Biodegradable microbeads with improved optical effects

Abstract

Biodegradable microbeads exhibiting excellent optical effects are provided. More specifically, biodegradable microparticles formed from biodegradable mixed cellulose esters are provided, which exhibit excellent optical effects such as haze transmittance, and are highly beneficial when used in the manufacture of cosmetic formulations. Furthermore, the produced microbeads exhibit improved solidity, sphericity, and smoothness.

Description

Technical Field

[0001] Microbeads are particles with a diameter of less than 1 millimeter (mm). These particles may be included in consumer products such as personal care products and cosmetics. Many of these microbead-containing products are designed to be applied and then washed or rinsed off the user's body. When microbead-containing products are washed or rinsed off the user's body, the particles are flushed into the drain and received by municipal water treatment facilities. In the past, many known microbeads were formed from plastic or polymer materials such as polyethylene, polypropylene, polymethyl methacrylate, nylon, polyurethane, etc. These materials generally have limited biodegradability. Furthermore, due to the small size of the particles, the ability to be captured in 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 microbeads can be ingested by wildlife or cause other environmental concerns. Therefore, the possibility of generating microbead particles from more environmentally friendly materials has recently been explored. However, consumers tend to have high expectations regarding the personal care products and / or cosmetics they use, including those containing microbeads. For example, consumers expect these personal care products and cosmetics to exhibit certain optical properties that allow the product to blend with the natural skin color and easily hide any undesirable blemishes.

Background Art

[0002] Therefore, it is desirable to develop biodegradable microbeads that meet environmental and consumer expectation criteria, particularly with regard to the optical properties of personal care products and cosmetics.

Summary of the Invention

[0003] In one aspect, the present technology relates to biodegradable microparticles containing a mixed cellulose ester, and these biodegradable microparticles exhibit at least 50 percent biodegradability and a haze (turbidity) transmittance of at least 10 percent in 60 days according to at least one of the OECD 301B, OECD 301C, or OECD 301F test methods. Further, the mixed cellulose ester has (a) an average degree of substitution (referred to as "DS Ac ") for acetyl substituents within the range of 0.1 to 2.3, (b) an average degree of substitution (referred to as "DS Pr ") for propionyl substituents or an average degree of substitution (referred to as "DS Bu ") for butyryl substituents within the range of 0.1 to 1.5, and (c) an average degree of substitution (referred to as "DS OH ") for hydroxyl substituents within the range of 0.6 to 2.8.

[0004] In one aspect, the present technology relates to biodegradable microparticles containing a mixed cellulose ester, and these biodegradable microparticles exhibit at least 50 percent biodegradability and a haze (turbidity) transmittance of at least 10 percent in 60 days according to at least one of the OECD 301B, OECD 301C, or OECD 301F test methods. Further, the mixed cellulose ester has (a) an average degree of substitution (referred to as "DS Ac ") for acetyl substituents within the range of 0.1 to 2.3, (b) an average degree of substitution (referred to as "DS Bu ") for butyryl substituents within the range of 0.1 to 1.5, and (c) an average degree of substitution (referred to as "DS OH ") for hydroxyl substituents within the range of 0.6 to 2.8.

[0005] In one aspect, the present technology relates to a process for forming biodegradable microparticles. Generally, this process includes: (a) forming a dope containing a mixed cellulose ester; (b) contacting at least a portion of the dope with an aqueous mixture under agitation, thereby forming a primary emulsion; (c) converting at least a part of the primary emulsion into a dispersion containing a solid phase and a liquid phase, wherein the solid phase contains biodegradable microparticles; and (d) recovering at least a part of the biodegradable microparticles from the dispersion. The biodegradable microparticles exhibit at least 50% biodegradability in 60 days and a haze transmittance of at least 10% according to at least one of the OECD 301B, OECD 301C, or OECD 301F test methods. Further, the mixed cellulose ester has (a) an average degree of substitution (「DS Ac 」) for acetyl substituents within the range of 0.1 to 2.3, (b) an average degree of substitution (「DS Pr 」) for propionyl substituents or an average degree of substitution (「DS Bu 」) for butyryl substituents within the range of 0.1 to 1.5, and (c) an average degree of substitution (「DS OH 」) for hydroxyl substituents within the range of 0.6 to 2.8.

Brief Description of the Drawings

[0006] [Figure 1] It is a schematic diagram of an exemplary process for producing cellulose ester microbeads. [Figure 2] It is a more detailed schematic diagram of an exemplary process for producing cellulose ester microbeads. [Figure 3] It is a schematic diagram of another process for producing cellulose ester microbeads by serial particle formation. [Figure 4] It is a schematic diagram of an alternative process for manufacturing cellulose ester microbeads by forming a separated dope and an aqueous mixture, and forming a composite emulsion / dispersion and particle hardening. [Figure 5]This is a schematic diagram of an alternative process for producing cellulose ester microbeads by forming a complex emulsion / dispersion. [Figure 6] This is a schematic diagram of an alternative process for producing cellulose ester microbeads by forming a complex emulsion / dispersion and hardening the particles. [Figure 7] This is a schematic diagram of an alternative process for producing cellulose ester microbeads by solvent flushing before particle hardening. [Modes for carrying out the invention]

[0007] This disclosure relates to compositions and processes for producing cured cellulose ester (CE) microbeads or jet-milled cellulose ester (CE) microbeads exhibiting excellent optical properties. The processes disclosed herein allow for control of the solidity of the produced microbeads so that they exhibit desirable tactile and optical qualities. For example, CE microbeads may have enhanced solidity, sphericity, and smoothness, low water content, and / or low free acid content. These qualities, in addition to the biodegradability of CE, make the CE microbeads produced herein desirable for use in personal care products, cosmetics, and the like.

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

[0009] A value may be expressed as "about" or "approximately" a given number. Similarly, a range may be expressed herein as "about" one particular value to and / or "about" another particular value. Where such a range is expressed, another aspect includes from one particular value to and / or other particular values. Similarly, where a value is expressed as an approximation using the preceding "about," it is understood that a particular value forms another aspect.

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

[0011] As used herein, when the term "and / or" is used in a list of two or more items, it means that any one of the listed items can be used by itself, or any combination of two or more of the listed items can be used. For example, if a composition is described as containing components A, B, and / or C, the composition may contain A only, B only, C only, 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 open-ended transitional clauses used to move the subject listed before the term to one or more elements listed after the term, the elements listed after the transitional clause are not necessarily the only elements constituting the subject.

[0013] As used herein, the terms “having,” “has,” and “have” have the same open-ended meaning as “comprising,” “comprises,” and “comprise” as defined above.

[0014] As used herein, the terms “including,” “includes,” and “include” have the same open-ended meaning as “comprising,” “comprises,” and “comprise” as defined above.

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

[0017] Regarding shape, "spherical, ellipsoidal, or spheroidal" means that the average sphericity of the particles is less than 70%. Regarding shape, "spherical, spherical, or spherical" means that the average sphericity of the particles is 70% or more.

[0018] The degree of substitution is hydroxyl, i.e., DS OHWhen referring to this, 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.

[0019] The description of this invention uses numerical ranges to quantify specific parameters relating to the invention. Where numerical ranges are provided, it should be understood that such ranges should be interpreted as providing literal support for claims that enumerate only the lower limit of the range, as well as claims that enumerate only the upper limit of the range. For example, a disclosed numerical range of 10 to 100 provides literal support for claims that enumerate "greater than 10" (no upper limit) and claims that enumerate "less than 100" (no lower limit).

[0020] This specification uses specific numerical values ​​to quantify certain parameters relating to the present invention, where these specific numerical values ​​are not part of an express numerical range. It should be understood that each specific numerical value provided herein should be interpreted 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 percent of the positive and negative values ​​of that number, rounded to two significant figures. The intermediate range associated with each specific numerical value is 30 percent of the positive and negative values ​​of that number, rounded to two significant figures. The narrow range associated with each specific numerical value is 15 percent of the positive and negative values ​​of that number, rounded to two significant figures. For example, if a specific temperature of 62°F is described herein, such a description verbally supports 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 these specific values. Thus, if the specification describes a first pressure of 110 psi and a second pressure of 48 psia (a difference of 62 psi), the broad, intermediate, and narrow ranges of the pressure difference between these two flows would be 25 to 99 psi, 43 to 81 psi, and 53 to 71 psi, respectively.

[0021] Throughout this application, where any patent or publication is referenced, the entirety of the disclosures of those references is intended to be incorporated by reference to this application to more fully explain the state of the art to which the present invention relates, to the extent that such disclosures are not inconsistent with the present invention.

[0022] Referring here to Figure 1, CE microbeads 112 may be prepared by combining 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 combined in unit 110 to form an initial emulsion. The initial emulsion includes a dispersed phase and a continuous phase. The dispersed phase includes at least a portion of CE 100 and at least a portion of solvent 102. The continuous phase includes at least a portion of water 104, at least a portion of hydrophilic colloid 106, and at least a portion of surfactant 108.

[0023] Once combined, the initial emulsion may be stirred in unit 110 to form a pre-cured dispersion comprising a solid phase and a liquid phase. This solid phase comprises initial microparticles containing at least a portion of CE 100 and at least a portion of solvent 102. This liquid 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. Additional water 104 (i.e., drowning solution / extractant) may be added to the pre-cured dispersion to increase the water concentration around the initial microparticles. An initial cured dispersion containing the initial microparticles and the drowning solution is then formed. The initial cured dispersion may be stirred in unit 110 to facilitate the transfer of the solvent from the initial microparticles to the drowning solution. This solvent transfer facilitates the curing of the initial microparticles, generating cured CE microbeads 112, which are incorporated into the solvent-containing drowning solution.

[0024] The CE microbeads 112 can be recovered from the dispersion 114 by first processing them in the solid / liquid separation unit 116. The solid flow 118 containing the CE microbeads 112 may be led to the solid processing unit 120, where the CE microbeads 112 are washed with water 122 and then dried to recover them, which will be described in more detail below. The liquid flow 124 formed from the drafting fluid containing the solvent may be led to the liquid processing unit 126. Optionally, the excess liquid flow 128 led from unit 110 and the wash water flow 130 from unit 120 may also be received in unit 126 for processing there.

[0025] In unit 126, the liquid received therein can be separated into at least a water-enriched flow 132 and a solvent-enriched flow 134. In some embodiments, the water-enriched flow 132 is recovered, and at least a portion of it can be used, for example, in unit 110. Furthermore, the solvent-enriched flow 134 may be recycled and used as at least a portion of the solvent for forming CE microbeads 112 in unit 110. Reuse of recovered water and / or solvent facilitates improvements in the economics of the CE microbead formation process described herein.

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

[0027] In general, the cellulose esters described herein, e.g., 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 a variety of grades and sources, such as 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, the cellulose triester may be hydrolyzed by adding a water-acid mixture, and this may be filtered to remove gel particles or fibers. Water is added to the mixture to precipitate the cellulose ester. The cellulose ester may then be washed with water to remove reaction byproducts, 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 (including the alkyl or aryl groups described herein that are suitable for use in the acyl substituents of 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, propionyl, butyl, pivaloyl, benzoyl, and naphthoyl chlorides or bromides. Suitable carboxylic acid esters include, but are not limited to, acetyl, propionyl, butyl, pivaloyl, benzoyl, and naphthoyl methyl esters. In one or more embodiments, the acylation reagent may 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 tributyrate, or mixed triesters of cellulose, such as cellulose acetate propionate and cellulose acetate butyrate. These cellulose triesters can be prepared by a number of 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 second 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 way generally have the following structure: [ka]

[0033] In the formula, R 2 , R 3 , and R 6 is hydrogen (however, R 2 , R 3 , and R 6 Alkyl-acyl groups (which are not hydrogen at the same time), and / or aryl-acyl groups (such as those mentioned above) that are bonded to cellulose via ester bonds.

[0034] The degree of polymerization ("DP") of the cellulose esters prepared by these methods may be at least 10. In other embodiments, the DP of the cellulose ester may be at least 50, at least 100, or at least 250. In other embodiments, the DP of the cellulose ester may be in the range of about 5 to about 100, or in the range of about 10 to about 50.

[0035] 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 (including the alkyl or aryl groups described herein that are suitable for use in the acyl substituents of 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, propionyl, butyl, pivaloyl, benzoyl, and naphthoyl chlorides or bromides. Suitable carboxylic acid esters include, but are not limited to, acetyl, propionyl, butyl, pivaloyl, benzoyl, and naphthoyl methyl esters. In one or more embodiments, the acylation reagent may 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.

[0036] In a first aspect, this application relates to a mixed ester cellulose ester ("MCE") having (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 ("DS") for the acetyl substituents of 0.1 to 2.3. Ac ) has an average degree of substitution for propionyl substituents of 0.1 to 1.5 ("DS Pr ) has, and the MCE has an average degree of substitution for hydroxyl substituents of 0.6 to 2.8 ("DS OH We disclose a mixed ester cellulose ester ("MCE") having the following properties.

[0037] In one embodiment, or in combination with any other embodiment, class, or subclass of this first embodiment, DS Acis 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, or 1.8~2.3, or 1.8~2.2, or 1.8~2.1, or 1.8~2.0, or 1.85~2.3, or 1.85~2.2, or 1.85~2.1, or 1.85~2.0, or 1.9~2.3, or 1.9~2.2, or 1.9~2.1, or 1.9~2.0. Furthermore, or alternatively, DS Ac This is less than 2.3, or less than 2.2, or less than 2.1, or less than 2.0, or less than 1.9, or less than 1.8, or less than 1.7, or less than 1.6, or less than 1.5, or less than 1.4, or less than 1.3, or less than 1.2, or less than 1.1, or less than 1.0, or less than 0.9, or less than 0.8, or less than 0.7, or less than 0.5, or less than 0.4, or less than 0.3.

[0038] 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.

[0039] In one embodiment, or in combination with any other embodiment, class, or subclass of this first embodiment, DS Pr is at least 0.1, or at least 0.2, or at least 0.3, or at least 0.4, or at least 0.5, or at least 0.6, or at least 0.7, or at least 0.8, or at least 0.9, or at least 1.0, or at least 1.1, or at least 1.2, or at least 1.3, or at least 1.4. Furthermore, or alternatively, DS Pr This is less than 1.5, or less than 1.4, or less than 1.3, or less than 1.2, or less than 1.1, or less than 1.0, or less than 0.9, or less than 0.8, or less than 0.7, or less than 0.5, or less than 0.4, or less than 0.3.

[0040] In one embodiment, or in combination with any other embodiment, class, or subclass of this first embodiment, DS PrThis refers to 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, or 0.1~0.5, or 0.1~0.4, 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 0.2~0.95, 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 0.25~0.85, 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 0.3~0.85, or 0.3~0.8, or 0.3~0.75, or 0.3~0.7, or 0.3~0.85, or 0.3~0.85, or 0.3~0.75, or 0.3~0.7 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, or 0.4~0.7, or 0.4~0.65, or 0.45~0.95, or The ranges are 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 0.5-0.65, or 0.1-0.9, or 0.1-0.85, or 0.1-0.8.

[0041] In one embodiment, or in combination with any other embodiment, class, or subclass of this first embodiment, DS OHis at least 0.6, or at least 0.7, or at least 0.8, or at least 0.9, or at least 1.0, or at least 1.1, or at least 1.2, or at least 1.3, or at least 1.4, or at least 1.5, or at least 1.6, or at least 1.7, or at least 1.8, or at least 1.9, or at least 2.0, or at least 2.1, or at least 2.2, or at least 2.3, or at least 2.4, or at least 2.5, or at least 2.6. Furthermore, or alternatively, DS OH This is less than 2.8, or less than 2.7, or less than 2.6, or less than 2.5, or less than 2.4, or less than 2.3, or less than 2.2, or less than 2.1, or less than 2.0, or less than 1.9, or less than 1.8, or less than 1.7, or less than 1.6, or less than 1.5, or less than 1.4, or less than 1.3, or less than 1.2, or less than 1.1, or less than 1.0, or less than 0.9, or less than 0.8.

[0042] In one embodiment, or in combination with any other embodiment, class, or subclass of this first embodiment, DS OH0.5~1.5, 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 0.55~1.5, 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 0.55~0.55~0.9, 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 0.15, or 0.6~1.1, or 0.6~1.15~1.05, or 0.6~1.0, or 0.6~0.95, or 0.6~0.9, 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 0.65~1.25, or 0.65~1.25, or 0.65~1.15, or 0.65~1.1, or 0.65~1.0 5, or 0.65-1.0, or 0.65-0.95, or 0.65-0.9, or 0.7-1.5, or 0.7-1.45, 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.

[0043] In one embodiment, or in combination with any other embodiment, class, or subclass of this first embodiment, DS Pr and DS AcThe 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.

[0044] In one embodiment, or in combination with any other embodiment, class, or subclass of this first embodiment, the mixed cellulose ester has a ratio of hydroxyl substituents to acetyl substituents of at least 0.4:1, or at least 0.5:1, or at least 0.6:1, or at least 0.7:1, or at least 0.8:1, or at least 0.9:1, or at least 1:1, or at least 1.1:1, or at least 1.2:1, or at least 1.3:1, or at least 1.4:1, or at least 1.5:1, or at least 1.6:1, or at least 1.7:1, or at least 1.8:1, or at least 1.9:2, or at least 2:1. Alternatively, the mixed cellulose esters have a ratio of hydroxyl substituents to acetyl substituents of less than 2:1, or less than 1.9:1, or less than 1.8:1, or less than 1.7:1, or less than 1.6:1, or less than 1.5:1, or less than 1.4:1, or less than 1.3:1, or less than 1.2:1, or less than 1.1:1, or less than 1:1.

[0045] In one embodiment, or in combination with any other embodiment, class, or subclass of this first embodiment, the MCE has a ratio of hydroxyl substituents to propionyl substituents of at least 0.4:1, or at least 0.5:1, or at least 0.6:1, or at least 0.7:1, or at least 0.8:1, or at least 0.9:1, or at least 1:1, or at least 1.1:1, or at least 1.2:1, or at least 1.3:1, or at least 1.4:1, or at least 1.5:1, or at least 1.6:1, or at least 1.7:1, or at least 1.8:1, or at least 1.9:2, or at least 2:1. Furthermore, or alternatively, the MCE has a ratio of hydroxyl substituents to propionyl substituents of less than 2:1, or less than 1.9:1, or less than 1.8:1, or less than 1.7:1, or less than 1.6:1, or less than 1.5:1, or less than 1.4:1, or less than 1.3:1, or less than 1.2:1, or less than 1.1:1, or less than 1:1.

[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, 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, or at least 90% biodegradability, or at least 95% biodegradability, according to at least one of the OECD 301B, OECD 301C, or OECD 301F test methods after 56 days.

[0047] 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, 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, or at least 90% biodegradability, or at least 95% biodegradability, according to at least one of the OECD 301B, OECD 301C, or OECD 301F test methods after 60 days.

[0048] In one embodiment, or in combination with any other embodiment, class, or subclass of this first embodiment, the MCE has a weight-average molecular weight 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.

[0049] In a second embodiment, this application provides a mixed ester 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 ("DS") for the acetyl substituents of 0.1 to 1.9. Ac ) has an average degree of substitution for propionyl substituents of 0.1 to 1.5 ("DS Pr ) and the MCE has an average degree of substitution for hydroxyl substituents of 0.7 to 2.8 ("DS OH We disclose a mixed ester cellulose ester ("MCE") having the following properties.

[0050] In one embodiment, or in combination with any other embodiment, class, or subclass of this second embodiment, DS Ac is at least 0.1, or at least 0.2, or at least 0.3, or at least 0.4, or at least 0.5, or at least 0.6, or at least 0.7, or at least 0.8, or at least 0.9, or at least 1.0, or at least 1.1, or at least 1.2, or at least 1.3, or at least 1.4, or at least 1.5, or at least 1.6, or at least 1.7, or at least 1.8, or at least 1.9, or at least 2.0. Furthermore, or alternatively, DS Ac This is less than 2.3, or less than 2.2, or less than 2.1, or less than 2.0, or less than 1.9, or less than 1.8, or less than 1.7, or less than 1.6, less than 1.5, or less than 1.4, or less than 1.3, or less than 1.2, or less than 1.1, or less than 1.0, or less than 0.9, or less than 0.8, or less than 0.7, or less than 0.5, or less than 0.4, or less than 0.3.

[0051] In one embodiment, or in combination with any other embodiment, class, or subclass of this second embodiment, DS Ac These are 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 0.7-0.9, or 0.7-1.0, or 0.7-1.1, or 0.7-1.2, or 0.8-0.9, or 0.8-1.0, or 0.8-1.1, or 0.8-1.2, or 0.9-1.0, or 0.9-1.1, or 0.9-1.2, or 1.0-1.1, or 1.0-1.2, or 1.1-1.2.

[0052] In one embodiment, or in combination with any other embodiment, class, or subclass of this second embodiment, DS Pris at least 0.1, or at least 0.2, or at least 0.3, or at least 0.4, or at least 0.5, or at least 0.6, or at least 0.7, or at least 0.8, or at least 0.9, or at least 1.0, or at least 1.1, or at least 1.2, or at least 1.3, or at least 1.4. Furthermore, or alternatively, DS Pr This is less than 1.5, or less than 1.4, or less than 1.3, or less than 1.2, or less than 1.1, or less than 1.0, or less than 0.9, or less than 0.8, or less than 0.7, or less than 0.5, or less than 0.4, or less than 0.3.

[0053] 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.

[0054] In one embodiment, or in combination with any other embodiment, class, or subclass of this second embodiment, DS OHis at least 0.6, or at least 0.7, or at least 0.8, or at least 0.9, or at least 1.0, at least 1.1, or at least 1.2, or at least 1.3, or at least 1.4, or at least 1.5, or at least 1.6, or at least 1.7, or at least 1.8, or at least 1.9, or at least 2.0, or at least 2.1, or at least 2.2, or at least 2.3, or at least 2.4, or at least 2.5, or at least 2.6. Furthermore, or alternatively, DS OH This is less than 2.8, or less than 2.7, or less than 2.6, or less than 2.5, or less than 2.4, or less than 2.3, or less than 2.2, or less than 2.1, or less than 2.0, or less than 1.9, or less than 1.8, or less than 1.7, or less than 1.6, or less than 1.5, or less than 1.4, or less than 1.3, or less than 1.2, or less than 1.1, or less than 1.0, or less than 0.9, or less than 0.8.

[0055] In one embodiment, or in combination with any other embodiment, class, or subclass of this second embodiment, DS OHThis 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.

[0056] 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.

[0057] 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.

[0058] In one embodiment, or in combination with any other embodiment, class, or subclass of this second embodiment, the mixed cellulose ester has a ratio of hydroxyl substituents to acetyl substituents of at least 0.4:1, or at least 0.5:1, or at least 0.6:1, or at least 0.7:1, or at least 0.8:1, or at least 0.9:1, or at least 1:1, or at least 1.1:1, or at least 1.2:1, or at least 1.3:1, or at least 1.4:1, or at least 1.5:1, or at least 1.6:1, or at least 1.7:1, or at least 1.8:1, or at least 1.9:2, or at least 2:1. Alternatively, this mixed cellulose ester has a ratio of hydroxyl substituents to acetyl substituents of less than 2:1, or less than 1.9:1, or less than 1.8:1, or less than 1.7:1, or less than 1.6:1, or less than 1.5:1, or less than 1.4:1, or less than 1.3:1, or less than 1.2:1, or 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 has a ratio of hydroxyl substituents to propionyl substituents of at least 0.4:1, or at least 0.5:1, or at least 0.6:1, or at least 0.7:1, or at least 0.8:1, or at least 0.9:1, or at least 1:1, or at least 1.1:1, or at least 1.2:1, or at least 1.3:1, or at least 1.4:1, or at least 1.5:1, or at least 1.6:1, or at least 1.7:1, or at least 1.8:1, or at least 1.9:2, or at least 2:1. Furthermore, or alternatively, the MCE has a ratio of hydroxyl substituents to propionyl substituents of less than 2:1, or less than 1.9:1, or less than 1.8:1, or less than 1.7:1, or less than 1.6:1, or less than 1.5:1, or less than 1.4:1, or less than 1.3:1, or less than 1.2:1, or less than 1.1:1, or less than 1:1.

[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, 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, or at least 90% biodegradability, or at least 95% biodegradability after 56 days by at least one of the OECD 301B, OECD 301C, or OECD 301F test methods.

[0061] 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, 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, or at least 90% biodegradability, or at least 95% biodegradability, according to at least one of the OECD 301B, OECD 301C, or OECD 301F test methods after 60 days.

[0062] In one embodiment, or in combination with any other embodiment, class, or subclass of this second embodiment, the MCE has a weight-average molecular weight 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.

[0063] In a third aspect, this application also relates to 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 ("DS") for the acetyl substituents of 0.1 to 2.4. Ac ) has, and the MCE has an average degree of substitution for the butyryl substituent of 0.1 to 1.5 ("DS Bu ) has, and the MCE has an average degree of substitution for hydroxyl substituents of 0.6 to 2.8 ("DS OH We also disclose mixed ester cellulose esters ("MCE") having the following properties.

[0064] In one embodiment, or in combination with any other embodiment, class, or subclass of this first embodiment, DS Ac is at least 0.1, or at least 0.2, at least 0.3, or at least 0.4, or at least 0.5, or at least 0.6, or at least 0.7, or at least 0.8, or at least 0.9, or at least 1.0, or at least 1.1, or at least 1.2, or at least 1.3, or at least 1.4, or at least 1.5, or at least 1.6, or at least 1.7, or at least 1.8, or at least 1.9, or at least 2.0. Furthermore, or alternatively, DS Ac is less than 2.3, or less than 2.2, or less than 2.1, or less than 2.0, or less than 1.9, or less than 1.8, or less than 1.7, or less than 1.6, or less than 1.5, or less than 1.4, or less than 1.3, or less than 1.2, or less than 1.1, or less than 1.0, or less than 0.9, or less than 0.8, or less than 0.7, or less than 0.5, or less than 0.4, or less than 0.3.

[0065] In one embodiment, or in combination with any other embodiment, class, or subclass of this third embodiment, DS Ac0.9~2.4, 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 0.9~1.8, or 0.9~1.7, or 0.9~1.6, or 0.9~1.4, or 0.9~1.3, or 0.9~1.2, or 0.9~1.1, or 0.9~1.0, or 0.92~2.4, or 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, or 0.9 6~2.3, 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, or 0.98~1.4, 0.98~1.3, or 0.98~1.2, or 0.98~1.1, or 0.98~1.0, or 1.0~2.4, 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 1.0~1.8, 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, or 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 1.3~1.3~2.4, 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 1.4~1.4~2.4, 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 1.4~2.0 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 1.5-1.5-1.7, 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 1.7~1.7~2.4, 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 1.8~2.3, or 1.8~2.1, or 1.8~2.0, or 1.8~2.0, or 1.8~2.0 The ranges are 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.

[0066] In one embodiment, or in combination with any other embodiment, class, or subclass of this third embodiment, DS Buis at least 0.2, or at least 0.3, or at least 0.4, or at least 0.5, or at least 0.6, or at least 0.7, or at least 0.8, or at least 0.9, or at least 1.0, or at least 1.1, or at least 1.2, or at least 1.3, or at least 1.4, or 0.18-0.23, or 0.18-0.22, or 0.18-0.21, or 0.18-0.20, or 0.18-0.19, or 0.19-0.23, or 0.19-0.22, or 0.19-0.21, or 0.19-0.2, or 0.2-0.23, or 0.2-0.22, or 0.2-0.21. Furthermore, or alternatively, DS Bu This is less than 1.5, or less than 1.4, or less than 1.3, or less than 1.2, or less than 1.1, or less than 1.0, or less than 0.9, or less than 0.8, or less than 0.7, or less than 0.5, or less than 0.4, or less than 0.3.

[0067] 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 0.2~1.35, 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, also 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, also 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.The ranges are 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, 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.

[0068] In one embodiment, or in combination with any other embodiment, class, or subclass of this third embodiment, DS OHThis is at least 0.6, or at least 0.7, or at least 0.8, or at least 0.9, or at least 1.0, or at least 1.1, or at least 1.2, or at least 1.3, or at least 1.4, or 0.5 to 0.95, or 0.5 to 0.93, or 0.5 to 0.91, or 0.5 to 0.9, or 0.5 to 0.85, or 0.5 to 0.80, or 0. 5~0.75, or 0.5~0.7, or 0.55~0.95, or 0.55~0.93, or 0.55~0.91, or 0.55~0.9, or 0.55~0.85, or 0.55~0.80, or 0.55~0.75, or 0.55~0.7, or 0.6~0.95, or 0.6~0.93, or 0.6~0.91, or 0.6~0.9, or 0.6~0.85, or 0 0.6~0.80, or 0.6~0.75, or 0.6~0.7, or 0.65~0.95, or 0.65~0.93, or 0.65~0.91, or 0.65~0.9, or 0.65~0.85, or 0.65~0.80, or 0.65~0.75, or 0.65~0.7, or 0.7~0.95, or 0.7~0.93, or 0.7~0.91, or 0.7~0.9, or 0.7~0.85, or 0.7~0.80, or 0.7~0.75, or 0.8~0.95, or 0.8~0.93, or 0.8~0.91, or 0.85~0.9, or 0.8~0.85, or 0.85~0.95, or 0.85~0.93, or 0.85~0.91, or 0.85~0.9, or 0.9~0.95, or 0.9~0.93, or 0.9~0.91. Furthermore, or alternatively, DS OH This is less than 2.8, less than 2.7, or less than 2.6, or less than 2.5, or less than 2.4, or less than 2.3, or less than 2.2, or less than 2.1, or less than 2.0, or less than 1.9, or less than 1.8, or less than 1.7, or less than 1.6, or less than 1.5, or less than 1.4, or less than 1.3, or less than 1.2, or less than 1.1, or less than 1.0, or less than 0.9, or less than 0.8.

[0069] In one embodiment, or in combination with any other embodiment, class, or subclass of this third embodiment, DS OH is 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 0.55~0.7, and also This is 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.

[0070] In one embodiment, or in combination with any other embodiment, class, or subclass of this third embodiment, DS Bu and DS Ac The 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.

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

[0073] In one embodiment, or in combination with any other embodiment, the mixed cellulose ester is cellulose acetate butyrate, or cellulose acetate butyrate, or a mixture thereof. In one class of this embodiment, the mixed cellulose ester is cellulose acetate butyrate. In one class of this embodiment, the mixed cellulose ester is cellulose acetate propionate. In one class of this embodiment, the mixed cellulose ester is a mixture comprising cellulose acetate butyrate or cellulose acetate propionate.

[0074] 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, 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, or at least 90% biodegradability in 56 days by at least one of the OECD 301B, OECD 301C, or OECD 301F test methods.

[0075] 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, 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, or at least 90% biodegradability, or at least 95% biodegradability, according to at least one of the OECD 301B, OECD 301C, or OECD 301F test methods after 60 days.

[0076] In one embodiment, or in combination with any other embodiment, class, or subclass of this third embodiment, the MCE has a weight-average molecular weight 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.

[0077] 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).

[0078] Solvent system A solvent system such as solvent 102 can generally solubilize CE to produce the dispersed / 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.

[0079] 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 acetate, C1-C4 alcohol, and water. The C1-C4 alkyl acetate may include one or more of methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, and sec-butyl acetate. The C1-C4 alcohol may 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).

[0080] In one embodiment or in combination with any embodiment referenced herein, if solvent 102 contains multiple solvent components, C1-C4 alkyl acetate may be present in one or more of the following amounts: (1) at least 10, or 25, 50, or 60, or 70 by weight percent; (2) 99, or 95, or 90, or 85, or 80 by weight percent or less; and (3) within the range of 10-99, or 25-95, or 50-90, or 70-85 by weight percent.

[0081] In one embodiment, or in combination with any embodiment referenced herein, if solvent 102 contains a plurality of solvent components, the C1-C4 alcohols are present in one or more of the following amounts: (1) at least 1, or 2, or 4, or 6, or 8, or 10 weight percent; (2) 80, or 60, or 40, or 30, or 20, or 15 weight percent or less; and (3) within the range of 1 to 80, or 2 to 60, or 4 to 40, or 6 to 30, or 8 to 20, or 10 to 15 weight percent.

[0082] 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, or 2, or 4, or 6, or 8 by weight percent; (2) 50, or 25, or 20, or 15 by weight percent or less; and (3) within the range of 1 to 50, or 2 to 25, 4 to 30, or 6 to 20, or 8 to 15 by weight percent.

[0083] In one embodiment, or in combination with any embodiment referenced herein, the 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 an amount ranging from 50 to 90, or 55 to 90, or 60 to 90, or 65 to 90, or 65 to 85, or 70 to 85, or 75 to 85 percent by weight; n-propanol is present in an amount ranging from 4 to 40, or 5 to 35, or 6 to 30, or 7 to 25, or 8 to 20, or 10 to 20, or 10 to 15 percent by weight; and water is present in an amount ranging from 4 to 30, or 5 to 25, or 6 to 20, or 7 to 15, or 8 to 12, or 9 to 12 percent by weight.

[0084] Surprisingly, water has been found to contribute to and / or enable the solubilization of certain mixed cellulose esters. In particular, water is found to be present in DS above a determined threshold.OH It has been found to contribute to, and / or enable, the solubilization of highly biodegradable mixed cellulose esters, such as those related to the value. These findings are disclosed in the following experimental section.

[0085] Hydrophilic colloid The 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 referenced herein, hydrophilic colloid 106 is a hydrophilic colloid. For example, hydrophilic colloid 106 may comprise at least one of gelatin, natural rubber, protein, or cellulose derivatives. Examples of cellulose derivatives include methylcellulose and carboxymethylcellulose, or both.

[0086] Hydrophilic colloids such as carboxymethylcellulose can be selected based on the desired viscosity of the resulting aqueous mixture. In combination with one embodiment or any embodiment referenced herein, "low" viscosity hydrophilic colloids have a viscosity in the range of 10 to 50 cps, "medium" viscosity hydrophilic colloids have a viscosity in the range of 400 to 800 cps, and "high" viscosity hydrophilic colloids have a viscosity in the range of 1500 to 3000 cps.

[0087] 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 may be distinguished from each other based on their hydrophilic-lipophilic equilibrium (HLB) number. For example, if the surfactant 108 comprises two individual emulsifiers, these emulsifiers may include a low-HLB emulsifier and a high-HLB emulsifier.

[0088] In one embodiment, or in combination with any embodiment referenced herein, the HLB number of the high HLB emulsifier is at least 6, or 8, or 10, or 12, or 14, or 16, or 18, and the HLB number of the low HLB emulsifier is 12, or 10, or 8, or 6, or 4 or less.

[0089] In one embodiment or in combination with any embodiment referenced herein, the HLB number of a high HLB emulsifier is greater than the HLB number of a low HLB emulsifier by at least one of the following: (1) at least 2, 4, 8, 10, 12, or 14; (2) 25, 20, or 15 or less; or (3) within the range of 2 to 25, 8 to 20, or 12 to 15.

[0090] 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.

[0091] 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 number greater than that of the low HLB emulsifier. In one embodiment, or in combination with any embodiment referenced herein, the third emulsifier is polyethylene glycerol ester of stearic acid.

[0092] If surfactant 108 is formed from all three emulsifiers, the low HLB emulsifier and the third emulsifier may be present in ratios of at least 0.25:1, or 0.5:1, or 0.75:1, or 1:1, or 1.25:1, or 1.5:1, or 1.75:1, or 2:1, and / or 5:1, or 4:1, or 3:1, or 2:1, or 1.75:1, or 1.5:1, or 1.25:1 or less. The low HLB emulsifier and the third emulsifier may define the combined emulsifier. Furthermore, high HLB emulsifiers and combined emulsifiers 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 5:1, 4:1, 3:1, 2:1, 1.75:1, 1.5:1, or 1.25:1 or less.

[0093] Referring here to Figure 2, the illustrated process for producing CE microbeads 112 includes the separate formation of CE dope 136 and aqueous mixture 138. Next, the CE dope 136 and aqueous mixture 138 are mixed to form CE microbeads 112. For example, the CE dope 136 may be formed in unit 140 and the aqueous mixture 138 may be formed in unit 142. The CE dope 136 and aqueous mixture 138 can then be combined in unit 144, as will be described in more detail below, to form an emulsion and / or dispersion.

[0094] In one embodiment, or in combination with any embodiment referenced herein, the CE dope 136 is formed from CE 100, solvent 102, water 104, and, in some embodiments, recycled solvent 146 derived from solvent-enriched flow 134.

[0095] In one embodiment, or in combination with any embodiment referenced herein, CE 100 is present in the CE dope in one or more of the following amounts: (1) at least 1, or 2, or 4, or 6, or 8, or 10 weight percent; (2) 80, or 60, or 40, or 30, or 20, or 15 weight percent or less; and (3) within the range of 1 to 80, or 2 to 60, or 4 to 40, or 6 to 30, or 8 to 20, or 10 to 15 weight percent.

[0096] In one embodiment, or in combination with any embodiment referred to herein, if the solvent 102 contains C1-C4 alkyl acetate, the C1-C4 alkyl acetate is present in CE dope 136 in one or more of the following amounts: (1) at least 10, 25, 50, 60, or 65 weight percent; (2) 95, or 90, or 85, or 80, or 75 weight percent or less; and (3) within the range of 10-95, or 25-90, or 50-85, or 65-75 weight percent.

[0097] In one embodiment, or in combination with any embodiment referenced herein, if the solvent 102 contains a C1-C4 alcohol, the C1-C4 alcohol is present in the CE-doped 136 in one or more of the following amounts: (1) at least 1, or 2, or 4, or 6, or 8 weight percent; (2) 50, or 25, or 20, or 15 weight percent or less; and (3) within the range of 1 to 50, or 2 to 25, or 4 to 30, or 6 to 20, or 8 to 15 weight percent.

[0098] In one embodiment, or in combination with any other embodiment, the solvent-to-CE ratio used in dissolving to form CE-doped 136 is at least 1:1, or 2:1, or 3:1, or 4:1, or 5:1, and / or 100:1, or 50:1, or 25:1, or 10:1 or less.

[0099] In one embodiment, or in combination with any embodiment referenced herein, if the solvent 102 contains water, the water is present in the CE-doped 136 in one or more of the following amounts: (1) at least 0.5, or 1, or 2, or 4, or 6 weight percent; (2) 40, or 25, or 15, or 10 weight percent or less; and (3) within the range of 0.5 to 40, or 1 to 25, or 2 to 15, or 4 to 20, or 6 to 10 weight percent.

[0100] In one particular embodiment, the CE-doped 136 is formed from CE 100, a solvent 102 containing ethyl acetate and n-propanol, and water 104. In such embodiments, CE is present in the CE-doped 136 in amounts ranging from 6 to 30, or 7 to 25, or 8 to 20, or 9 to 20, or 10 to 15, or 12 to 15 weight percent; ethyl acetate is present in the CE-doped 136 in amounts ranging from 50 to 85, or 55 to 85, or 60 to 85, or 65 to 85, or 70 to 85, or 75 to 85 weight percent; n-propanol is present in the CE-doped 136 in amounts ranging from 4 to 30, or 6 to 25, or 8 to 20, or 10 to 20, or 12 to 15 weight percent; and water is present in the CE-doped 136 in amounts ranging from 4 to 20, or 5 to 18, or 6 to 16, or 7 to 14, or 8 to 12 weight percent.

[0101] In one embodiment, or in combination with any embodiment referenced herein, CE100, solvent 102, and water 104 are combined 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, or 20, or 25, or 30°C and / or 45, or 40, or 35, or 30, or 25, or 20°C or less) for a duration of at least 1, or 2, or 5, or 10, or 15, or 20, or 25, or 30, or 45, or 60, or 120, or 240 minutes and / or for the length of time required to produce a substantially homogeneous mixture.

[0102] In one embodiment, or in combination with any embodiment referenced herein, the aqueous mixture 138 is formed from water 104, a hydrophilic colloid 106, a surfactant 108, and, in some embodiments, a recycled solvent 146 derived from the solvent-enriched flow 134. Optionally, additional solvent 148 may be added to units 140 and / or 142 as needed to maintain the concentration(s) of the solvent component at a preferred level.

[0103] In one embodiment, or in combination with any embodiment referenced herein, the ratio of the recycled solvent portion to the fresh solvent portion used in the unit 140 and / or 142 is at least 2.5:1, or 10:1, 25:1, 50:1, 75:1, 90:1, 95:1, or 99:1 by weight, and / or 1000:1, 500:1, 200:1, or 100:1 or less by weight.

[0104] In one embodiment, or in combination with any embodiment referenced herein, the composition of the recycled solvent differs from the composition of the fresh solvent by a total of 10, 5, 2, or 1 weight percent.

[0105] In one embodiment, or in combination with any embodiment referenced herein, the fresh solvent and recycled solvent portions have substantially the same composition.

[0106] 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 percent by weight; (2) 99, 97, 95, 94, or 92 percent by weight or less; and (3) in the range of 40 to 99, 70 to 95, or 85 to 92 percent by weight.

[0107] 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, or 0.005, or 0.01, or 0.05, or 0.1 weight percent; (2) 15, or 10, or 5, or 2, or 1 weight percent or less; and (3) within the range of 0.001 to 15, or 0.01 to 5, or 0.1 to 2 weight percent.

[0108] 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, or 0.01, or 0.05, or 0.1, or 0.5 weight percent; (2) 15, or 10, or 5, or 2, or 1.5 weight percent or less; and (3) within the range of 0.005 to 15, or 0.05 to 5, or 0.5 to 1.5 weight percent.

[0109] 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 high-low HLB emulsifier ratio of at least 0.25:1, or within the range of 0.5:1, 1:1, 1.5:1, or 1.75:1, and / or 10:1, 5:1, 3:1, or 2.5:1 or less, and / or within the range of 0.25:1 to 10:1, 0.5:1 to 5:1, or 1:1 to 3:1.

[0110] Referring again to Figure 2, in some embodiments, an additional solvent 148 and / or recycled solvent 146 are received in unit 142. In such embodiments, the solvent used to form the CE-doped 136 and aqueous mixture 138 is a common C1-C4 alkyl acetate. The use of at least one common component in the solvent systems received in units 140 and 142 facilitates the simplification of solvent separation, recovery, and reuse as described herein.

[0111] 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 weight percent; (2) 50, 40, 30, 20, or 15 weight percent or less; and (3) within the range of 1-50, 2-40, or 6-20 weight percent.

[0112] In one embodiment, or in combination with any embodiment referenced herein, C1-C4 alkyl acetate is present in aqueous mixture 138 in weight percent of C1-C4 alkyl acetate in water at 20°C, with solubility not exceeding 25, 20, 15, 10, 5, or 2 weight percent.

[0113] 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 of 2-25, 4-20, 6-15, or 8-10 weight percent. 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 5-50, 10-40, 15-35, or 10-30 weight percent.

[0114] In one particular embodiment, the aqueous mixture 138 is formed 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 weight percent; 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 weight percent; 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 weight percent; and C1-C4 alkyl acetate is 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 weight percent.

[0115] 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 combined 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 100, 75, 50, 40, 35, 30, 25, or 20°C or lower, for a duration of at least 1, 2, 5, 10, 15, 20, 25, 30, 45, 60, 120, or 240 minutes, and / or for a length of time required to produce a substantially homogeneous mixture, depending on the viscosity of the hydrophilic colloid used.

[0116] Formation of emulsions / dispersions Once formed, the CE dope 136 and aqueous mixture 138 can be combined in unit 144 to produce the emulsion and / or dispersion described above.

[0117] In one embodiment, or in combination with any embodiment referenced herein, the ratio of CE dope 136 to aqueous mixture 138 combined in unit 144 to form an initial emulsion 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.

[0118] In one embodiment, or in combination with any embodiment referenced herein, the initial emulsion contains at least 10, 20, 30, 40, 50, or 60 percent by weight of water and / or no more than 90, 80, 70, 60, 50, or 40 percent by weight of water.

[0119] Once combined, 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 electronic), and film emulsion formation.

[0120] In one embodiment, or in combination with any embodiment referenced herein, the CE dope and aqueous mixture are recirculated through a high-shear mixer to disperse the solid phase into the liquid phase, accelerate the hardening of the solid phase, and generate initial fine particles. This shearing may occur as the CE dope 136 and aqueous mixture 138 are supplied to unit 144, and / or after a predetermined amount of CE dope 136 and aqueous mixture 138 have entered unit 144.

[0121] In one embodiment, or in combination with any embodiment referenced herein, the combined CE dope and aqueous mixture are recirculated through a high-shear mixer (based on the total volume of the high-shear mixer used) for at least 1, 2, 3, 4, or 5 residence times and / or 20, 15, 10, 9, or 8 residence times or less. Furthermore, the high-shear mixing is performed for a duration of at least 1, 2, 5, 10, 15, 20, 25, 30, 45, 60, 120, or 240 minutes and / or for the length of time necessary to recirculate the volume of the mixture for its predetermined residence time.

[0122] To generate initial fine particles that form CE microbeads as described herein, the combined CE dope and aqueous mixture is stirred in unit 144. The stirring performed in unit 144 can be quantified by at least one of the following: (1) impeller tip velocity, (2) impeller Reynolds number, and (3) power-to-mass ratio. In one embodiment, or in combination with any embodiment referenced herein, high-shear mixing is performed at impeller tip velocities of at least 25, 50, 75, 100, 150, 200, 250, or 300 cm / s and / or 1000, 500, 400, 300, 200, or 100 cm / s 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 15000, 10000, 8000, 6000, 5000, 4000, or 3000. In one embodiment, or in combination with any embodiment referenced herein, high shear mixing is performed at power-to-mass ratios 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 10.0, 7.5, 5.0, 4.0, 3.0, 2.5, 2.0, 1.5, 1.0, 0.5, or 0.1 or less.

[0123] As used herein, terms such as “solid,” “solid phase,” “particle,” and “fine particles” refer to semi-solid materials that retain their discrete properties (i.e., flow together) when the surrounding aqueous / continuous phase is removed.

[0124] Hardening by extractant A pre-cured dispersion 150 formed in unit 144 and containing initial particles (i.e., solid phase) is led to a curing unit 152, where the initial particles can be converted into cured CE microbeads 112. In unit 152, the initial particles contained within the pre-cured dispersion 150 are contacted with an extractant 154 (i.e., a drafting solution) to produce a cured dispersion 156. That is, the contact step facilitates the desolvation of the initial particles and their curing into CE microbeads. In one embodiment, or in combination with any embodiment referenced herein, the extractant is water. Alternatively, the extractant may be methanol, ethanol, or a combination thereof.

[0125] In one embodiment, or in combination with any embodiment referenced herein, the pre-cured dispersion and the extractant are mixed in unit 152 in an extractant-to-dispersion weight ratio of at least 0.5:1, 1:1, 1.5:1, 2:1, or 1.5:1 and / or 10:1, 8:1, 6:1, 4:1, or 3:1 or less.

[0126] In one embodiment, or in combination with any embodiment referenced herein, the weight ratio of extractant to pre-cured particles used in the contact step is at least 2:1, 5:1, 10:1, 20:1, 30:1, or 40:1, and / or 200:1, 100:1, 80:1, 60:1, or 50:1 or less.

[0127] As a result, in one embodiment, or in combination with any embodiment referred to herein, the cured dispersion 156 contains one or more of the following amounts of water: (1) at least 25, 50, 60, 70, 80, 85, or 90 weight percent; (2) 99, 97.5, 95, 92.5, 90, 80, 70, 60, or 50 weight percent or less; and (3) one or more of the following amounts of water: within the range of 50-99, 70-95, or 80-92.5 weight percent.

[0128] In one embodiment, or in combination with any embodiment referenced herein, the cured dispersion 156 has water at a weight concentration of at least 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5 times more and / or 100 times, 70 times, 50 times, 25 times, 15 times, 10 times, 5 times, or 2.5 times more than the weight concentration of water in the initial emulsion.

[0129] In one embodiment, or in combination with any embodiment referenced herein, the curing of the fine particles is carried out under agitation. The agitation carried out in unit 152 can be quantified by at least one of the following: (1) impeller tip velocity, (2) impeller Reynolds number, and (3) power-to-mass ratio. In one embodiment, or in combination with any embodiment referenced herein, the conversion / curing is carried out at an impeller tip velocity of at least 25, 50, 75, 100, 150, 200, 250, or 300 cm / s and / or 1000, 500, 400, 300, 200, or 100 cm / s or less. In one embodiment, or in combination with any embodiment referenced herein, conversion / curing is performed at impeller Reynolds numbers of at least 500, 1000, 1500, 2000, 3000, 4000, 5000, or 6000, and / or 15000, 10000, 8000, 6000, 5000, 4000, or 3000 or less. In one embodiment, or in combination with any embodiment referenced herein, conversion / curing is performed at power-to-mass ratios 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 10.0, 7.5, 5.0, 4.0, 3.0, 2.5, 2.0, 1.5, 1.0, 0.5, or 0.1 or less.

[0130] Furthermore, the conversion / curing is carried out for a period of at least 0.1, 0.5, 1, 2, 4, 6, 8, 10, or 20 minutes, and / or for no more than 12, 8, 6, 4, or 2 hours, and at a temperature of at least 0, 5, or 10°C and / or no more than 100, 75, 50, or 25°C.

[0131] In one embodiment, or in combination with any embodiment referred to herein, the conversion / curing is carried out in a single container or in multiple containers. Multiple containers may be required depending on the yield of CE microbeads to be manufactured and the volume of available containers used for curing. In embodiments in which multiple containers are used, a first portion of the pre-cured dispersion 150 may be received in a first curing unit, and a second portion of the pre-cured dispersion may be received in a second curing unit. Flow communication may then be provided between the separate curing units to facilitate mass transfer so as to accelerate the desolvation of the initial particles.

[0132] In one embodiment, or in combination with any embodiment referenced herein, the pre-cured dispersion 150 has a solids content of at least 0.5, 1, 2, 3, or 4 and / or 40, 30, 20, 10, or 6 by weight percent.

[0133] As a result of curing, in one embodiment, or in combination with any embodiment referenced herein, the cured dispersion 156 has a solids content of at least 0.05, 0.1, 0.5, or 1 weight percent, and / or 20, 10, 5, 2, or 1 weight percent or less.

[0134] In one embodiment, or in combination with any embodiment referenced herein, the solids content of the pre-cured dispersion is at least 1.5, 2, 3, or 4 times, and / or 20, 10, 8, or 6 times, than the solids content of the cured dispersion. In other words, in unit 152, the solvent is extracted from the initial microparticles to produce a cured dispersion 156 containing cured CE microbeads 112 and a drafting solution containing the solvent.

[0135] Isolation / Separation of CE Microbeads The CE microbeads 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 referred to herein, isolation may be performed by at least one, at least two, or all three of the following: (1) flushing one or more liquid components from the cured CE microbeads; (2) filtering the cured CE microbeads away from one or more liquid components; and (3) centrifuging, redispersing, and drying the cured microbeads.

[0136] The processing of solids and / or the isolation of CE microbeads may be carried out in a single unit, as shown in Figure 1, or in multiple units, as shown in Figure 2. As shown in 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 microbeads and residual liquid. In one embodiment, or in combination with any embodiment referenced herein, the wet solids flow 160 has a solids content of at least 10, 20, 25, 30, 35, 40, or 45 weight percent and / or 60, 65, 50, 45, or 40 weight percent or less. This allows the wet solids flow 160 to be transported to downstream units with reduced concerns about blockage and processing.

[0137] Next, the wet solids flow 160 may optionally be processed in a washing unit 164 and a second solids / liquid separation unit 166. In unit 164, the cured CE microbeads are washed with water 122 to produce a washed solids flow 168. The washed solids flow 168 is then processed in unit 166 by at least one, at least two, or all three of the following: (1) flushing one or more liquid components from its cured CE microbeads; (2) filtering the cured CE microbeads to remove them from one or more liquid components; and (3) centrifuging, redispersing, and drying the cured microbeads. This second solids / liquid separation step facilitates a reduction in the solvent content in the liquid surrounding the cured CE microbeads.

[0138] The washing solution 130 is recovered from the second solids / liquid separation step and can then be recycled for use as at least part of the aqueous mixture in unit 142 and / or for use as at least part of the drafting solution in unit 152.

[0139] In one embodiment, or in combination with any embodiment referenced herein, at least 1, 5, or 10 weight percent and / or 90, 50, 20, or 10 weight percent or less of the aqueous mixture 138 is the recycled cleaning solution.

[0140] In one embodiment, or in combination with any embodiment referenced herein, at least 1, 5, or 10 weight percent and / or 90, 50, 20, or 10 weight percent or less of the drafting fluid 154 used in unit 152 is recycled cleaning fluid.

[0141] The wet solid material 172 discharged from unit 166 is then received by drying unit 170. In one embodiment or in combination with any embodiment described herein, drying is carried out by applying heat while agitating in unit 170. Such agitation promotes the reduction of aggregation of the recovered CE microbeads 112. The properties of the recovered CE microbeads 112 are described in further detail below.

[0142] In one embodiment, or in combination with any embodiment referenced herein, the drying unit 170 is a rotary cone dryer.

[0143] Liquid treatment and recycling The separated mother liquor stream 162 discharged from unit 164 can be treated to recover water and / or solvent. The recovered water and / or solvent can then be recycled into one or more of the units shown in Figure 2 to enhance the economic efficiency of the microbead formation process described herein.

[0144] 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. As shown in 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 include residual amounts of hydrophilic colloid, surfactant, and any components used to produce the mixed cellulose ester.

[0145] The mother liquor flow 162 is heated (174) and then separated in unit 176 into at least two separate flows, such as a solvent-enriched flow 134 and a water-enriched (solvent-depleted) flow 132. The mother liquor flow 162 may be separated in unit 176 using any suitable technique. In one embodiment, or in combination with any embodiment described herein, the separation of liquids may be carried out by distillation or the like.

[0146] In one embodiment, or in combination with any embodiment referenced herein, the water enrichment flow 132 comprises one or more of the following: (1) water, (2) surfactant, (3) hydrophilic colloid, and (4) C1-C4 alkyl acetate.

[0147] Therefore, the water enrichment flow 132 can be cooled (181) and then recycled into one or more units shown in Figure 2. For example, the composition of the water enrichment flow 132 allows it to be recycled into at least one of the units 142 as a flow 178 for use in forming an aqueous mixture 138, and / or into unit 152 as a flow 180 for use in desolvating initial particulate matter, thereby reducing the amount of water required for such processes. Any excess not needed by these processes may be purged from the system and used, for example, for wastewater treatment.

[0148] In one embodiment or in combination with any embodiment referenced herein, the ratio of recycled water in the flow 180 used in the curing step to recycled water in the flow 178 used in forming the aqueous mixture 138 is at least 1:1, 1.5:1, 2:1, 3:1, 4:1, and / or 20:1, 10:1, 8:1, or 6:1 or less.

[0149] In one embodiment or in combination with any embodiment referenced herein, the ratio of recycled water to purged water in the flow 180 used in the curing step is at least 1:1, 1.5:1, 2:1, 3:1, 4:1, and / or 20:1, 10:1, 8:1, or 6:1 or less.

[0150] In one embodiment or in combination with any embodiment referenced herein, at least 75, 90, 95, 98, 99, or 100 percent by weight of the extractant used in unit 152 is recycled water recovered downstream from unit 152, for example, water contained in the water enrichment flow 132 that is recycled to unit 152.

[0151] In one embodiment, or in combination with any embodiment referenced herein, freshwater 154 is added to unit 152 for use in the curing step.

[0152] In one embodiment or in combination with any embodiment described herein, the ratio of the total amount of fresh water added to the purge water is at least 0.25:1, 0.5:1, 0.75:1, or 0.9:1, and / or 4:1, 2:1, 1.5:1, 1.25:1, or 1.1:1 or less.

[0153] In one embodiment, or in combination with any embodiment referenced herein, the solvent-enriched flow 134 comprises one or more of (1) C1-C4 alkyl acetate; (2) C1-C4 alcohol; and (3) water.

[0154] Therefore, the solvent-enriched stream 134 can be recycled into one or more units shown in Figure 2. For example, depending on the composition of the solvent-enriched stream 134, it can be recycled into at least one of the units 140 for use as part of the solvent in the formation of the CE-doped 136, and / or into unit 142 for use in the formation of the aqueous mixture 138. Any excess material not needed in these processes can be purged from the system.

[0155] In one embodiment, or in combination with any embodiment referenced herein, at least 75, 90, 95, 98, 99, or 100 percent by weight of the solvent used in the unit 140 used to form the CE dope 136 is recycled solvent 146.

[0156] In one embodiment, or in combination with any embodiment referenced herein, freshwater 104 is added to unit 142 for use in forming an aqueous mixture 138.

[0157] In one embodiment, or in combination with any embodiment referenced herein, the ratio of the total amount of water in streams 178 and 180 to the total amount of added fresh water 104 in unit 142 is at least 2:1, 4:1, 6:1, or 8:1.

[0158] 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 acetate, and / or an azeotropic mixture of water and C1-C4 alcohol, derived from the water-enriched flow 132.

[0159] Hydroxyl is generally a strong hydrogen bonding agent. 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 carbon number (i.e., C1-C4) increases. Therefore, a low carbon number binary solvent system without water is more suitable for DS 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 [a certain characteristic] could not be dissolved. Therefore, it was found that the dissolution of the mixed CE described herein into the solvent system is promoted when a strong hydrogen bonding agent (i.e., water) that is essentially sterically unhindered is present in a solvent system containing a high-carbon alcohol.

[0160] In one embodiment, or in combination with any embodiment referenced herein, the recycled solvent 146 contains at least 1, 2, 4, 6, or 8 weight percent, and / or 50, 40, 30, 20, or 10 weight percent or less of water.

[0161] In one embodiment, or in combination with any embodiment referenced herein, the recycled solvent 146 contains at least one azeotropic mixture, the azeotropic mixture containing water and another component.

[0162] In one embodiment, or in combination with any embodiment referenced herein, the azeotrope may be 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.

[0163] In one embodiment, or in combination with any embodiment referenced herein, the recycled solvent 146 contains a plurality of azeotropes. In one embodiment, or in combination with any embodiment referenced herein, the plurality of azeotropes contains a plurality of binary azeotropes. In one embodiment, or in combination with any embodiment referenced herein, the components of the solvent system are selected so that the recycled solvent 146 does not contain any ternary azeotropes, thereby simplifying the recovery and recycling of the solvent.

[0164] In one embodiment, or in combination with any embodiment referenced herein, the solvent-enriched stream 134 contains a ternary azeotrope in an amount of less than 10% by weight, less than 1% by weight, less than 0.1% by weight, or 0.0% by weight.

[0165] 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.

[0166] Additional Embodiments Referring here to Figure 3, the CE microbeads 112 are produced by serial particle formation. In an exemplary embodiment, particle formation begins in unit 142, in which water 104, hydrophilic colloid 106, surfactant 108, and, in some embodiments, recycled solvent 146 derived from solvent-enriched flow 134 are combined to form an aqueous mixture 138.

[0167] The aqueous mixture 138 is discharged from unit 142 and received in dispersion forming unit 182. In unit 182, the aqueous mixture 138 is mixed with CE 100, solvent 102, and optionally, recycled solvent 146 derived from solvent enrichment flow 134. Thus, rather than forming the CE dope 136 and aqueous mixture 138 in separate units, the aqueous mixture 138, CE 100, and solvent 102 are combined in a common unit to form the initial emulsion.

[0168] 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 combined CE dope and aqueous mixture is recirculated through a high-shear mixer to disperse the solid phase into the liquid phase of the initial emulsion, thereby accelerating the hardening of the solid phase and generating initial fine particles.

[0169] To generate initial fine particles, the combined aqueous mixture 138, CE100, and solvent 102 are stirred in unit 182. The stirring performed in unit 182 can be quantified by at least one of the following: (1) impeller tip velocity, (2) impeller Reynolds number, and (3) power-to-mass ratio. In one embodiment, or in combination with any embodiment referenced herein, high-shear mixing is performed at impeller tip velocities of at least 25, 50, 75, 100, 150, 200, 250, or 300 cm / s and / or 1000, 500, 400, 300, 200, or 100 cm / s 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 15000, 10000, 8000, 6000, 5000, 4000, or 3000. In one embodiment, or in combination with any embodiment referenced herein, high shear mixing is performed at power-to-mass ratios 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 10.0, 7.5, 5.0, 4.0, 3.0, 2.5, 2.0, 1.5, 1.0, 0.5, or 0.1 or less.

[0170] Next, the pre-cured dispersion 150 is discharged from unit 182, and the cured CE microbeads 112 are recovered therefrom as described above.

[0171] Referring to Figure 4, the CE microbeads 112 are produced by a combination of separated dope and aqueous mixture formation, as well as emulsion / dispersion formation and particle curing. In an exemplary embodiment, particle formation begins as shown in Figure 2, at which point the CE dope 136 and aqueous mixture 138 are formed as separate units.

[0172] In Figure 4, however, the CE dope 136 and aqueous mixture 138 are supplied to a common emulsion / dispersion forming and particle curing unit 184. In unit 184, the CE dope 136 and aqueous mixture 138 are combined and stirred to form an initial emulsion as described herein. Once the initial emulsion is formed, the extractant 154 is supplied directly to unit 184 to desolvate the initial particles.

[0173] Referring to Figure 5, the CE microbeads 112 are produced by emulsion / dispersion composite formation. 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 microparticles. The pre-cured dispersion is received in unit 152, and the initial microparticles are desolvented as described herein.

[0174] Referring to Figure 6, the CE microbeads 112 are produced by a combination of emulsion / dispersion formation and particle hardening. In an exemplary embodiment, particle formation is initiated by mixing all of the following in a common unit 188: CE 100, solvent 102, water 104, hydrophilic colloid 106, surfactant 108, and optionally recycled solvent 146 and recycled water 178. In unit 188, these components are combined and stirred to form an initial emulsion as described herein. Once the initial emulsion is formed, the extractant 154 is supplied directly to unit 188 to desolvate the initial microparticles.

[0175] Referring to Figure 7, the CE microbeads 112 are generated by solvent flushing prior to particle curing. In an exemplary embodiment, the pre-cured dispersion 150 discharged from unit 144 is received in the flash unit 190, rather than in the particle curing unit 152. In unit 144, at least a portion of the solvent in the pre-cured dispersion 150 is removed from its liquid phase, thereby forming a solvent-depleted dispersion 192 with reduced solvent content. The solvent-depleted dispersion 192 is received in unit 152, where the pre-cured particles contained therein are cured as described above. The flash solvent stream 194 discharged from unit 190 is led to unit 176 for liquid processing and recycling.

[0176] In one embodiment, or in combination with any embodiment referred to herein, removal in unit 144 is performed by permeate evaporation, cross-flow membrane filtration (ultrafiltration or nanofiltration), flashpot, spraypot, or wiped film evaporation.

[0177] In one embodiment, or in combination with any embodiment referenced herein, the removal in unit 144 reduces the solvent in the dispersion by at least 30 weight percent, at least 50 weight percent, at least 75 weight percent, at least 90 weight percent, 30 to 90 weight percent, or 50 to 75 weight percent.

[0178] In one embodiment, or in combination with any embodiment referenced herein, the solvent-depleted dispersion 192 has a solids content of at least 3, 4, 5, or 6 weight percent, and / or 40, 30, 20, or 10 weight percent or less.

[0179] In one embodiment, or in combination with any embodiment referenced herein, the volume ratio of the drowning fluid to the dispersion used in unit 152 is 2.5:1, 2:1, 1.75:1, 1.5:1, 1.25:1, or less than 1.1.

[0180] Cured or jet-milled CE microbeads The cured or jet-milled CE microbeads 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. Where used herein, the terms “fine particles, microparticles,” “beads,” and “microbeads” may be used synonymously with the terms “cured CE microbeads” or “jet-milled CE microbeads.”

[0181] In one embodiment, or in combination with any embodiment referenced herein, CE microbeads are produced at rates of at least 50, 100, 250, 500, 1000, 2500, 5000, or 10000 kg / day and / or at rates of 100000, 75000, 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.

[0182] In one embodiment, or in combination with any embodiment referenced herein, the CE is supplied to unit 140 at speeds of at least 50, 100, 250, 500, 1000, 2500, 5000, or 10000 kg / day and / or at speeds of 100000, 75000, or 50000 kg / day or less.

[0183] 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 no more than 100000, 75000, or 50000 kg / day.

[0184] In one embodiment, or in combination with any embodiment referenced herein, water is supplied to unit 152 at a rate of at least 50, 100, 250, 500, 1000, 2500, 5000, or 10000 kg / day and / or no more than 100000, 75000, or 50000 kg / day.

[0185] In one embodiment, or in combination with any embodiment referenced herein, the cured CE microbeads have a hardness at 20°C greater than the hardness at 20°C of initial fine particles contained in and / or formed by any process described herein.

[0186] In one embodiment, or in combination with any embodiment referenced herein, the cured CE microbeads have a hardness of at least 1.1, 1.25, 1.5, 1.75, or 2 times that of the initial microparticles.

[0187] In one embodiment, or in combination with any embodiment referenced herein, the cured CE microbeads have a solvent content of less than 100, 50, 25, or 10 ppm.

[0188] In one embodiment, or in combination with any embodiment referred to herein, the cured or jet-milled CE microbeads have a solvent content lower than that of the initial fine particles.

[0189] In one embodiment, or in combination with any embodiment referenced herein, the cured or jet-milled CE microbeads have a solvent content of less than 0.99, 0.95, 0.9, 0.8, 0.7, 0.6, or 0.5 ppm of the solvent content of the initial fine particles.

[0190] In one embodiment, or in combination with any embodiment referenced herein, the cured or jet-milled CE microbeads have a solvent content that is at least 1, 2, 4, 8, 12, 16, or 20 weight percent less than the solvent content of the initial fine particles.

[0191] In one embodiment, or in combination with any embodiment referenced herein, the cured or jet-milled CE microbeads have a D50 volume-based particle size that is within 50, 25, 15, 10, 5, or 2 percent of the D50 particle size of the initial fine particles.

[0192] In one embodiment, or in combination with any embodiment referenced herein, the cured or jet-milled CE microbeads have a D50 volume-based particle size of less than 0.99, 0.95, 0.9, 0.8, 0.7, 0.6, or 0.5 of the initial fine particles.

[0193] In one embodiment, or in combination with any embodiment referenced herein, cured or jet-milled CE microbeads are available in the following counts: 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, 5~15 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, 20-100, 20-80, 20- The particles have a D50 volume-based particle size in the range of 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, hardened or jet-milled CE microbeads may have D50 volume-based particle sizes 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.

[0194] As used herein, the term “D50 volume-based” means that, on a volume basis, 50% of the beads have a maximum dimension of no more than the stated value (e.g., 10 microns). The D50 value may also be treated as the median particle size. To ensure that a representative D50 value is obtained, the sample size of beads should be at least 0.5 grams. The sample size of microbeads is then dispersed and mixed in 1.5 ounces of an aqueous solution of isopropanol or surfactant (one drop of 5% (v / v) IgePal® CO-630 surfactant). 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 obscuration rate may be set to 2% to 5%, and the sample measurement time should be set to 3 seconds for both red and blue light measurements. The dispersed sample is added until the desired obscuration 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. Subsequently, once the light energy has stabilized after sonication (usually less than 1 minute), the dispersed sample is measured again.

[0195] In one embodiment, or in combination with any embodiment referenced herein, cured or jet-milled CE microbeads have a D10 volume-based particle size of 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, hardened or jet-milled CE microbeads may have D10 volume-based particle sizes 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.

[0196] As used herein, the term “D10 volume-based” means that, based on volume, 10% of the beads have a maximum dimension of no more than the stated value (e.g., 10 microns). To ensure that a representative D10 value is obtained, the sample size of beads should be at least 0.5 grams. The sample size of microbeads is then dispersed and mixed in 1.5 ounces of an aqueous solution of isopropanol or surfactant (one drop of 5% (v / v) IgePal® CO-630 surfactant). 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 obscuration rate may 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 obscuration 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. Subsequently, once the light energy stabilizes after sonication (usually less than 1 minute), the dispersed sample is measured again.

[0197] In one embodiment, or in combination with any embodiment referenced herein, cured or jet-milled CE microbeads are 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, 1 The particles have a D90 volume-based particle size in the range of 0-20, 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, hardened or jet-milled CE microbeads may have D90 volume-based particle sizes 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.

[0198] As used herein, the term “D90 volume-based” means that, based on volume, 90% of the beads have a maximum dimension of no more than the stated value (e.g., 10 microns). To ensure that a representative D90 value is obtained, the sample size of the beads should be at least 0.5 grams. The sample size of microbeads is then dispersed and mixed in 1.5 ounces of an aqueous solution of isopropanol or surfactant (one drop of 5% (v / v) IgePal® CO-630 surfactant). 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 obscuration rate may 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 obscuration 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. Subsequently, once the light energy stabilizes after sonication (usually less than 1 minute), the dispersed sample is measured again.

[0199] In one embodiment, or in combination with any embodiment referenced herein, cured or jet-milled CE microbeads are divided into 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, and 10 The particles have a D100 volume-based particle size in the range of ~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, hardened or jet-milled CE microbeads may have D100 volume-based particle sizes 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.

[0200] As used herein, the term “D10 volume-based” means that, based on volume, 100% of the beads have a maximum dimension of no more than the stated value (e.g., 10 microns). To ensure that a representative D100 value is obtained, the sample size of the beads should be at least 0.5 grams. The sample size of the microbeads is then dispersed and mixed in 1.5 ounces of an aqueous solution of isopropanol or surfactant (one drop of 5% (v / v) IgePal® CO-630 surfactant). The D100 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 D100 value is the Malvern Mastersizer 3000 from Malvern Panalytical. When using the Malvern Mastersizer, the obscuration rate may 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 obscuration 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. Subsequently, once the light energy stabilizes after sonication (usually less than 1 minute), the dispersed sample is measured again.

[0201] In one embodiment, or in combination with any embodiment referred to herein, the cured or jet-milled CE microbeads are in a quantity of at least 10, or at least 20, or at least 30, or at least 40, or at least 50, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 96, or at least 97, or at least 98, or 20-100, or 20-90, or 20-80, and It has an average sphericity of 20-70, or 20-60, or 30-100, or 30-90, or 30-80, or 30-70, or 30-60, or 40-100, or 40-90, or 40-80, or 40-70, or 40-60, or 50-100, or 50-90, or 50-80, or 50-70, or 50-60, or 60-100, or 60-90, or 60-80, or 60-70, or 70-100, or 70-90, or 70-80, or 80-100, or 80-90, or 90-100 percent. Furthermore, or alternatively, cured or jet-milled CE microbeads may have an average sphericity of 99, 95, 90, 80, 70, 60, 50, 40, or 30 percent or less.

[0202] 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 microbeads; (2) selecting a square sample window centered on the SEM containing exactly 30 microbeads whose entire circumference is clearly visible (i.e., not blocked) on this SEM image; (3) measuring the maximum and minimum diameters of the 30 clearly visible microbeads within this sample window (each extended through the center of gravity of the particle and 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.

[0203] In one embodiment, or in combination with any embodiment referenced herein, the cured or jet-milled CE microbeads exhibit a unimodal particle size distribution having spans of at least 0.5, at least 0.55, at least 0.60, at least 0.65, at least 0.70, at least 0.75, at least 0.80, at least 0.85, at least 0.9, at least 0.95, at least 1.0, at least 1.05, at least 1.1, at least 1.15, at least 1.2, or at least 1.25. In one embodiment, or in combination with any embodiment referenced herein, the cured or jet-milled CE microbeads 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 3.0, 2.9, 2.8, 2.7, 2.6, 2.5, 2.4, 2.3, 2.2, 2.1, 2.0, 1.9, 1.8, less than 1.7, 1.6, or 1.5. In certain embodiments, cured or jet-milled CE microbeads exhibit a unimodal particle size distribution with 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 one prominent peak in its size distribution. This is in contrast to a multimodal particle size distribution, which has two or more peaks in its particle size distribution. The “span” of a unimodal peak can be measured using the following formula, with respect to the D10, D50, and D90 values ​​of the particles. (D x (90)-D x (10)) / D x (50) In the formula, "x" is the specified particle size.

[0204] In one embodiment, or in combination with any embodiment referenced herein, cured or jet-milled CE microbeads have an average smoothness of at least 10, 20, 30, 40, 50, 60, 70, 80, 90, 95, 95, 97, 98, or 99 percent. Furthermore, or alternatively, cured or jet-milled CE microbeads may have an average smoothness of 99, 95, 90, 80, 70, 60, 50, 40, or 30 percent or less.

[0205] 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 microbeads, (2) selecting a square sample window centered on the SEM center containing exactly 10 microbeads whose entire periphery is clearly visible (i.e., not blocked), (3) binarizing the sample window by manual binarization with upper and lower thresholds selected to match the precise shape of the dark region of the particles, (4) for each of the 10 microbeads, selecting a square window in which the length and width of the center of the particle or near it is approximately 1 / 3 of the particle diameter (before binarizing the particle), (5) obtaining the smoothness of the 10 individual particles by dividing the dark region area within the square window by the total area of ​​the square window and multiplying the result by 100%, and (6) averaging the smoothness of these 10 individual particles to obtain the average smoothness.

[0206] In one embodiment, or in combination with any embodiment referred to herein, cured or jet-milled CE microbeads, when measured by ISO9277 using Micromeritics ASAP 2020 equipment 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, 4.9, 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 8.0m 2 / g, and / or 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2.5, 2, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, or 1.3m 2 It has an average betting surface area of ​​less than / g.

[0207] In one embodiment, or in combination with any embodiment referenced herein, cured or jet-milled CE microbeads have a BET average pore diameter of at least 25, 30, 35, 40, 45, 50, 55, 56, 57, 58, or 59 angstroms and / or less than 75, 70, 65, or 60 angstroms, as measured according to ISO9277 and ISO15901-02 using Micromeritics ASAP 2020 equipment and nitrogen gas.

[0208] In one embodiment, or in combination with any embodiment referenced herein, cured or jet-milled CE microbeads have a BJH average pore diameter of at least 50, 60, 70, 80, 90, 100, 110, 120, 125, or 130 angstroms and / or less than 200, 190, 180, 170, 160, 150, 140, or 130 angstroms, as measured according to ISO 15901-02 using Micromeritics ASAP 2020 equipment and nitrogen gas.

[0209] In one embodiment, or in combination with any embodiment referenced herein, cured or jet-milled CE microbeads, when measured according to ISO 15901-02 using Micromerics ASAP 2020 equipment and nitrogen gas, have a density of at least 0.5, 1.0, 1.1, 1.2, 1.3, 1.4, or 1.5 and / or 2.5, 2.0, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, or 1.3 m 2 It has a BJH surface area of ​​17 to 3,000 angstroms with pores less than 1g.

[0210] In one embodiment, or in combination with any embodiment referenced herein, cured or jet-milled CE microbeads have a BJH volume of pores between 17 and 3,000 angstroms of at least 0.001, 0.002, 0.003, or 0.004 and / or less than 0.1, 0.05, or 0.01 mL / g, as measured according to ISO 15901-02 using Micromeretics ASAP 2020 equipment and nitrogen gas.

[0211] In one embodiment, or in combination with any embodiment referenced herein, cured or jet-milled CE microbeads have a true specific gravity of at least 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9 and / or 1.5, 1.4, 1.3, 1.2, 1.1, 1.0, 0.9, 0.8, 0.7, or 0.6 or less, as measured according to JIS Z8807-1976.

[0212] In one embodiment, or in combination with any embodiment referenced herein, cured or jet-milled CE microbeads have a bulk specific gravity of at least 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, or 0.8 and / or 1.4, 1.3, 1.2, 1.1, 1.0, 0.9, 0.8, 0.7, 0.6, or 0.5 or less, as measured according to JIS 1201-1.

[0213] In one embodiment, or in combination with any embodiment referenced herein, the cured or jet-milled CE microbeads have a polydispersity index of less than 0.8, 0.7, 0.6, 0.5, 0.4, or 0.3.

[0214] In one embodiment, or in combination with any embodiment referenced herein, the cured or jet-milled CE microbeads have a surfactant content of less than 200, 150, 100, 50, 20, 10, 7.5, 5, 2.5, or 1 ppmw.

[0215] In one embodiment, or in combination with any embodiment referenced herein, the cured or jet-milled CE microbeads have a plasticizer content of less than 200, 150, 100, 50, 20, 10, 7.5, 5, 2.5, or 1 ppmw.

[0216] In one embodiment, or in combination with any embodiment referenced herein, the cured or jet-milled CE microbeads have a butyric acid content of less than 500, 400, 300, 200, 100, 50, 20, 10, 7.5, 5, 2.5, or 1 ppmw.

[0217] In one embodiment, or in combination with any embodiment referenced herein, the cured or jet-milled CE microbeads have an acetic acid content of less than 500, 400, 300, 200, 100, 50, 20, 10, 7.5, 5, 2.5, or 1 ppmw.

[0218] In one embodiment, or in combination with any embodiment referenced herein, cured or jet-milled CE microbeads have a propionic acid content of less than 500, 400, 300, 200, 100, 50, 20, 10, 7.5, 5, 2.5, or 1 ppmw.

[0219] The butyric acid, acetic acid, and propionic acid content of cured or jet-milled CE microbeads can be measured via gas chromatography ("GC"). In one GC method, the butyric acid, acetic acid, and propionic acid content can be measured by adding approximately 100 mg of cured or jet-milled CE microbeads to a tare-filled 4-dram vial, followed by the addition of an internal standard solution of a 90:10 dichloromethane / methanol mixture containing nonane. 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 the sample is then vortexed. Approximately 100 mg of the supernatant is transferred to a GC vial 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, a second GC methodology involves preparing the sample by adding approximately 30 mg of cured or jet-milled CE microbeads, followed by an internal standard solution containing decane in pyridine and 1.0 mL of BSTFA, to a tare-filled GC vial. The vial is heated at 80°C for 30 minutes and 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.

[0220] In one embodiment, or in combination with any embodiment referenced herein, cured or jet-milled CE microbeads have a sulfuric acid content of less than 500, 400, 300, 200, 100, 50, 20, 10, 7.5, 5, 2.5, or 1 ppmw. The sulfuric acid content of cured or jet-milled CE microbeads can be measured by the following methodology: First, the test sample is added to 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 blank are titrated with 0.05 N potassium hydroxide in methanol using an automated titrator equipped with a composite glass potential measuring 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.

[0221] In one embodiment, or in combination with any embodiment referenced herein, cured or jet-milled CE microbeads have a CE content of at least 50, 55, 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99 weight percent of mixed cellulose esters of the first, second, and / or third embodiments (including any class or subclass of these embodiments). Furthermore, or alternatively, cured or jet-milled CE microbeads may have a CE content of less than 99.9, 99.5, 99, 98, 97, 96, 95, 94, 93, 92, 91, 90, 89, 88, 87, 86, or 85 weight percent of mixed cellulose esters of the first, second, and / or third embodiments (including any class or subclass of these embodiments). In certain embodiments, the cured or jet-milled CE microbeads may essentially consist of a mixed cellulose ester of the first, second, and / or third embodiment (including any class or subclass of these embodiments).

[0222] In one embodiment, or in combination with any embodiment referenced herein, the cured or jet-milled CE microbeads may contain 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 cellulose acetate exhibiting 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, or at least 90% biodegradability, or at least 95% biodegradability in 60 days according to at least one of the OECD 301B, OECD 301C, or OECD 301F test methods.

[0223] In one embodiment, or in combination with any embodiment referenced herein, the cured or jet-milled CE microbeads may contain at least 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 weight percent of additional biodegradable cellulose esters different from the mixed cellulose esters of the first, second, and / or third embodiments. Furthermore, or alternatively, the cured or jet-milled CE microbeads may contain less than 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5 weight percent of additional biodegradable cellulose esters different from the mixed cellulose esters of the first, second, and / or third embodiments.

[0224] In one embodiment, or in combination with any embodiment referenced herein, the cured or jet-milled CE microbeads have a water content of one or more of the following amounts: (1) greater than 0 weight percent; (2) 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, or 0.05 weight percent or less; and (3) within the range of 0 to 10, 0 to 5, 0 to 4, 0 to 3, or 1.3 weight percent.

[0225] In one embodiment, or in combination with any embodiment referenced herein, cured or jet-milled CE microbeads 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, or at least 90% biodegradability, or at least 95% biodegradability after 56 days by at least one of the OECD 301B, OECD 301C, or OECD 301F test methods.

[0226] In one embodiment, or in combination with any embodiment referenced herein, cured or jet-milled CE microbeads 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, or at least 90% biodegradability, or at least 95% biodegradability after 60 days by at least one of the OECD 301B, OECD 301C, or OECD 301F test methods.

[0227] In one embodiment, or in combination with any other embodiments referenced herein, cured or jet-milled CE microbeads exhibit an oil absorption of at least 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100 mL per 100 g, when measured using test method ASTM D281 with mineral oil instead of castor oil.

[0228] In one embodiment, or in combination with any other embodiment referenced herein, cured or jet-milled CE microbeads exhibit zeta potentials 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 -45mV. Furthermore, or alternatively, cured or jet-milled CE microbeads may exhibit zeta potentials of less than -5mV, less than -10mV, less than -15mV, less than -20mV, less than -25mV, less than -30mV, less than -35mV, less than -40mV, less than -45mV, less than -50mV, less than -55mV, less than -60mV, or less than -65mV.

[0229] The zeta potential was measured by dispersing microbeads in water by vortex mixing for 30 seconds. The microbead concentration was controlled 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. Next, the Smolkovsky model was used to calculate the zeta potential.

[0230] In one embodiment, or in combination with any other embodiment referenced herein, cured or jet-milled CE microbeads exhibit a haze transmittance of at least 10, at least 15, at least 20, at least 25, at least 30, at least 35, at least 40, or at least 45 percent. Furthermore, or alternatively, cured or jet-milled CE microbeads may exhibit a haze transmittance of less than 90, or less than 85, or less than 80, or less than 75, or less than 70, or less than 65, or less than 60, or less than 55, or less than 50, or less than 45, or less than 40 percent, or less than 35 percent, or less than 32 percent, or less than 30 percent. The haze transmittance can be measured by forming an aqueous emulsion containing 5 wt percent or 7 wt percent biodegradable beads using a BYK gloss meter and BYK turbidity Gard I.

[0231] The detailed procedure for measuring haze (turbidity) is described below. A W / O emulsion for measuring turbidity % 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) in the following weight concentrations: 59:2:1. Phase B was prepared using caprylic / capric triglyceride (MKing Cosmertics), C12-15 alkyl benzoate (MKing Cosmes), Emlium Illustro (Gattefosse), bentonite gel ISD V (Elementis), and microbead powder in the following weight concentrations: 12.5:12.5:5:3:5. Phase A was prepared by mixing the listed components. Phase B was prepared without microbead powder by overhead stirring until all components were dissolved. Next, phase A is added to phase B while stirring at 1000 rpm until completely mixed. Then, the microbead powder is added to the mixture while stirring at 1000 rpm for 5 minutes. The resulting mixture is homogenized using Ultrax Turax at 10,000 rpm for 5 minutes. The haze transmittance of the drawdown film (38 μm) after drying at 50°C for 5 minutes is measured using BYK Haze Gard I.

[0232] In one embodiment, or in combination with any other embodiment referenced herein, cured or jet-milled CE microbeads 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%, as measured using a BYK Haze-Gard I unit.

[0233] Cosmetic formulations Cured or jet-milled CE microbeads produced by the processes disclosed herein may be used to produce a variety of cosmetic compositions. Cosmetic compositions may be produced by (1) providing a plurality of cured or jet-milled CE microbeads; (2) combining these cured or jet-milled CE beads with one or more cosmetic additives to form a pre-cosmetic mixture; and (3) forming a cosmetic composition from this pre-cosmetic mixture.

[0234] In one embodiment, or in combination with any other embodiment, this application discloses a cosmetic composition comprising any of the CE microbeads (cured or jet-milled) disclosed herein.

[0235] In one embodiment, or in combination with any other embodiments 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 weight percent of cured or jet-milled CE microbeads. Furthermore, or alternatively, the cosmetic composition may contain 99, 90, 80, 70, 60, 50, 40, 30, 25, 20, 15, 10, or less than 5 weight percent of or jet-milled cured CE microbeads. For example, this cosmetic composition may contain 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 weight percent of cured or jet-milled CE microbeads.

[0236] 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, tablet, foot powder, baby powder, shaving cream, or shaving gel.

[0237] In one embodiment, or in combination with any other embodiments referenced herein, the cosmetic composition may be a loose powder, compressed powder, gel, emulsion, liquid, or aerosol.

[0238] In one embodiment, or in combination with any other embodiment referenced herein, the cosmetic composition comprises at least 1, 2, 3, 4, or 5 cosmetic additives in weight percent 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. Furthermore, or alternatively, the cosmetic composition may comprise at least 1, 2, 3, 4, or 5 cosmetic additives in weight percent of less than 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, or 50. For example, a cosmetic composition may contain at least one, two, three, four, or five cosmetic additives in weight percent 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.

[0239] In general, cosmetic additives may 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.

[0240] 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.

[0241] 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.

[0242] 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.

[0243] 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.

[0244] 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.

[0245] In one embodiment, or in combination with any other embodiment referred to herein, this ester is derived from 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, neopentyl glycoside 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.

[0246] In one embodiment, or in combination with any other embodiment referenced herein, the hydrocarbons include paraffin, petrolatum, and / or microcrystalline waxes.

[0247] In one embodiment, or in combination with any other embodiment referenced herein, the surfactant includes anionic surfactants, cationic surfactants, and / or nonionic surfactants.

[0248] In one embodiment, or in combination with any other embodiment referenced herein, the thickener includes guar gum, pectin, starch, gelatin, collagen, cellulose derivatives, and / or mannan.

[0249] experiment Abbreviation CAB is cellulose acetate butyrate; DSOH is the average degree of substitution of hydroxyl substituents; DSAc is the average degree of substitution of acetyl substituents; DSBu is the average degree of substitution of butyryl substituents; and PS means D(4,3) particle size.

[0250] To measure the solubility of cellulose acetate butyrate (CAB), Example 1, and other CEs in a solvent system containing ethyl acetate (EA), n-propanol (nPrOH), and water, CE dopes were prepared as shown in Table 3 below. The preparation of Example 1 is shown below.

[0251] Example 1: Cellulose acetate butyrate (DS) Ac =1.87, DS Bu =0.22, DS OH =0.91M w =90766) Cellulose and an acid mixture [cellulose (4.3 parts) and AcOH (11.8 parts)] were added to a stirred reactor and immersed without heating, then the mixture was heated to 55°C. Sulfuric acid was added, and the reaction mixture was cooled to 30°C. Subsequently, a mixture of Ac2O (8.9 parts) and Bu2O (5.6 parts) (i.e., the acylation solution) was added, and the mixture was cooled to approximately 9°C while stirring. The resulting reaction mixture was heated to 50°C, and the reaction mixture was stirred until acylation was complete and the desired molecular weight was achieved. A mixture of BuOH (18 parts) and H2O (7.4 parts) was added to this reaction mixture. The mixture was then stirred at 68°C for 1020 minutes. Next, the mixture was quenched by conventional methods, precipitated in water, washed, and dried.

[0252] General procedure for the preparation of cellulose esters A cellulose mixture [cellulose and AcOH] ("cellulose mixture") and sulfuric acid, Ac2O, and Bu2O ("acylation solution") were cooled to 30°C in a stirred reactor, and the reaction mixture was cooled to approximately 7°C while stirring. Additional sulfuric acid was added to the target amount, and the resulting reaction mixture was heated to 45°C to 65°C while stirring until the reagents were used up. This reaction mixture was treated with aqueous solutions of AcOH and BuOH ("hydrolysis solution") and stirred at 68°C under hydrolysis conditions. Next, the reaction mixture was quenched, neutralized, precipitated, washed, and dried using a general method.

[0253] Examples 2-5 were prepared by adapting the general procedure for preparing cellulose esters using the reagents and conditions shown in Table 1. Table 2 shows the various degrees of substitution and molecular weights of Examples 2-5. [Table 1]

[0254] Degree of substitution The degree of substitution of substituents on the cellulose ester skeleton is calculated using proton nuclear magnetic resonance spectroscopy. Gel permeation chromatography is performed on cellulose ester in stabilized tetrahydrofuran. The apparatus is an Agilent 1260, which consists 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 sample in 10 ml of solvent by adding 10 microliters of toluene as a flow marker, and stirring with a stirring rod in an 8-drum screw-cap vial until dissolved.

[0255] molecular weight The molecular weight is determined by gel permeation chromatography. Gel permeation chromatography is carried out on the cellulose ester in stabilized tetrahydrofuran. The instrument is an Agilent 1260, which consists of a degassing device, an isocratic pump with a flow rate of 1.0 milliliter per minute, an autosampler with an injection volume of 25 microliters, a column oven set at 28 °C, and a refractive index detector at 28 °C. The column set consists of an 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 about 4 million to 162. A 10-microliter toluene used as a flow marker is added, and a sample weighing about 25 milligrams in 10 milliliters of solvent is measured. A stir bar is added to an 8-drum screw-cap vial and stirred until dissolved to prepare the sample.

[0256] Preparation of CE Dope The CE dope was prepared by filling a dry 250 mL one-neck round-bottom flask equipped with a magnetic stirrer with the respective amounts of the solvent system. The solvent system was stirred and then the respective amounts / types of CAB were placed into the flask. The CAB was added to the flask by slowly weighing the solid such that the stirring vortex was able to move the solid particles into the solvent system without forming a large mass of powder at the top of the liquid phase. The mixture of solvent and CAB was stirred at room temperature for 45 minutes. If the mixture became homogeneous within this period, the dope was determined to be "soluble". If solid particles remained undissolved in the solvent system at 60 minutes, the dope was determined to be "insoluble".

[0257] In Dopants 1-1, 1-2, and 1-3, the solvent system contained ethyl acetate and n-propanol in various amounts but did not contain water. In Dopants 1-1a, 1-2a, and 1-3a, water was added to the solvent system. That is, the solvent systems of Dopants 1-1 and 1-1a, 1-2 and 1-2a, and 1-3 and 1-3a contained the same amounts of ethyl acetate and n-propanol, and the only difference between the respective dopants was the addition of water.

[0258] In Dopant 1-4a, the amount of CAB contained in the CE dopant was increased to match the mass % of CAB in the dopants without water (i.e., Dopants 1-1, 1-2, and 1-3).

Table 2

[0259] Notably, the CE dopants without water were unable to solubilize the CE contained therein. For example, Dopant 1-1 provided a lumpy and heterogeneous mixture, and Dopants 1-2 and 1-3 initially provided a stirrable slurry but became lumpy and heterogeneous after a few minutes. [[ID=I5]]

[0260] In comparison, Dopant 1-1a provided a stirrable slurry rather than a lump. Dopants 1-2a and 1-3a provided homogeneous mixtures in which the CE dissolved in the solvent system within 3 minutes.

[0261] As shown in Dopant 1-4a, by increasing the mass of CE contained in the CE dopant, a homogeneous mixture in which the CE dissolved in the solvent system within 3 minutes was also provided. That is, the increase in the CAB% of the CE dopant did not seem to adversely affect the solubility of the CE in the solvent system.

[0262] Emulsion Process for Particle Preparation A clean, dry 3-liter kettle flask (with baffles) was equipped with a two-stage overhead mechanical stirrer and a bottom dropout valve. 700–1,300 g of deionized water, 6–13 g of Tergitol 15-S-40, and 0–1.0 g of PEG-100 stearic acid were added to the kettle. Over 15 minutes, 7–12 g of colloidal protectant (low, medium, or high viscosity carboxymethylcellulose or methylcellulose) was added to the stirred aqueous mixture. The mixture was stirred at ambient temperature for 1 hour or until homogenized.

[0263] Another clean, dry 2-liter kettle flask equipped with an overhead mechanical stirrer and a bottom dropout valve was prepared. A doped solution consisting of 10–100% cellulose ester was prepared using 0–5.0 parts of C1-C4 alkyl acetate, 0–1.0 part of C1-C3 alcohol, and 0–0.80 parts of deionized water (based on the mass of cellulose ester used). The mixture was stirred at ambient temperature until homogeneous.

[0264] The doping solution was added to a 3-liter kettle over 30 minutes with vigorous stirring (250-500 rpm). After addition, the emulsion was recirculated for 45-60 minutes at a rate of 100-300 mL / min through a flow cell containing a high-shear mixer (0-12,000 rpm).

[0265] After the high-shear mixing time was complete, the emulsion was then pumped at 300 mL / min into a 5-gallon bucket equipped with a single-stage overhead mechanical agitator containing 4000-6000 g of deionized water, and stirred at 250-500 rpm for 0-16 hours. After the holding time, the volume was centrifuged to separate the spherical particles. These particles were suspended in 1-2 L of deionized water and centrifuged again. This washing process was repeated once.

[0266] The fine particles were placed in a Sigma Blade Mixer and dried under vacuum (100-400 mmHg) at 50-100°C for 16 hours. A typical recovery yield is 75-85%.

[0267] Jet mill grinding process for preparing fine particles Several jet mill configurations can be used to reduce particle size. Such configurations are discussed in A. Chamayo and JA Dodds, Air Jet Milling, Handbook of Powder Technology, volumes 12, Chapter 8, 2007 ("Chamayo"). Figure 7 in Chamayo shows an example of a fluidized bed opposed jet mill that can be used to reduce the size of cellulose ester particles, as listed in Table 4 below. Using the jet mill process, the average particle size of cellulose ester was reduced from 300–900 μm to approximately 10 μm. The fluidized bed opposed jet mill operates as follows: Cellulose ester is placed in a hopper and introduced into the top of the mill, typically in a double-valve configuration (or via an injector) ("FEED IN"). The cellulose ester particles fall to the bottom of the mill by gravity, where they are pushed into one of three geometrically oriented high-pressure airflows, thereby forming a so-called "grinding zone." Within this grinding zone, the cellulose ester particles are reduced in size through interparticle collisions. Subsequently, the reduced-size particles are transported upward by mass transport in the vertical airflow (fluidized bed) and eventually carried into the classifier. The classifier allows for the removal of particles smaller than the desired minimum size from the mill ("FINE OUT"). Particles larger than the maximum size are excluded from the classifier, returned to the fluidized bed, and eventually returned to the grinding zone where they are further reduced in size. Particles that fall within the desired size range are discharged from the classifier into the appropriate product container. Many control parameters exist to optimize productivity, particle size, and particle size distribution shape, and these include, but are not limited to, classifier rotor speed, air nozzle pressure, and bed level. [Table 3]

[0268] Description of the OECD 301F exam In this experiment, a known concentration of the test substance, which functions as a nominal organic carbon source, is inoculated into the measured volume of inorganic culture medium. The medium is placed in a sealed flask and stirred at a constant temperature (within the range of +1°C or less) for a maximum of 60 days.

[0269] Oxygen consumption is determined by one of two methods: by measuring the amount of oxygen (electrolytically produced) required to maintain a constant gas volume in the respiratory flask, or by monitoring changes in volume or pressure (or a combination thereof) within the apparatus.

[0270] All 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 material is calculated by subtracting the oxygen uptake by a blank inoculum (which is performed in parallel). This value is expressed as a percentage of the theoretical oxygen demand (ThOD) or, less ideally, the chemical oxygen demand (COD).

[0271] Haze (turbidity) measurement The haze (turbidity) percentage of the formulation was measured using the BYK HazeGuard instrument. The HazeGuard instrument generates a light beam, which strikes the sample, where some of the light is transmitted and enters an integrating sphere to measure the transmitted haze. It uses both unidirectional illumination and diffuse visualization.

[0272] Haze (turbidity) measurement procedure Clean the Gorilla Glass with acetone or ethyl alcohol and confirm that there are no streaks on the substrate. Use a 1.5 - mil square draw - down bar to draw down the formulation on the Gorilla Glass. Pull the bar down from top to bottom at a constant speed / constant pressure to create a uniform test sample on the substrate. The sample should be uniform and have an equal thickness. Place the sample in an oven and dry it at 35 - 40 °C for 5 minutes. After removing the sample from the oven, cool it completely. Place the draw - down sample in front of a haze sensor for haze measurement. Obtain three readings with one sample at the top, middle, and bottom of the draw - down. Perform three draw - downs per sample. Average the nine readings and report the percentage of haze. <000,0963> Haze (turbidity) of particles in a single - oil dispersion Table 5 shows the haze (turbidity) of various particles in a single - oil dispersion. The dispersion was either 5 wt% or 7 wt% in dimethicone. A mixer was used to completely disperse the particles in dimethicone.

[0274] All of the added particles showed higher haze values compared to the dimethicone oil base material. The cellulose ester particles showed equivalent or better haze % compared to the external reference (benchmark) particles. It can be concluded that the cellulose ester particles imparted an enhanced optical effect by showing a higher haze (turbidity) %. [Table 4]

Claims

1. Biodegradable fine particles containing mixed cellulose esters, The biodegradable fine particles exhibit at least 50 percent biodegradability and at least 10% haze transmission 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) Average degree of substitution for acetyl substituents in the range of 0.1 to 2.3 ("DS Ａｃ "), (b) Average degree of substitution of propynyl substituents in the range of 0.1 to 1.5 ("DS Ｐｒ ) or average degree of substitution of butyl substituents ("DS Ｂｕ "), and (c) Average degree of substitution for hydroxyl substituents in the range of 0.6 to 2.8 ("DS ＯＨ The biodegradable fine particles having ''.

2. The biodegradable microparticles according to claim 1, wherein the biodegradable microparticles exhibit a haze transmittance of at least 15, at least 20, at least 25, at least 30, at least 35, at least 40, or at least 45 percent as measured using a BYK Haze-Gard I unit, and / or the biodegradable microparticles exhibit a haze transmittance of less than 90, or less than 85, or less than 80, or less than 75, or less than 70, or less than 65, or less than 60, or less than 55, or less than 50, or less than 45, or less than 40 percent, or less than 35 percent, or less than 32 percent, or less than 30 percent.

3. The biodegradable fine particles are at least 0.5, at least 0.55, at least 0.60, at least 0.65, at least 0.70, at least 0.75, at least 0.80, at least 0.85, at least 0.9, at least 0.95, at least 1.0, at least 1.05, at least 1.1, at least 1.15, at least 1.2, or at least 1.25, and / or less than 3.0, 2.9, less than 2.8, less than 2.7, less than 2.6, 2 Biodegradable fine particles according to any one of claims 1 to 2, exhibiting a unimodal particle size distribution with a span of less than 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, or less than 1.6, or 1 to 2, or 1 to 1.8, or 1 to 1.6, or 1.1 to 2, or 1.1 to 1.8, or 1.1 to 1.6, or 1.2 to 2, or 1.2 to 1.8, or 1.2 to 1.

6.

4. The biodegradable fine particles according to any one of claims 1 to 3, wherein the biodegradable fine particles have a D50 volume-based particle size in the range of 5 to 20, or 5 to 15, or 5 to 10, or 6 to 20, or 6 to 15, or 6 to 10, or 7 to 20, or 7 to 15, or 7 to 10, or 8 to 20, or 8 to 15, or 8 to 10, or 9 to 20, or 9 to 15, or 9 to 10, or 10 to 20, or 10 to 15 microns.

5. The biodegradable microparticles according to any one of claims 1 to 4, wherein the biodegradable microparticles exhibit at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95 percent biodegradability in 60 days according to at least one of the OECD 301B, OECD 301C, or OECD 301F test methods; and / or the mixed cellulose ester exhibits at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95 percent biodegradability in 60 days according to at least one of the OECD 301B, OECD 301C, or OECD 301F test methods.

6. Said DS Ａｃ Biodegradable fine particles according to any one of claims 1 to 5, wherein the ratio 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, or 1.8 to 2.3, or 1.8 to 2.2, or 1.8 to 2.1, or 1.8 to 2.0, or 1.85 to 2.3, or 1.85 to 2.2, or 1.85 to 2.1, or 1.85 to 2.0, or 1.9 to 2.3, or 1.9 to 2.2, or 1.9 to 2.1, or 1.9 to 2.

0.

7. Said DS Ａｃ The biodegradable fine particles according to any one of claims 1 to 6, wherein the particle size 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, 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.

8. Said DS Ｐｒ The biodegradable fine particles according to any one of claims 1 to 7, wherein the amount is at least 0.2, or at least 0.3, or at least 0.4, or at least 0.5, at least 0.6, or at least 0.7, or at least 0.8, or at least 0.9, or at least 1.0, or at least 1.1, at least 1.2, or at least 1.3, or at least 1.

4.

9. Said DS Ｐｒ The biodegradable fine particles according to any one of claims 1 to 8, wherein the amount 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.

10. the DS Ｂｕ is at least 0.2, or at least 0.3, or at least 0.4, or at least 0.5, or at least 0.6, or at least 0.7, or at least 0.8, or at least 0.9, or at least 1.0, at least 1.1, or at least 1.2, or at least 1.3, or at least 1.4, or 0.18 to 0.23, or 0.18 to 0.22, or 0.18 to 0.21, or 0.18 to 0.20, or 0.18 to 0.19, or 0.19 to 0.23, or 0.19 to 0.22, or 0.19 to 0.21, or 0.19 to 0.2, or 0.2 to 0.23, 0.2 to 0.22, or 0.2 to 0.21; and / or DS Ｂｕ is less than 1.5, or less than 1.4, or less than 1.3, or less than 1.2, or less than 1.1, or less than 1.0, or less than 0.9, or less than 0.8, or 0.7, or less than 0.5, or less than 0.4, or less than 0.3, The biodegradable fine particles according to any one of claims 1 to 9.

11. Said DS ＯＨ However, at least 0.6, or at least 0.7, or at least 0.8, or at least 0.9, or at least 1.0, or at least 1.1, or at least 1.2, or at least 1.3, or at least 1.4, or 0.5 to 0.95, or 0.5 to 0.93, or 0.5 to 0.91, or 0.5 to 0.9, or 0.5 to 0.85, or 0.5 to 0.80, or 0.5 to 0.75, or 0.5-0.7, or 0.55-0.95, or 0.55-0.93, or 0.55-0.91, or 0.55-0.9, or 0.55-0.85, or 0.55-0.80, or 0.55-0.75, or 0.55-0.7, or 0.6-0.95, or 0.6-0.93, or 0.6-0.91, or 0.6-0.9, or 0.6-0.85, or 0.6-0. 80, or 0.6-0.75, or 0.6-0.7, or 0.65-0.95, or 0.65-0.93, or 0.65-0.91, or 0.65-0.9, or 0.65-0.85, or 0.65-0.80, or 0.65-0.75, or 0.65-0.7, or 0.7-0.95, or 0.7-0.93, or 0.7-0.91, or 0.7-0.9, or 0.7-0.85 , or 0.7 to 0.80, or 0.7 to 0.75, or 0.8 to 0.95, or 0.8 to 0.93, or 0.8 to 0.91, or 0.8 to 0.9, or 0.8 to 0.85, or 0.85 to 0.95, or 0.85 to 0.93, or 0.85 to 0.91, or 0.85 to 0.9, or 0.9 to 0.95, or 0.9 to 0.93, or 0.9 to 0.91, and / or in the formula, the DS ＯＨ The biodegradable microparticles according to any one of claims 1 to 10, wherein the coefficient is less than 2.7, or less than 2.6, or less than 2.5, less than 2.4, or less than 2.3, or less than 2.2, less than 2.1, or less than 2.0, or less than 1.9, or less than 1.8, or 1.7, or less than 1.6, or less than 1.5, or less than 1.4, or less than 1.3, or less than 1.2, or less than 1.1, or less than 1.0, or less than 0.

9.

12. The biodegradable fine particles according to any one of claims 1 to 11, wherein the mixed cellulose ester is cellulose acetate butyrate, cellulose acetate butyrate, or a mixture thereof.

13. The biodegradable fine particles according to any one of claims 1 to 12, wherein the mixed cellulose ester is cellulose acetate butyrate.

14. The biodegradable fine particles according to any one of claims 1 to 13, wherein the biodegradable fine particles contain at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 99 percent by weight of a mixed cellulose ester, and / or the biodegradable fine particles constitute less than 99 percent by weight, or less than 95 percent by weight, or less than 90 percent by weight, or less than 85 percent by weight, or less than 80 percent by weight, or less than 75 percent by weight, or less than 70 percent by weight of the mixed cellulose ester.

15. The biodegradable fine particles according to any one of claims 1 to 14, wherein the biodegradable fine particles essentially consist of the mixed cellulose ester.

16. The biodegradable fine particles consist of at least 10, or at least 20, or at least 30, or at least 40, or at least 50, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 96, or at least 97, or at least 98, or 20 to 100, or 20 to 90, or 20 to 80, or 20 to 70, or 20 to 60, or 30 to 100, or 30 to 90, or 30 to 80, or 30 to 70, or 30 to 60, or 40 to 100, or 40 to 90, or 40 to 80, or 40 to 70, or The biodegradable fine particles according to any one of claims 1 to 15, wherein the fine particles have a sphericity of 40 to 60, or 50 to 100, or 50 to 90, or 50 to 80, or 50 to 70, or 50 to 60, or 60 to 100, or 60 to 90, or 60 to 80, or 60 to 70, or 70 to 100 percent, or 70 to 90 percent, or 70 to 80 percent, or 80 to 100 percent, or 80 to 90 percent, or 90 to 100 percent, and / or the biodegradable fine particles have a sphericity of less than 100 percent, or less than 95 percent, or less than 90 percent, or less than 80 percent, or less than 70 percent, or less than 60 percent, or less than 50 percent.

17. The biodegradable microparticles according to any one of claims 1 to 16, wherein, as measured using the ASTM D281 test method in which mineral oil is used instead of castor oil, the biodegradable microparticles exhibit an oil absorption of at least 30 mL per 100 g, at least 35 mL per 100 g, or at least 40 mL per 100 g, or at least 45 mL per 100 g, or at least 50 mL per 100 g, or at least 55 mL per 100 g, or at least 60 mL per 100 g.

18. A process for forming biodegradable microparticles, (a) Forming a dope containing a mixed cellulose ester, wherein the mixed cellulose ester is (i) Average degree of substitution for acetyl substituents in the range of 0.1 to 2.3 ("DS Ａｃ "), (ii) Average degree of substitution of propynyl substituents in the range of 0.1 to 1.5 ("DS Ｐｒ ) or average degree of substitution of butyl substituents ("DS Ｂｕ "), and (iii) Average degree of substitution for hydroxyl substituents in the range of 0.6 to 2.8 ("DS ＯＨ "), including; (b) bringing at least a portion of the dope into contact with an aqueous mixture under stirring to form an initial emulsion; (c) Converting at least a portion of the initial emulsion into a dispersion comprising a solid phase and a liquid phase, wherein the solid phase comprises biodegradable fine particles; (d) The process of recovering at least a portion of the biodegradable particulate matter from the dispersion, wherein the biodegradable particulate matter exhibits at least 50 percent biodegradability in 60 days according to at least one of the OECD 301B, OECD 301C, or OECD 301F test methods, and the biodegradable particulate matter exhibits at least 10 percent haze transmission.

19. The process according to claim 18, wherein the biodegradable particulate matter exhibits a haze transmittance of at least 15, at least 20, at least 25, at least 30, at least 35, at least 40, or at least 45 percent, and / or the biodegradable particulate matter exhibits a haze transmittance of less than 90, or less than 85, or less than 80, or less than 75, or less than 70, or less than 65, or less than 60, or less than 55, or less than 50, or less than 45, or less than 40 percent, or less than 35 percent, or less than 32 percent, or less than 30 percent.

20. A process according to any one of claims 18 to 19, wherein the biodegradable particulate matter comprises at least 0.5, or at least 0.55, or at least 0.60, or at least 0.65, or at least 0.70, or at least 0.75, or at least 0.80, or at least 0.85, or at least 0.9, or at least 0.95, or at least 1.0, or at least 1.05, or at least 1.1, or at least 1.15, or at least 1.2, or at least 1.25; and / or 3.0 It exhibits a unimodal particle size distribution with spans of 1.5, or less than 2.9, or less than 2.8, or less than 2.7, or less than 2.6, or less than 2.5, or less than 2.4, or less than 2.3, or less than 2.2, or less than 2.1, or less than 2.0, or less than 1.9, or less than 1.8, or less than 1.7, or less than 1.6, or 1 to 2, or 1 to 1.8, or 1 to 1.6, or 1.1 to 2, or 1.1 to 1.8, or 1.1 to 1.6, or 1.2 to 2, or 1.2 to 1.8, or 1.2 to 1.6; and / or The biodegradable fine particles are in the order of 1 to 100, or 1 to 80, or 1 to 70, or 1 to 60, or 1 to 50, or 1 to 40, or 1 to 35, or 1 to 30, or 1 to 25, or 1 to 20, or 1 to 15, or 1 to 10, or 2 to 100, or 2 to 80, or 2 to 70, or 2 to 60, or 2 to 50, or 2 to 40, or 2 to 35, or 2 to 30, or 2 to 25, or 2 to 20, or 2 to 15, or 2 to 10, or 3 ~100, or 3~80, or 3~70, or 3~60, or 3~50, or 3~40, or 3~35, or 3~30, or 3~25, or 3~20, or 3~15, or 3~10, or 5~100, or 5~80, or 5~70, or 5~60, or 5~50, or 5~40, or 5~35, or 5~30, or 5~25, or 5~20, or 5~15, or 5~10, or 10~100, or 10 ~80, or 10~70, or 10~60, or 10~50, or 10~40, or 10~35, or 10~30, or 10~25, or 10~20, or 10~15, or 15~100, or 15~80, or 15~70, or 15~60, or 15~50, or 15~40, or 15~35, or 15~30, or 15~25, or 15~20, or 20~100, or 20~80, or 20~70, or The process having a D50 volume-based particle size in the range of 20-60, or 20-50, or 20-40, or 20-35, or 20-30, or 25-100, or 25-80, or 25-70, or 25-60, or 25-50, or 25-40, or 25-35, or 25-30, or 30-100, or 30-80, or 30-70, or 30-60, or 30-50, or 30-40, or 30-35 microns.

21. The process according to any one of claims 18 to 20, wherein the biodegradable fine particles exhibit at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95 percent biodegradability in 60 days by at least one of the OECD 301B, OECD 301C, or OECD 301F test methods; and / or the mixed cellulose ester exhibits at least 40, or at least 45, or at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95 percent biodegradability in 60 days by at least one of the OECD 301B, OECD 301C, or OECD 301F test methods.

22. Said DS ＯＨ However, at least 0.6, or at least 0.7, or at least 0.8, or at least 0.9, or at least 1.0, or at least 1.1, or at least 1.2, or at least 1.3, or at least 1.4, or 0.5 to 0.95, or 0.5 to 0.93, or 0.5 to 0.91, or 0.5 to 0.9, or 0.5 to 0.85, or 0.5 to 0.80, or 0.5 to 0 .75, or 0.5-0.7, or 0.55-0.95, or 0.55-0.93, or 0.55-0.91, or 0.55-0.9, or 0.55-0.85, or 0.55-0.80, or 0.55-0.75, or 0.55-0.7, or 0.6-0.95, or 0.6-0.93, or 0.6-0.91, or 0.6-0.9, or 0.6-0.85, or 0.6-0.8 0, or 0.6-0.75, or 0.6-0.7, or 0.65-0.95, or 0.65-0.93, or 0.65-0.91, or 0.65-0.9, or 0.65-0.85, or 0.65-0.80, or 0.65-0.75, or 0.65-0.7, or 0.7-0.95, or 0.7-0.93, or 0.7-0.91, or 0.7-0.9, or 0.7-0.85, or 0.7 to 0.80, or 0.7 to 0.75, or 0.8 to 0.95, or 0.8 to 0.93, or 0.8 to 0.91, or 0.8 to 0.9, or 0.8 to 0.85, or 0.85 to 0.95, or 0.85 to 0.93, or 0.85 to 0.91, or 0.85 to 0.9, or 0.9 to 0.95, or 0.9 to 0.93, or 0.9 to 0.91; and / or, where the DS ＯＨ The process according to any one of claims 18 to 21, wherein the coefficient is less than 2.7, or less than 2.6, or less than 2.5, or less than 2.4, or less than 2.3, or less than 2.2, or less than 2.1, or less than 2.0, or less than 1.9, or less than 1.8, or 1.7, or less than 1.6, or less than 1.5, or less than 1.4, or less than 1.3, or less than 1.2, or less than 1.1, or less than 1.0, or less than 0.

9.

23. The biodegradable fine particles according to any one of claims 18 to 22, wherein the mixed cellulose ester is cellulose acetate butyrate.

24. The biodegradable fine particles consist of at least 10, or at least 20, or at least 30, or at least 40, or at least 50, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 96, or at least 97, or at least 98, or 20-100, or 20-90, or 20-80, or 20-70, or 20-60, or 30-100, or 30-90, or 30-80, or 30-70, or 30-60, or 40-100, or 40-90, or 40-80, or 40-70, or 40 The biodegradable microparticles according to any one of claims 18 to 23, wherein the sphericity of the microparticles is ~60, or 50 to 100, or 50 to 90, or 50 to 80, or 50 to 70, or 50 to 60, or 60 to 100, or 60 to 90, or 60 to 80, or 60 to 70, or 70 to 100 percent, or 70 to 90 percent, or 70 to 80 percent, or 80 to 100 percent, or 80 to 90 percent, or 90 to 100 percent, and / or the biodegradable microparticles are less than 100 percent, or less than 95 percent, or less than 90 percent, or less than 80 percent, or less than 70 percent, or less than 60 percent, or less than 50 percent.

25. The process according to any one of claims 18 to 24, wherein the biodegradable fine particles, as measured using the ASTM D281 test method, exhibit an oil absorption of at least 30 mL per 100 g, at least 35 mL per 100 g, at least 40 mL per 100 g, at least 45 mL per 100 g, at least 50 mL per 100 g, at least 55 mL per 100 g, or at least 60 mL per 100 g.

26. A cosmetic composition comprising biodegradable fine particles according to any one of claims 1 to 17.

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