to be removed from the mill ("FINE OUT"). Particles larger than the maximum size are excluded from the classifier, returned to the fluidized bed, and eventually fall back into the grinding zone for further grinding. Particles within the desired size range are removed from the classifier into appropriate product containers. Many control parameters exist to optimize productivity, particle size, and particle size distribution shape. Such parameters include, but are not limited to, the classifier rotor speed, air nozzle pressure, and bed level.

[0265] Emulsion process Prepare a clean, dry 3-liter kettle flask (with baffles). It is fitted with a two-stage overhead mechanical stirrer and a bottom dropout valve. Add 700–1,300 g of deionized water, 6–13 g of Tergitol 15-S-40, and 0–1.0 g of PEG-100 stearate to the kettle. Over 15 minutes, add 7–12 g of colloidal protectant (low, medium, or high viscosity carboxymethylcellulose or methylcellulose) to the stirred aqueous mixture. Stir the mixture at room temperature for 1 hour or until homogenized.

[0266] Prepare another clean, dry 2-liter kettle flask, fitted with an overhead mechanical stirrer and a bottom dropout valve. Prepare a doped solution consisting of 10–100% cellulose ester using 0–5.0 parts C1–C4 alkyl acetate, 0–1.0 part C1–C3 alcohol, and 0–0.80 parts deionized water (based on the mass of cellulose ester used). Stir the mixture at room temperature until homogeneous.

[0267] Add the doping solution to a 3-liter kettle over 30 minutes while stirring vigorously (250-500 rpm). Once the addition is complete, pass the emulsion through a flow cell containing a high-shear mixer (0-12,000 rpm) and recirculate it at a rate of 100-300 mL / min for 45-60 minutes.

[0268] After the high-shear mixing time is complete, the emulsion is then pumped into a 5-gallon bucket at a rate of 300 mL / min. The 5-gallon bucket is equipped with a single-stage overhead mechanical agitator and holds 4000-6000 g of deionized water. The pumped emulsion is stirred at 250-500 rpm for 0-16 hours. After the holding time, the emulsion is centrifuged to separate the spherical particles. The particles are suspended in 1-2 L of deionized water and centrifuged again. This washing process is repeated once.

[0269] Put the microparticles into a Sigma blade mixer and dry them at 50 - 100 °C under vacuum (100 - 400 mmHg) for 16 hours. The recovery rate is about 75 - 85%. The typical / target particle size data is as follows. D(10) = 3.07 μm, D(50) = 8.20 μm, D(90) = 22.6 μm, and the volume-based average particle size is about 11.3 μm.

[0270] Characterization of Microparticles The microparticles were characterized by measuring the particle size (PS), oil absorption, and surface area (SSA / BET).

[0271] Particle Size The particle size distribution and the average / arithmetic mean particle size were determined by analyzing the microparticles by light scattering using a Malvern Mastersizer 3000 (HydroMV dispersion unit) according to the following procedure. 1. Sample Preparation a. Pour 1.5 ounces of isopropanol into a 2.5-ounce glass jar. b. Scoop 0.5 grams of the sample into the jar and shake vigorously. 2. Initial Setup of the Instrument a. Completely fill the HydroMV dispersion unit with isopropanol and set the stirring speed to 3,500 RPM. b. Circulate the isopropanol for about 1 minute, then open the drain valve and release the liquid into a drainage bucket. c. Repeat steps a and b (the dispersion unit needs to be washed twice). d. Fill the HydroMV dispersion unit about half full with isopropanol and set the stirring speed to 3,500 RPM. Circulate the isopropanol for 5 minutes until the energy on the detector stabilizes. e. Set the stirring speed to 3,000 RPM, then initialize the instrument and measure the background. 3. Sample Measurement a. Set the light obscuration rate between 2 - 5%. Set the sample measurement time to 3 seconds for both red light and blue light. b. Add the sample suspension dropwise until the desired light obscuration rate (about 4%) is obtained. c. Measure the sample. d. After the first measurement, the sample is sonicated at 50% power for 120 seconds. e. After sonication, wait until the light energy stabilizes (usually less than 1 minute), then measure the sample again. 4. Cleanup a. Open the drain valve and release the liquid containing the sample into the drain bucket. b. Repeat steps 2a to 2c to clean the dispersion unit. c. After measuring all cellulose ester samples, wash the HydroMV dispersion unit twice with Millipore water. d. Close the HydroMV distributed unit and shut down the software.

[0272] Using the procedure described above, the D10 particle size, D50 particle size, and D90 particle size, as well as the D[4,3] average particle size, can be determined. Unless otherwise specified in the examples, particle size (PS) refers to the D[4,3] average particle size.

[0273] Oil absorption amount The oil absorption capacity of the tested microparticles was determined by measuring the oil absorption amount using the ASTM D281 standard test method. In this method, a known amount of microparticles was weighed into a glass vial, and olive oil was carefully added drop by drop using a plastic pipette. After each drop, the microparticles were thoroughly mixed with the oil by scraping with a sharp steel spatula. The test was completed when sufficient oil had completely permeated the particles, creating a hard, putty-like paste that did not break down or separate. The dropping bottle containing the oil was accurately weighed. The oil absorption capacity or uptake of the microparticles was calculated using the following formula: A = initial weight of the dropping bottle containing oil, B = final weight of the dropping bottle containing oil, W = weight of the starting microparticle sample (grams). Oil absorption amount (g / g or g / 100g) = (AB) / W

[0274] SSA / BET The surface area of ​​the microparticles was measured using the Micrometrics ASAP 2020 instrument in accordance with ISO 9277, by the gas absorption BET method.

[0275] The measurements were performed using the following procedure. 1) Degas a 0.5-1 gram sample overnight at 60°C. If degassing is insufficient, increase the temperature by 10°C. However, keep the temperature below 100°C to avoid irreversible surface changes. 2) Determine the sample mass by the weight difference between the empty sample tube and the sample tube containing the sample after degassing. 3) Krypton adsorption at 77K is used for specific surface area analysis. 4) Collect seven relative pressures ranging from 0.06 to 0.20 and fit them to a BET specific surface area analysis.

[0276] The test results for PS, oil absorption, and surface area of ​​the tested particles are shown in Table 1.2 below. [Table 2]

[0277] Biodegradability test Specific cellulose esters and fine particles from the above examples were tested according to the OECD 301B or OECD 301F test method to determine their biodegradability.

[0278] Description of the OECD 301B exam A known concentration of the test substance is added to a predetermined volume of inorganic culture medium. The test substance is used as a nominal organic carbon source. Then, carbon dioxide-free air is aerated through the culture medium at a controlled rate, either in the dark or under diffuse light conditions.

[0279] Over a period of 60 days, the decomposition of the test substance is monitored by measuring the amount of carbon dioxide produced. The carbon dioxide is captured using barium hydroxide or sodium hydroxide and quantified by titrating the remaining hydroxide, or by measuring the inorganic carbon.

[0280] The amount of carbon dioxide produced from the test substance is expressed as a percentage of theoretical carbon dioxide (ThCO2) after adjusting for the carbon dioxide produced by the culture without the test substance. Furthermore, the degree of biodegradation can be determined by analyzing the change in dissolved organic carbon (DOC) concentration at the beginning and end of the incubation period.

[0281] Description of the OECD 301F exam Add the known concentration of the test substance to the measured volume of inorganic culture medium. The test substance is used as a nominal organic carbon source. Place the culture medium in a sealed flask and stir at a constant temperature (within the range of +1°C or less) for a maximum of 60 days.

[0282] Oxygen consumption is measured by one of two methods: first, by measuring the amount of oxygen (electrolytically generated) required to maintain a constant gas volume in the respiratory flask; and second, by monitoring changes in volume or pressure (or a combination of both) within the device.

[0283] Any carbon dioxide produced during this process is absorbed using a solution of potassium hydroxide or another suitable absorbent. The amount of oxygen utilized by the microbial community during the biodegradation of the test substance is determined by subtracting the amount of oxygen taken up by a culture without the test substance (this is done in parallel). This value is expressed as a percentage of the theoretical oxygen demand (ThOD) or, less ideally, the chemical oxygen demand (COD).

[0284] These tests were performed on cellulose ester Examples 1-3, 1-4, 1-5, 1-6, and CA-398-6, as well as on fine particle Examples 2-1, 2-2, and Comparative Example 1. The results are shown in Table 1.3 below. [Table 3]

[0285] Table 1.3 shows that the biodegradability percentage of the fine particles is higher than that of the raw material cellulose ester used to prepare the fine particles, and that Examples 1-4 have the highest biodegradability percentage among the cellulose esters tested.

[0286] Cosmetic formulations Examples of cosmetic formulations prepared and tested include water / oil (W / O) type liquid foundation, W / O type sunscreen, lipstick, and W / O type lotion.

[0287] Water-based / oil (W / O) liquid foundation Table 2 lists the ingredients used in the preparation of the W / O type liquid foundation formulation. [Table 4]

[0288] Preparation of W / O type liquid foundation The W / O type liquid foundation formulation was prepared according to the following process. 1. Combine phase A (first dissolve polyhydroxystearic acid) and pass it through a 3-roll mill three times. 2. Combine phase B and mix using an overhead agitator (large dissolving machine / 400 RPM). 3. Add phase A to phase B and homogenize for 5 minutes using Ultra Turax (5000 RPM). 4. Add phase C and stir with a magnetic stirrer bar until dissolved. 5. While mixing with Ultra Turax (10000 RPM), slowly add phase C to phases A and B. 6. Homogenize at 10,000 rpm for 10 minutes. While mixing at 7,500 RPM, add the components of phase D one by one to the emulsion. 8. Add fine particles while mixing with Ultra Turax at 10,000 rpm.

[0289] test In the test of the W / O type liquid foundation, an optical effect test and a sensory panel evaluation were conducted.

[0290] The optical effect was evaluated by using an in vitro skin-mimicking substrate formed of a textured synthetic leather having a topography pattern. The procedure for applying the formulation to the substrate is as follows. 1. Cut a large piece of synthetic leather with scissors into small squares of 5×5 cm 2 size. 2. Gently mix the cosmetic formulation with a pipette or a wooden stick. 3. Weigh 0.05 g of the cosmetic formulation in total with an analytical balance and evenly drop it onto nine different points on the textured leather substrate. 4. Spread the cosmetic by rubbing it in a circular motion with a gloved finger for 1 minute. 5. Visually evaluate the sample with the dried cosmetic for 5 minutes (at an angle of about 45 degrees), and conduct an evaluation (1 - 5) of the optical effect and coverage. Confirm that the lighting conditions are the same for all evaluations. 6. Take a photo for the purpose of record keeping. [Table 5]

[0291] Also, the optical effect test was conducted on commercially available liquid foundation products. The results are shown in Table 4. [Table 6]

[0292] The sensory panel test was conducted by 5 - 10 sensory testers. Numbers or letters were randomly assigned to the products, and a blind test was conducted. A small amount (10 - 30 mg) of the product was applied to the back of the hand, and then gently rubbed and spread in a circular motion with a fingertip. Each tester was required to evaluate each of the following sensory characteristics in order from low to high intensity on a scale of 1 - 5.

[0293] Spreading: Evaluate how well the sample spreads and maintains uniform coverage when applied to skin in a moist state. A score of 1 indicates difficulty in consistently spreading, while a score of 5 indicates very easy consistent spreading.

[0294] Slipperiness: Evaluate how well the sample slides or moves (or is smooth) when applied to the skin. 1 is difficult to move, 5 is very easy to move.

[0295] Smoothness: After application and drying, evaluate the smoothness of the sample. 1 is rough, 5 is very smooth.

[0296] Coverage: Evaluates the uniformity of color / pigment fixation after the sample has been applied and dried. 1 is non-uniform, 5 is very uniform.

[0297] Soft focus: This evaluates how well a soft focus blurs / hides blemishes / defects optically by controlling light scattering to conceal imperfections, showing how diffusely the light is reflected in the covered area. A score of 1 indicates poor blurring / hideability, while a score of 5 indicates very good blurring / hideability.

[0298] Gloss suppression: Evaluate how well the coated sample suppresses gloss (or shine) and reduces contrast with skin. A score of 1 indicates a glossy or shiny appearance with high contrast, while a score of 5 indicates a very uniform (no gloss) appearance with low contrast.

[0299] After each evaluation, any product residue on the skin was wiped off, and the next product was evaluated. The results, representing the average evaluation of each characteristic, are shown in Table 5 below. [Table 7]

[0300] The shapes of specific microparticles were identified and are shown in Table 6 below. The effect of shape on sensory evaluation was assessed. The results are shown in Table 7 below. [Table 8] [Table 9]

[0301] Tables 5-7 show that, generally, larger particle sizes result in higher ratings for spreadability, slipperiness, and smoothness, while having less impact on the evaluation of soft-focus and gloss suppression effects (see Table 5). Furthermore, spherical shapes result in higher ratings for spreadability, slipperiness, and smoothness, while generally leading to lower ratings for coverage, soft-focus, and gloss suppression effects (see Tables 6 and 7).

[0302] Water / oil (W / O) type sunscreen Table 8 lists the ingredients used in the preparation of the W / O type sunscreen formulation. [Table 10]

[0303] Preparation of W / O type sunscreen The W / O type sunscreen formulation was prepared according to the following process. 1. Combine phase B (oil phase) and mix using a large dissolving machine with overhead stirring at 400 RPM. 2. Heat the oil phase to 50°C. 3. Add phase C (aqueous phase) and stir with a magnetic stirrer until well combined. 4. Add the zinc oxide dispersion (phase A) to the oil phase. 5. Once Phase A is thoroughly mixed with Phase B, transfer to a Silverson mixer and mix at 5000 RPM for 5 minutes. 6. While mixing with a Silverson mixer (10000 RPM), slowly add phase CD to phases AB. 7. Homogenize at 10,000 rpm for 10 minutes. Phase E (fine particles) is added later while mixing with a Silverson at 8.10000 RPM.

[0304] test In the W / O (water-free) sunscreen testing, the sun protection factor (SPF) and absorbance at different wavelengths were determined. SPF was determined according to standard industry practices for in vitro SPF measurement. Further formulations were prepared in the same manner as above, but these formulations did not contain zinc oxide dispersion paste (UV protectant), and the absorbance was tested with and without the UV protectant. Absorbance was measured using a spectrophotometer. The tested formulations and results are shown in Tables 9 and 10 below. [Table 11] [Table 12]

[0305] Tables 9 and 10 show that the formulation containing the fine particles of Example 2-1 has a higher SPF than the formulation containing nylon 12 or PMMA, and that the formulation containing the fine particles of Example 2-1 increased UV absorption when a UV protection agent was present.

[0306] lipstick Table 11 lists the ingredients used in the preparation of the lipstick formulation. [Table 13]

[0307] Lipstick preparation The lipstick formulation was prepared according to the following process. Lipstick base: 1. Heat part A to 80°C under propeller mixing. 2. Add part B. Mix for 10 minutes until uniform. 3. Add part C. Mix until uniform. 4. Allow to cool. Incorporate different microparticles / powders into the lipstick base. 1. Weigh out the required amount of lipstick base. 2. Heat to 80°C under propeller mixing. 3. Add the fine particles to the melted lipstick base and mix for 10 minutes until uniform. 4. Pour the mixture into the lipstick mold and allow it to cool.

[0308] test In the lipstick tests, the ability of the lipstick to color the substrate was determined by measuring the change in color in response to the amount of fine particles / powder added.

[0309] Tested particles / powders: Lipstick samples were prepared by adding 0, 1, 3, 6, and 9% of fine particles / powder to a lipstick base. The fine particles / powder used are listed in Table 12. [Table 14]

[0310] Color testing methods: Lipstick is applied to a silicone substrate (which mimics skin). A consistent application method to the substrate sample is used to compare different formulations. The L*a*b* color values ​​of the colored sample are measured using a handheld spectrophotometer (Konica Minolta 2600d). From these values, Delta L* and Delta a* are calculated, with 0% additive as the initial value. A decrease in the L* value indicates that the sample is darker (or more strongly colored), and an increase in the Delta a* value indicates an increase in red (the pigment used in the lipstick base is Red 40 Lake). Coverage uniformity is evaluated on a scale of 0 to 5 by visually assessing the sample (5 = best color uniformity). The results are shown in Tables 13-15 below. [Table 15]

[0311] Table 13 shows that, similar to nylon 12, the addition of the fine particles of Example 2-1 reduced the Delta L* value, and both materials resulted in a darker (or stronger) color of the applied lipstick and the desired effect. The best results were obtained with a 6% addition. Example 2-1 performed better in terms of color intensity compared to silica, PMMA, and starch, with cellulose providing the greatest increase in color intensity. [Table 16]

[0312] Table 14 shows that, similar to nylon 12, the addition of the fine particles from Example 2-1 increased the red color (or the delta a* value). The best results were obtained with a 6% addition. Example 2-1 showed better performance in increasing red color compared to silica, PMMA, and starch, with cellulose increasing the red color the most. [Table 17]

[0313] Table 15 shows that Example 2-1 and silica exhibited the best pigment distribution and coverage uniformity, followed by nylon 12 and PMMA. Cellulose and starch had the worst coverage uniformity.

[0314] W / O type lotion Table 16 lists the ingredients used in the preparation of the non-polar oil-based simple W / O type lotion formulation. [Table 18]

[0315] Preparation of W / O type lotion The W / O type lotion formulation was prepared according to the following process. 1. Combine phase A and mix with an overhead mixer (500 rpm) until uniform. 2. Add phase B and stir until dissolved (using a magnetic stirrer bar). 3. Add phase B to phase A while mixing with high shear (Ultra Turax mixer at 10,000 rpm). 4. Homogenize at 10,000 rpm for 5 minutes.

[0316] test In the W / O type lotion test, a gloss reduction test was performed. The gloss reduction was evaluated using a BYK MicroTRI gloss meter. Sample preparation and gloss reduction measurement were performed according to the following procedure. 1. Cut out a template using painted tape that matches the bottom of the gloss meter and attach it to the bottom of the instrument before taking a measurement (to prevent leakage onto the instrument's components). Using a 2.4 mil square-down bar, the formulation sample is applied to the Leneta paper by pulling the bar down from the top edge to the bottom edge of the Leneta paper at a constant speed / pressure. 3. First, measure the gloss at three angles (20°, 60°, and 85°), and then measure the gloss every 5 minutes for 30 minutes. This is because high-gloss surfaces with a gloss unit (GU) of 70 or more should be measured using the 20° angle, while semi-gloss surfaces with a GU in the range of 10 to 70 should be measured using the 60° angle. 4. After the initial measurement, ensure the gloss meter is returned to the exact same position for subsequent measurements to obtain accurate data. The measuring instrument should also transfer a mark to the drawdown film indicating the location of the previous measurement. 5. Without moving the gloss meter, take three measurements for each sample, obtain the average measurement value, and perform two drawdowns for each sample material. 6. For comparison and recording purposes, use the GU value at a 60° angle and record the data every 30 minutes.

[0317] The gloss reduction value is determined by setting the initial value to 0% additive amount (or base lotion) and recording the gloss reduction as a percentage change (decrease) in GU. The test formulations and the fine particles used to reduce gloss are shown in Table 17. [Table 19]

[0318] Table 17 shows that the lotion formulation containing the fine particles of Example 2-1 had the greatest reduction in gloss.

[0319] Cellulose ester solubility test To measure the solubility of CE such as cellulose acetate butyrate (CAB) (Example 1-1) in a solvent system containing ethyl acetate (EA), n-propanol (nPrOH), and water, CE dopes were prepared as shown in Table 18 below. The preparation of Example 3-1 is shown below.

[0320] Preparation of CE dope CE dopes were prepared by adding the respective amounts of solvent system, as shown in Table 18, to a dry 250 mL single-neck round-bottom flask equipped with a magnetic stirrer. The solvent system was stirred, and then the respective amounts / types of CAB were added to the flask. The CAB was added to the flask by slowly metering the solids at a rate that allowed the stirring vortex to move the solid particles into the solvent system without forming large clumps of powder at the top of the liquid phase. The solvent-CAB mixture was stirred at room temperature for 45 minutes. If the mixture became homogeneous during this period, the dope was determined to be "soluble". If the solid particles remained undissolved in the solvent system after 60 minutes, the dope was determined to be "insoluble".

[0321] In dopes 3-1, 3-2, and 3-3, the solvent system contained varying amounts of ethyl acetate and n-propanol, but no water. In dopes 3-1a, 3-2a, and 3-3a, water was added to the solvent system. That is, the solvent systems of dopes 3-1 and 3-1a, dopes 3-2 and 3-2a, and dopes 3-3 and 3-3a contained the same amounts of ethyl acetate and n-propanol, with the only difference between the dopes being the addition of water.

[0322] In dope 3-4, the amount of CAB in the CE dope was increased so that its mass percentage of CAB matched that of the water-free dope (i.e., dopes 3-1, 3-2, and 3-3). [Table 20]

[0323] Notably, CE dopes without water were unable to solubilize the CE contained within them. For example, dope 3-1 resulted in a lumpy, heterogeneous mixture, while dopes 3-2 and 3-3 initially produced a stirable slurry, but became lumpy and heterogeneous after a few minutes.

[0324] On the other hand, dope 3-1a yielded a stirable slurry rather than a lumpy one. Dopes 3-2a and 3-3a yielded a homogeneous mixture in which CE dissolved in the solvent system within 3 minutes.

[0325] As observed in dope 3-4, even when the mass of CE contained in the CE dope was increased, a homogeneous mixture in which CE dissolved in the solvent system within 3 minutes was obtained. In other words, it was not considered that increasing the CAB% of the CE dope adversely affected the solubility of CE in the solvent system.

Claims

1. A cosmetic composition comprising biodegradable microparticles, wherein the biodegradable microparticles comprise a mixed cellulose ester, The biodegradable fine particles exhibit at least 50% biodegradation in 60 days according to at least one of the OECD 301B, OECD 301C, or OECD 301F test methods. The aforementioned mixed cellulose ester, (a) For acetyl substituents, the average degree of substitution is in the range of 0.1 to 2.3 ("DS Ａｃ "), (b) The average degree of substitution of the propynyl substituent is in the range of 0.1 to 1.5 ("DS Ｐｒ ) or the average degree of substitution of the butyryl substituent in the range of 0.1 to 1.5 ("DS Ｂｕ "), and (c) Average degree of substitution of hydroxyl substituents in the range of 0.6 to 2.8 ("DS ＯＨ The cosmetic composition having the following characteristics:

2. The cosmetic composition according to claim 1, wherein the cosmetic composition contains at least 0.1, at least 0.5, at least 1, at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9, at least 10, at least 11, at least 12, at least 13, at least 14, or at least 15% by weight of the biodegradable fine particles.

3. The cosmetic composition according to claim 1 or 2, wherein the biodegradable fine particles have an average sphericity of less than 50% or less than 40%.

4. The cosmetic composition according to any one of claims 1 to 3, wherein the cosmetic composition is a foundation, sunscreen, lipstick, mascara, eyeshadow, lotion, dry shampoo, liquid shampoo, body wash, lotion, hair conditioner, skin moisturizer, face wash, tablet, foot powder, baby powder, shaving cream, or shaving gel.

5. The cosmetic composition contains at least one, two, three, four, or five cosmetic additives in an amount of at least 1% by weight to less than 60% by weight. The cosmetic composition according to any one of claims 1 to 4, wherein the cosmetic additive comprises a colorant, oil, wax, fatty acid, alcohol, ester, hydrocarbon, silicone oil, surfactant, metal soap, humectant, thickener, UV absorber, antioxidant, oil absorber, exfoliant, water, or a combination thereof.

6. The biodegradable fine particles exhibit a unimodal particle size distribution having a span of at least 0.5 and / or less than 3.

0. The cosmetic composition according to any one of claims 1 to 5, wherein the biodegradable fine particles have a D[4,3] particle size in the range of 1 to 50 microns.

7. The butyric acid content of the biodegradable fine particles is less than 100 ppm by weight, and / or The cosmetic composition according to any one of claims 1 to 6, wherein the acetic acid content of the biodegradable fine particles is less than 500 ppm by weight.

8. The cosmetic composition according to any one of claims 1 to 7, wherein the biodegradable fine particles exhibit at least 55% biodegradability or at least 60% biodegradability in 60 days according to at least one of the OECD 301B test method, the OECD 301C test method, or the OECD 301F test method.

9. The cosmetic composition according to any one of claims 1 to 8, wherein the mixed cellulose ester exhibits a biodegradability of at least 45%, at least 50%, at least 55%, or at least 60% in 60 days according to at least one of the OECD 301B, OECD 301C, or OECD 301F test methods.

10. Said DS Ａｃ The cosmetic composition according to any one of claims 1 to 9, wherein the amount is at least 1.

5.

11. Said DS Ａｃ The cosmetic composition according to any one of claims 1 to 10, wherein the ratio is less than 2.

3.

12. Said DS Ｐｒ The cosmetic composition according to any one of claims 1 to 11, wherein the ratio is at least 0.

1.

13. Said DS Ｐｒ The cosmetic composition according to any one of claims 1 to 12, wherein the amount is less than 0.

5.

14. The DS Ｂｕ is at least 0.1 or at least 0.2, and the cosmetic composition according to any one of claims 1 to 13.

15. Said DS Ｂｕ The cosmetic composition according to any one of claims 1 to 14, wherein the amount is less than 0.5 or less than 0.

3.

16. Said DS ＯＨ The cosmetic composition according to any one of claims 1 to 15, wherein the ratio is at least 0.

7.

17. Said DS ＯＨ The cosmetic composition according to any one of claims 1 to 16, wherein the ratio is less than 1.

2.

18. The cosmetic composition according to any one of claims 1 to 17, wherein the biodegradable fine particles comprise at least 75% by weight of the mixed cellulose ester.

19. The cosmetic composition according to any one of claims 1 to 18, wherein the biodegradable fine particles essentially consist of the mixed cellulose ester.

20. The cosmetic composition according to any one of claims 1 to 19, wherein the polydispersity index of the biodegradable fine particles is less than 0.

8.

21. The cosmetic composition according to any one of claims 1 to 20, wherein the biodegradable fine particles have a sphericity of at least 10%.

22. The cosmetic composition according to any one of claims 1 to 21, wherein the biodegradable fine particles, when measured by the ASTM D281 test method using mineral oil instead of castor oil, exhibit an oil absorption capacity of at least 50 mL per 100 g.

23. A cosmetic composition comprising 0.5 to 15% by weight of biodegradable fine particles, wherein the biodegradable fine particles comprise a mixed cellulose ester. The biodegradable fine particles exhibit at least 50% biodegradation in 60 days according to at least one of the OECD 301B, OECD 301C, or OECD 301F test methods. The biodegradable fine particles are 0.1 to 15 m ２ Having an average BET surface area within the range of / g, The aforementioned mixed cellulose ester, (a) For acetyl substituents, the average degree of substitution is in the range of 1.5 to 2.3 ("DS Ａｃ "), (b) The average degree of substitution of the butyryl substituent is in the range of 0.1 to 0.3 ("DS Ｂｕ "), and (c) Average degree of substitution of hydroxyl substituents within the range of 0.7 to 1.1 ("DS ＯＨ The cosmetic composition having the following characteristics:

24. The cosmetic composition according to claim 23, wherein the biodegradable fine particles essentially consist of the mixed cellulose ester.

25. Said DS ＯＨ The cosmetic composition according to any one of claims 23 to 24, wherein the value is in the range of 0.7 to 1.

0.

26. A method for preparing a cosmetic composition, (a) comprising preparing a plurality of biodegradable fine particles comprising a mixed cellulose ester, wherein the biodegradable fine particles exhibit at least 50% biodegradation in 60 days according to at least one of the OECD 301B test method, the OECD 301C test method, or the OECD 301F test method, and the mixed cellulose ester (i) The average degree of substitution of acetyl substituents is in the range of 1.5 to 2.3 ("DS Ａｃ "), (ii) For propynyl substituents, the average degree of substitution is in the range of 0.1 to 0.3 ("DS Ｐｒ ) or the average degree of substitution of the butyryl substituent in the range of 0.1 to 0.3 ("DS Ｂｕ "), and (iii) Average degree of substitution for hydroxyl substituents in the range of 0.7 to 1.1 ("DS ＯＨ The method further has, (b) Preparing a preliminary cosmetic mixture by mixing the biodegradable fine particles with one or more cosmetic additives, (c) preparing the cosmetic composition from the preliminary cosmetic mixture, The method wherein the cosmetic composition contains at least 2% by weight of the biodegradable fine particles.

27. The method according to claim 26, wherein the biodegradable fine particles are produced by jet mill grinding and have an average sphericity in the range of 5 to 30%.

28. The method according to any one of claims 26 to 27, wherein the cosmetic composition is a foundation, sunscreen, lipstick, mascara, eyeshadow, lotion, dry shampoo, liquid shampoo, body wash, lotion, hair conditioner, skin moisturizer, face wash, tablets, foot powder, baby powder, shaving cream, or shaving gel.

29. The method according to any one of claims 26 to 28, wherein the biodegradable fine particles have a D[4,3] average particle size in the range of 1 to 10 microns.

30. The method according to any one of claims 26 to 29, wherein the biodegradable fine particles exhibit at least 60% biodegradation in 60 days according to the OECD 301F test method.

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