Cellulose ester polymer composition having a low coefficient of friction

Abstract

Provided is an improved polymer composition based on a cellulose ester (such as CAP) that reduces the coefficient of friction of a polymer composition or a product manufactured therefrom without impairing other desirable properties. A cellulose ester composition comprising: (a) at least one cellulose ester; (b) at least one impact modifier in an amount of about 1 to about 15% by weight; (c) at least one friction modifier selected from waxes and siloxanes in an amount of about 0.1 to about 15% by weight; and (d) optionally, one or more plasticizers in an amount of 0 to about 15% by weight, wherein the composition has an HDT value exceeding 85°C at 0.455 MPa and a notched Izod impact strength value measured in accordance with ASTM D256 for a 3.2 mm thick bar at 23°C exceeding 80 J / m, which is after conditioning the bar at 230°C and 50% RH for 48 hours.

Description

Technical Field

[0001] The present invention generally belongs to the field of polymer science. In particular, the present invention relates to specific cellulose ester polymer compositions having a low coefficient of friction.

Background Art

[0002] Cellulose ester polymers, particularly mixed ester polymers such as cellulose acetate propionate (CAP) polymers, are useful in the manufacture of various molded plastic products. Cellulose esters are bio-based and can be obtained from renewable resources such as cotton linters, wood pulp, corn fibers, other agricultural resources, and bacterial cellulose. Commercially available cellulose esters used in thermoformed products usually contain a significant amount of plasticizer to enable processing and give sufficient strength to the molded product.

[0003] CAP polymers tend to have a moderate to high coefficient of friction (COF). If the COF is excessively high, it may be difficult or impossible to use in certain applications. For example, the operation of changing the tribological behavior of a polymer such as the coefficient of friction by incorporating additives may result in a significant reduction in physical properties or a trade-off in the performance of the base resin accordingly.

[0004] Assembly toys, i.e., toy building blocks, are an example of molded plastic products where the coefficient of friction is an important property. This is because it determines the effort required for a person to assemble or disassemble the toy building blocks. Therefore, there is a need for an improved polymer composition based on cellulose esters (such as CAP) that reduces the coefficient of friction of the polymer composition or the products manufactured therefrom without impairing other desirable properties.

Summary of the Invention

[0005] The friction of bio-based cellulose mixed ester (such as CAP) polymers has generally been found to be too high to allow for repeated interactions between similar materials required in many applications. As a result, high forces are required for the bonding and / or separation of articles, leading to excessive wear of the polymer due to repeated use and / or the possibility of polymer-to-polymer bonding (such as friction welding). Current materials for such applications may be insufficient according to specific application requirements or, otherwise, have limitations or drawbacks, such as lack of transparency or inclusion of substances that are currently or potentially of concern. It would also be beneficial to provide suitable materials with sustainability characteristics, such as being bio-based. Existing, unmodified cellulose polymers may have certain drawbacks, such as being bio-based but lacking sufficient toughness and friction profiles suitable for specific applications.

[0006] The present invention proposes means for reducing the friction of cellulose ester (e.g., CAP) polymers by incorporating various new combinations of additives. In embodiments, the reduction in the coefficient of friction is achieved by incorporating additives including wax and / or organosiloxane, while a sufficient balance of other properties, such as toughness and rigidity, is achieved by incorporating other specific additives, such as impact modifiers. Further, in certain embodiments, specific properties, such as impact toughness, are improved while reducing friction performance and maintaining transparency.

[0007] The provided friction-modified cellulose ester (e.g., CAP) polymer has increased ductility exhibiting an adjustable friction profile comparable to conventional engineering polymers such as acrylonitrile-butadiene-styrene polymer (ABS) or polycarbonate, and can exhibit a similar frictional response (static and dynamic coefficients of friction) over a wide range of contact pressures and part geometries. Notably, however, the physical properties such as toughness and modulus of elasticity after modification are maintained compared to ABS. Further, some embodiments provide means for maintaining transparency in addition to maintaining toughness / rigidity.

[0008] The present invention discloses a modified cellulose ester composition that is particularly suitable for use in the manufacture of injection-molded toy assembly blocks made of a biobased material having a desirable combination of physical and mechanical properties such as a satisfactory coefficient of friction and toughness. Embodiments of the present invention are described herein with reference to the following drawings.

Brief Description of the Drawings

[0009]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0010] In a first aspect, there is provided a cellulose ester composition comprising at least one cellulose ester, at least one impact modifier, at least one friction modifier selected from wax and siloxane, and optionally one or more plasticizers. In embodiments, the cellulose ester composition has a heat distortion temperature (HDT) above 85°C. Unless otherwise specified herein, the HDT is measured in accordance with ASTM D648 at a stress level of 0.455 MPa after conditioning at 70°C for 4 hours. It has been found that a cellulose ester composition having a high HDT can be provided in combination with good toughness and friction properties (described in more detail herein).

[0011]

[0012] ​In one embodiment, a cellulose ester composition is provided that does not contain a plasticizer, but contains 1 to 30 wt%, or 1 to 15 wt%, or 2 to 10 wt%, or 10 to 30 wt%, or 15 to 30 wt% of an impact modifier, based on the total weight of the cellulose ester composition, has an HDT value exceeding 85°C, and has a notched Izod impact strength value exceeding 80 J / m.

[0013] In another embodiment, a melt-processable cellulose ester composition that does not contain a plasticizer is provided. In the embodiment, the melt-processable cellulose ester composition contains 1 to 30 wt%, or 1 to 15 wt%, or 2 to 10 wt%, or 10 to 30 wt%, or 15 to 30 wt% of an impact modifier, based on the total weight of the cellulose ester composition, has an HDT value exceeding 85°C, a notched Izod impact strength value exceeding 80 J / m, and a spiral flow value of at least 15 inches when measured at 240°C.

[0014] In another embodiment, the melt-processable cellulose ester composition contains 2 wt% to 15 wt% of an impact modifier, based on the total weight of the cellulose ester composition, has an HDT value exceeding 85°C, a notched Izod impact strength value exceeding 80 J / m, and a viscosity of less than 10,000 P at 240°C and 400 rad / sec.

[0015] In another embodiment, a cellulose ester composition is provided in which the total DS / AGU ranges from about 2 to about 2.99, the DS / AGU of acetyl ranges from about 0 to about 2.2, and the remaining ester groups include propionyl, butyryl, or combinations thereof.

[0016] In one embodiment, a melt-processable cellulose ester composition is described that contains up to 15 wt%, or up to 10 wt% of a plasticizer; 1 to 30 wt%, or 1 to 15 wt%, or 2 to 10 wt% of an impact modifier; has an HDT value exceeding 85°C, and has a notched Izod impact strength value exceeding 80 J / m.

[0017] In another embodiment, based on the total weight of the cellulose ester composition, up to 15 wt% or up to 10 wt% of a plasticizer; 1-30 wt%, or 1-15 wt%, or 2-10 wt% of an impact modifier, based on the total weight of the cellulose ester composition; and having an HDT value above 85°C, a notched Izod impact strength value above 80 J / m, and a spiral flow value of at least 15 inches when measured at 240°C, a melt-processable cellulose ester composition is described.

[0018] In another embodiment, based on the total weight of the cellulose ester composition, up to 15 wt% or up to 10 wt% of a plasticizer; 1-30 wt%, or 1-15 wt%, or 2-10 wt% of an impact modifier, based on the total weight of the cellulose ester composition; and having an HDT value above 85°C and a notched Izod impact strength value above 80 J / m, and a viscosity at 240°C and 400 rad / sec of less than 10,000 P, a melt-processable cellulose ester composition is described.

[0019] In other embodiments, the melt-processable cellulose ester compositions described above optionally contain some plasticizer. In an embodiment, the plasticizer is present in an amount that does not substantially lower the HDT of the cellulose ester composition as compared to a similar composition without the plasticizer. In an embodiment, as a result of including the plasticizer, the HDT does not change (e.g., decrease) by more than 10%, or 5%, or 2%.

[0020] In one embodiment, a cellulose ester composition is provided that includes at least one cellulose ester, at least one impact modifier, and optionally at least one plasticizer. In one embodiment, the cellulose ester is CAP and the composition includes 0-5 wt%, 0-2 wt%, less than 0-2 wt%, or 0-1 wt% of a plasticizer. In one embodiment, the cellulose ester is CAP and no plasticizer is included.

[0021] In another embodiment, a cellulose ester composition is provided that includes at least one cellulose ester, at least one impact modifier, and at least one plasticizer. In one embodiment, the cellulose ester is cellulose acetate (CA) and includes 1 to 15 wt% plasticizer. In embodiments, the cellulose ester is CA and the composition includes 1 to 10 wt%, or less than 1 to 10 wt%, or 1 to 9 wt% plasticizer.

[0022] In one aspect, a cellulose ester composition is provided that includes: (a) at least one cellulose ester; (b) at least one impact modifier in an amount in the range of about 1 to about 30 wt%; (c) at least one friction modifier in an amount in the range of about 0.1 to about 12 wt% selected from waxes and siloxanes; and (d) optionally, one or more plasticizers in an amount in the range of 0 to about 30 wt%. In each case, the wt% is based on the total weight of the cellulose ester composition.

[0023] In an embodiment, a cellulose ester composition is provided that includes, based on the total weight of the composition, 67 to 99% by weight of at least one cellulose ester, 1 to 30% by weight of at least one impact modifier, 0.1 to 5% by weight of at least one friction modifier, and 0 to 3% by weight of at least one plasticizer, where the cellulose ester is selected from one or more of cellulose propionate (CP), cellulose butyrate (CB), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose propionate butyrate (CPB), cellulose tripropionate (CTP), or cellulose tributyrate (CTB); where the impact modifier is an acrylic core-shell impact modifier; and where the composition has an HDT value exceeding 85° C. and a notched Izod impact strength value, measured in accordance with ASTM D256 on a bar having a thickness of 3.2 mm at 23° C., exceeding 80 J / m, which is the value after conditioning the bar at 23° C. and 50% RH for 48 hours.

[0024] In another aspect, the cellulose ester composition further comprises a polymer aliphatic polyester ("PAP"). In embodiments, the PAP is a polymer aliphatic polyester comprising residues of one or more C2 to C4 alkanediols and residues of one or more C4 to C8 alkyl dicarboxylic acids, or comprising residues of a ring-opening lactone. In embodiments, the PAP comprises residues of one C2 to C4 alkanediol and residues of a C4 to C6 alkyl dicarboxylic acid. In embodiments, the PAP comprises residues of ethylene glycol or 1,4-butanediol and residues of succinic acid, glutaric acid and / or adipic acid. In embodiments, the PAP comprises residues of ethylene glycol or 1,4-butanediol and residues of succinic acid. In embodiments, the PAP is selected from poly(butylene succinate) or poly(ethylene succinate). In embodiments, the PAP is selected from poly(butylene adipate) or poly(ethylene adipate). In embodiments, the PAP is poly(butylene succinate) (PBS). In another embodiment, the aliphatic polyester comprises residues of the ring-opening of a lactone such as caprolactone (cyclic ester). In embodiments, the PAP can be a copolymer comprising, for example, residues of succinic acid and adipic acid. In embodiments, the PAP has a number average molecular weight (Mn) greater than 2000, or 3000 or more, or 5000 or more, or 7000 or more, or 8000 or more, or 9000 or more, or 9500 or more, or 10000 or more. In embodiments, the number average molecular weight (Mn) of the PAP ranges from 5000 to 20000, or 8000 to 20000, or 8000 to 15000, or 9000 to 12000. The molecular weight (and Mn) can be determined using gel permeation chromatography (GPC) with a refractive index detector using a methylene chloride solvent and polystyrene standards. In one embodiment, the PAP is poly(butylene succinate) with an Mn in the range of 5000 to 20000; or 10000 to 20000; or 15000 to 20000.

[0025] In an embodiment, the PAP can be any poly(butylene succinate) material. In an embodiment, the PAP is selected from poly(butylene succinate) random copolymers obtained from succinic acid or succinate, 1,4-butanediol, and other dicarboxylic acids or alkylene diols such as adipic acid, glutaric acid, succinic acid with a substituted side chain, suberic acid, 1,3-propanediol, and other substituted glycols. Examples of poly(butylene succinate) materials include poly(butylene succinate-co-butylene adipate) (PBSA), poly(butylene succinate-co-butylene terephthalate), poly(butylene succinate-co-propylene succinate), poly(butylene succinate-co-butylene methyl succinate), poly(butylene succinate-co-butylene dimethyl succinate), poly(butylene succinate-co-butylene phenyl succinate), and blends of poly(butylene succinate) including poly(butylene adipate), poly(ethylene succinate), and / or poly(ethylene adipate), but are not limited thereto. In one embodiment, the PAP is poly(butylene succinate) (PBS).

[0026] In certain embodiments, the MFR of the PAP measured at 190 °C with a load of 2.16 kg according to the ASTM D1238 test method is less than 30, or less than 25, or less than 20, or less than 15, or less than 10, or less than 6, or about 5 or less. In an embodiment, the MFR of the PAP is at least 0.5, or 1, or 2.

[0027] In an embodiment, the MFR (190°C, 2.16 kg) of the PAP is in the range of 0.5 to 30, or 0.5 to 25, or 0.5 to 20, or 0.5 to 15, or 0.5 to 10, or 0.5 to 6, or 0.5 to 5. In an embodiment, the elongation at break of the PAP is 100% or more, or 150% or more, or 200% or more, or 250% or more. In one embodiment, the cellulose ester composition comprises at least one PAP having an MFR (190°C, 2.16 kg) of 10 or less and an elongation at break of 100% or more. In a particular embodiment, the amount of PAP in the cellulose ester composition is 0.5 to 40% by weight, or 1 to 35% by weight, or 1 to 30% by weight, or 1 to 25% by weight, or 1 to 20% by weight, or 1 to 15% by weight, or 1 to 10% by weight, or 1 to 8% by weight, or 2 to 30% by weight, or 2 to 20% by weight, or 2 to 10% by weight, or 2 to 8% by weight, or 2.5 to 30% by weight, or 2.5 to 25% by weight, or 2.5 to 20% by weight, or 2.5 to 15% by weight, or 2.5 to 10% by weight, or 2.5 to 8% by weight, or 3 to 30% by weight, or 3 to 25% by weight, or 3 to 20% by weight, or 3 to 15% by weight, or 3 to 10% by weight, or 3 to 8% by weight, or 4 to 30% by weight, or 4 to 25% by weight, or 4 to 20% by weight, or 4 to 15% by weight, or 4 to 10% by weight, or 4 to 8% by weight, or 5 to 30% by weight, or 5 to 25% by weight, or 5 to 20% by weight, or 5 to 15% by weight, or 5 to 10% by weight, or 5 to 8% by weight, or 7 to 18% by weight, or 8 to 12% by weight based on the total cellulose ester composition.In certain embodiments, the composition comprises at least one impact modifier in an amount of from 1 to 20 wt%, or from 1 to 15 wt%, or from 1 to 10 wt%, or from 1 to 8 wt%, or from 2 to 15 wt%, or from 2 to 10 wt%, or from 2 to 8 wt%, or from 3 to 15 wt%, or from 3 to 10 wt%, or from 3 to 8 wt%, or from 4 to 15 wt%, or from 4 to 10 wt%, or from 4 to 8 wt%, and optionally at least one monomer plasticizer in addition to the PAP, and the amount of PAP in the cellulose ester composition is from 0.5 to 40 wt%, or from 1 to 35 wt%, or from 2 to 30 wt%, or from 2 to 20 wt%, or from 2 to 10 wt%, or from 3 to 10 wt%, or from 3 to 8 wt%, or from 3 to 7 wt%, or from 4 to 8 wt%, or from 4 to 7 wt%, or from 5 to 7 wt% based on the total cellulose ester composition.

[0028] Cellulose ester In embodiments, the cellulose ester utilized in the present invention can be any known in the art. The cellulose esters that can be used in the present invention generally include repeating units of the following structure: JPEG2025520397000002.jpg4593where R 1 , R 2 , and R 3It is independently selected from the group consisting of hydrogen and linear alkanoyl having 2 to 10 carbon atoms. In the case of cellulose esters, the substitution level is usually expressed by the degree of substitution (DS), which is the average number of non-OH substituents per anhydroglucose unit (AGU). Generally, conventional cellulose contains three hydroxy groups in each AGU unit that can be substituted; therefore, DS can take values from zero to 3. However, for low molecular weight cellulose mixed esters, due to the contribution of end groups, the total degree of substitution may slightly exceed 3. Natural cellulose is a large polysaccharide with a degree of polymerization of 250 to 5,000 even after pulping and purification. Therefore, the assumption that the maximum DS is 3.0 is approximately correct. However, when the degree of polymerization is low, such as in low molecular weight cellulose mixed esters, the end groups of the polysaccharide backbone become relatively more important, and the DS may be in a range exceeding 3.0. Low molecular weight cellulose mixed esters will be described in more detail later in this disclosure. Since DS is a statistical average value, even if the value is 1, it is not guaranteed that all AGUs have a single substituent. In some cases, there may be unsubstituted anhydroglucose units or those with two or three substituents, and usually, the value is a non-integer. The total DS is defined as the average number of all substituents per anhydroglucose unit. The degree of substitution per AGU may also mean a specific substituent such as hydroxy, acetyl, butyryl, or propionyl. In an embodiment, the degree of polymerization of the cellulose ester is lower than that of natural cellulose. In an embodiment, n is an integer in the range of 25 to 250, or 25 to 200, or 25 to 150, or 25 to 100, or 25 to 75.

[0029] In an embodiment, the cellulose ester used can be a cellulose triester or a secondary cellulose ester. Examples of cellulose triesters include, but are not limited to, cellulose triacetate, cellulose tripropionate, or cellulose tributyrate. Examples of secondary cellulose esters include cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate. For the purposes of the present disclosure, cellulose acetate (CA) includes cellulose acetate and / or cellulose diacetate unless otherwise specified.

[0030] In one embodiment, the cellulose ester can be selected from cellulose acetate (CA), cellulose propionate (CP), cellulose butyrate (CB), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose propionate butyrate (CPB), cellulose acetate isobutyrate (CAIB), etc., or combinations thereof. Examples of such cellulose esters are described in U.S. Pat. Nos. 1,698,049, 1,683,347, 1,880,808, 1,880,560, 1,984,147, 2,129,052, and 3,617,201, which are hereby incorporated by reference in their entirety to the extent not inconsistent with the description herein. In one embodiment, the cellulose ester is CAP.

[0031] In one embodiment, the cellulose ester can be selected from cellulose propionate (CP), cellulose butyrate (CB), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose propionate butyrate (CPB), cellulose tripropionate (CTP), or cellulose tributyrate (CTB), but not from cellulose acetate (CA).

[0032] In an embodiment, the cellulose ester has at least two glucose anhydride rings and can have from at least 50 to a maximum of 5,000 glucose anhydride rings. The number of glucose anhydride units per molecule is defined as the degree of polymerization (DP) of the cellulose ester. In an embodiment, the cellulose ester can have an intrinsic viscosity (IV) of about 0.2 to about 3.0 deciliters / gram, or about 0.5 to about 1.8, or about 1 to about 1.5 when measured at a temperature of 25 °C for a 0.25 g sample in 100 ml of a 60 / 40 weight ratio solution of phenol / tetrachloroethane. Examples of cellulose esters include, but are not limited to, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose propionate butyrate, and the like. In an embodiment, the cellulose ester useful in the present invention has a DS / AGU of about 2 to about 2.99, and the substituted ester can include any one of acetyl, propionyl, and butyryl, or any combination thereof. In another embodiment, the total DS / AGU ranges from about 2 to about 2.99, the DS / AGU of acetyl ranges from about 0 to 2.2, and the remaining ester groups include propionyl, butyryl, or a combination thereof.

[0033] In another embodiment, the total DS / AGU ranges from about 2 to about 2.99, the DS / AGU of acetyl ranges from about 0 to 1.2, and the remaining ester groups include propionyl, butyryl, or a combination thereof. In another embodiment, the total DS / AGU ranges from about 2 to about 2.99, the DS / AGU of acetyl ranges from about 0 to 0.5, and the remaining ester groups include propionyl, butyryl, or a combination thereof.

[0034] In certain embodiments, the cellulose ester has a total weight % of propionyl in the range of 5 to 52%, or 10 to 52%, or 15 to 52%, or 20 to 52%, or 25 to 52%, or 30 to 52%, or 35 to 52%, or 40 to 52%, or 45 to 52%, or 49 to 52%, or 5 to 50%, or 10 to 50%, or 15 to 50%, or 20 to 50%, or 25 to 50%, or 30 to 50%, or 35 to 50%, or 40 to 50%, or 45 to 50%, or 5 or more and less than 50%, or 10 or more and less than 50%, or 15 or more and less than 50%, or 20 or more and less than 50%, or 25 or more and less than 50%, or 30 or more and less than 50%, or 35 or more and less than 50%, or 40 or more and less than 50%, or 45 or more and less than 50%, or 35 or more and less than 50%, or 40 or more and less than 50%, or 45 or more and less than 50%, or 5 to 38%, or 10 to 38%, or 15 to 38%, or 20 to 38%, or 25 to 38%, or 30 to 38%, or 35 to 38%, or 5 to 35%, or 5 to 35%, or 10 to 35%, or 15 to 35%, or 20 to 35%, or 25 to 35%, or 30 to 35%, or 5 to 30%, or 10 to 30%, or 15 to 30%, or 20 to 30%, or 25 to 30%, or 5 to 20%, or 10 to 20% based on the total weight of the cellulose ester polymer.

[0035] In certain embodiments, the cellulose ester has a total weight % of butyryl in the range of 5 to 57%, or 10 to 57%, or 15 to 57%, or 20 to 57%, or 25 to 57%, or 30 to 57%, or 35 to 57%, or 40 to 57%, or greater than 40 to 57%, or 41 to 57%, or 45 to 57%, or 50 to 57%, or 5 to 55%, or 10 to 55%, or 15 to 55%, or 20 to 55%, or 25 to 55%, or 30 to 55%, or 35 to 55%, or 40 to 55%, or greater than 40 to 55%, or 41 to 55%, or 45 to 55%, or 50 to 55%, or 5 to 50%, or 10 to 50%, or 15 to 50%, or 20 to 50%, or 25 to 50%, or 30 to 50%, or 35 to 50%, or 40 to 50%, or greater than 40 to 50%, or 41 to 50%, or 45 to 50%, or 5 to 45%, or 10 to 45%, or 15 to 45%, or 20 to 45%, or 25 to 45%, or 30 to 45%, or 35 to 45%, or 40 to 45%, or greater than 40 to 45%, or 41 to 45%, or 5 to 35%, or 10 to 35%, or 15 to 35%, or 20 to 35%, or 25 to 35%, or 30 to 35%, or 5 or more and less than 32%, or 10 or more and less than 32%, or 15 or more and less than 32%, or 20 or more and less than 32%, or 25 or more and less than 32%, or 5 to 30%, or 10 to 30%, or 15 to 30%, or 20 to 30%, or 25 to 30% based on the total weight of the cellulose ester polymer.

[0036] In certain embodiments, the cellulose ester is cellulose propionate butyrate or cellulose acetate propionate butyrate, and the combined content of propionate and butyryl is in the range of 15% to 55%, or 15% to 50%, or 15% to 45%, or 15% to 40%, or 15% to 35%, or 15% to 30%, or 15% to 25%, or 15% to 20%, or 20% to 55%, or 20% to 50%, or 20% to 45%, or 20% to 40%, or 20% to 35%, or 20% to 30%, or 20% to 25%, or 25% to 55%, or 25% to 50%, or 25% to 45%, or 25% to 40%, or 25% to 35%, or 25% to 30%, or 30% to 55%, or 30% to 50%, or 30% to 45%, or 30% to 40%, or 30% to 35%, or 35% to 55%, or 35% to 50%, or 35% to 45%, or 35% to 40%, 40% to 55%, or 40% to 50%, or 40% to 45%, or 40% to 55%, or 40% to 55%, or 40% to 55%, or 40% to 45%, or 45% to 55%, or 45% to 50%, or 50% to 55% of the total weight of the polymer.

[0037] In one embodiment, the cellulose ester is CA. In certain embodiments, the cellulose ester has a total acetyl weight percentage in the range of 5 to 45%, or 10 to 45%, or 15 to 45%, or 20 to 45%, or 25 to 45%, or 30 to 45%, or 35 to 45%, or 40 to 45%, or 5 to 40%, or 10 to 40%, or 15 to 40%, or 20 to 40%, or 25 to 40%, or 30 to 40%, or 35 to 40%, or 5 to 35%, or 10 to 35%, or 15 to 35%, or 20 to 35%, or 25 to 35%, or 30 to 35%, or 5 to 30%, or 10 to 30%, or 15 to 30%, or 20 to 30%, or 25 to 30%, or 5 to 25%, or 10 to 25%, or 15 to 25%, or 20 to 25% based on the total weight of the cellulose ester polymer.

[0038] In certain embodiments, the cellulose ester has a total propionyl weight percentage in the range of 1 to 20%, or 1 to 15%, or 1 to 10%, or 1 to 5%, or 2 to 20%, or 2 to 15%, or 2 to 10%, or 2 to 5%, or 3 to 20%, or 3 to 15%, or 3 to 10%, or 3 to 5%, or 4 to 20%, or 4 to 15%, or 4 to 10%, or 5 to 20%, or 5 to 15%, or 5 to 10% based on the total weight of the cellulose ester polymer.

[0039] In certain embodiments, the cellulose ester has a total butyryl weight percentage in the range of 1 to 20%, or 1 to 15%, or 1 to 10%, or 1 to 5%, or 2 to 20%, or 2 to 15%, or 2 to 10%, or 2 to 5%, or 3 to 20%, or 3 to 15%, or 3 to 10%, or 3 to 5%, or 4 to 20%, or 4 to 15%, or 4 to 10%, or 5 to 20%, or 5 to 15%, or 5 to 10% based on the total weight of the cellulose ester polymer.

[0040] In an embodiment, any of the above cellulose esters may also contain up to 10%, preferably from 0.5% to 5%, of residual hydroxy units.

[0041] The cellulose ester can be produced by any method known in the art. Examples of processes for producing cellulose esters are described in Kirk - Othmer, "Encyclopedia of Chemical Technology", 5th Edition, Volume 5, Wiley - Interscience, New York (2004), pages 394 - 444. Cellulose, which is the starting material for producing cellulose esters, is available in various grades and sources such as cotton linter, softwood pulp, hardwood pulp, corn fiber and other agricultural resources, bacterial cellulose, etc.

[0042] One method for producing a cellulose ester is to mix cellulose with a suitable organic acid, acid anhydride, and catalyst to esterify the cellulose. The cellulose is then converted to cellulose triester. Next, ester hydrolysis is carried out by adding a water - acid mixture to the cellulose triester, and then filtration can be performed to remove gel particles or fibers. Next, water is added to the mixture to precipitate the cellulose ester. The cellulose ester can then be washed with water to remove reaction by - products and dehydrated and dried.

[0043] The cellulose triester to be hydrolyzed may have three substituents independently selected from alkanoyl groups having 2 to 10 carbon atoms. Examples of cellulose triesters include cellulose triacetate, cellulose tripropionate, and cellulose tributyrate, or mixed triesters of cellulose such as cellulose acetate propionate and cellulose acetate butyrate. These cellulose esters can be prepared by many methods known to those skilled in the art. For example, cellulose esters can be prepared by heterogeneously acylating cellulose in a mixture of a carboxylic acid and an anhydride in the presence of a catalyst such as H2SO4. Cellulose triesters can also be prepared by homogeneously acylating cellulose dissolved in a suitable solvent such as LiCl / DMAc or LiCl / NMP.

[0044] Those skilled in the art will understand that the commercial term "cellulose triester" also includes cellulose esters that are not completely substituted with acyl groups. For example, cellulose triacetate commercially available from Eastman Chemical Company, Kingsport, Tennessee, USA, typically has a DS of about 2.85 to about 2.99.

[0045] After esterifying cellulose to a triester, a portion of the acyl substituents can be removed by hydrolysis or alcoholysis to obtain a secondary cellulose ester. As described above, depending on the specific method used, the distribution of acyl substituents can be random or non-random. Secondary cellulose esters can also be prepared directly without hydrolysis by using a limited amount of acylating reagent. This process is particularly useful when the reaction is carried out in a solvent that dissolves cellulose. All of these methods produce cellulose esters useful in the present invention.

[0046] In one embodiment, the secondary cellulose ester useful in the present invention has an absolute weight average molecular weight (Mw) of about 5,000 to about 400,000 as measured by gel permeation chromatography (GPC) according to ASTM D6474. To calculate the absolute weight average molecular weight value (Mw) of the CE, the following method is used. The solvent is THF stabilized with a BHT preservative. The equipment for the THF / cellulose ester procedure consists of the following Agilent 1200 series components: a degasser, an isocratic pump, an autosampler, a column oven, a UV / Vis detector, and a refractive index detector. The test temperature is 30 °C and the flow rate is 1.0 ml / min. Prepare a sample solvent of 25 mg of cellulose ester in 10 ml of THF containing a BHT preservative and a 10 μl toluene flow marker. The injection volume is 50 μl. The column set is 5 μm PLgel, Guard + Mixed C + OligoPore manufactured by Polymer Laboratories. Detection is performed by refractive index. The calibrant is a monodisperse polystyrene standard from Polymer Laboratories, Mw = 580 - 3,220,000. The universal calibration parameters are as follows: PS (K = 0.0001280, a = 0.7120) and CE (K = 0.00007572, a = 0.8424). The above universal calibration parameters were determined by light scattering and viscosity measurements to obtain the correct weight average molecular weight. In a further embodiment, Mw is from about 15,000 to about 300,000. In even further embodiments, Mw ranges from about 10,000 to about 250,000; from about 15,000 to 200,000; from about 20,000 to about 150,000; from about 50,000 to about 150,000, or from about 70,000 to about 120,000.

[0047] In an embodiment, the polymer-based resin comprises a cellulose ester having an absolute weight average molecular weight in the range of about 40,000 Da to about 200,000 Da, measured according to ASTM D5296, using tetrahydrofuran as a solvent at a flow rate of 1 mL / min. In certain embodiments, the cellulose ester has an absolute weight average molecular weight, measured according to ASTM D5296, using tetrahydrofuran as a solvent at a flow rate of 1 mL / min, in the range of about 50,000 Da to about 200,000 Da, or 50,000 Da to about 170,000 Da, or 50,000 Da to about 120,000 Da, or 50,000 Da to about 90,000 Da, or 60,000 Da to about 200,000 Da, or 60,000 Da to about 170,000 Da, or 60,000 Da to about 120,000 Da, or 60,000 Da to about 90,000 Da, or 90,000 Da to about 170,000 Da, or 90,000 Da to about 120,000 Da, or 120,000 Da to about 170,000 Da, or 120,000 Da to about 200,000 Da.

[0048] Commercially available secondary cellulose esters can be prepared by the initial acid-catalyzed heterogeneous acylation of cellulose to form cellulose triesters. After a homogeneous solution is obtained in the corresponding carboxylic acid of the cellulose triester, the cellulose triester is hydrolyzed until the desired degree of substitution is obtained. After isolation, a random secondary cellulose ester is obtained. That is, the relative degree of substitution (RDS) of each hydroxy is approximately equal.

[0049] Some examples of cellulose esters that can be useful in the present invention can be prepared using techniques known in the art and are available from Eastman Chemical Company, Kingsport, Tennessee, USA, such as, for example, Eastman™ cellulose acetate propionate CAP 482-20, Eastman™ cellulose acetate propionate CAP 141-20, Eastman™ cellulose acetate butyrate CAB 381-20, cellulose acetate butyrate CAB 171-15, and Eastman™ cellulose acetate CA 398-30, etc.

[0050] In an embodiment, the cellulose ester utilized in the present invention can also contain chemical functionality and is described herein as a derivatized, modified, or functionalized cellulose ester. The functionalized cellulose ester can be produced by reacting the free hydroxy groups of the cellulose ester with a bifunctional reactant having one linking group for grafting to the cellulose ester and one functional group for providing a new chemical group to the cellulose ester. Examples of such bifunctional reactants include succinic anhydride which is linked via an ester bond to provide acid functionality; mercaptopropyltrimethoxysilane which is linked via an alkoxysilane bond to provide mercapto functionality; and isocyanatoethyl methacrylate which is linked via a urethane bond to provide methacrylate functionality.

[0051] In one embodiment, the functionalized cellulose ester is produced by reacting the free hydroxy groups of the cellulose ester with a bifunctional reactant to produce a cellulose ester having at least one functional group selected from the group consisting of unsaturated (double bond), carboxylic acid, acetoacetic acid, acetoacetic acid imide, mercapto, melamine, and long-chain alkyl chain.

[0052] Bifunctional reactants for producing cellulose esters containing unsaturated (double bond) functional groups are described in U.S. Patent Nos. 4,839,230, 5,741,901, 5,871,573, 5,981,738, 4,147,603, 4,758,645, and 4,861,629, all of which are incorporated by reference to the extent not inconsistent with the description herein. In one embodiment, the cellulose ester containing unsaturation is produced by reacting a cellulose ester containing residual hydroxy groups with an acrylic compound and m-isopropenyl-α,α'-dimethylbenzyl isocyanate. The grafted cellulose ester is a urethane-containing product having pendant (meth)acrylate and α-methylstyrene moieties. In another embodiment, the cellulose ester containing unsaturation is produced by reacting maleic anhydride with a cellulose ester in the presence of an alkaline earth metal or ammonium salt of a lower alkyl monocarboxylic acid catalyst, and at least one saturated monocarboxylic acid has 2 to 4 carbon atoms. In another embodiment, the cellulose ester containing unsaturation is produced from the reaction product of (a) at least one cellulose polymer having isocyanate-reactive hydroxy functionality, and (b) at least one hydroxy-reactive poly(α,β ethylenically unsaturated) isocyanate.

[0053] Bifunctional reactants for producing cellulose esters having carboxylic acid functionality are described in U.S. Patent Nos. 5,384,163, 5,723,151, and 4,758,645, all of which are incorporated by reference to the extent not inconsistent with the description herein. In one embodiment, a cellulose ester having carboxylic acid functionality is produced by reacting a cellulose ester with a monoester or diester of maleic acid or fumaric acid, thereby obtaining a cellulose derivative having double bond functionality. In another embodiment, a cellulose ester containing carboxylic acid functionality has a first and a second residue, the first residue being the residue of a cyclic dicarboxylic anhydride and the second residue being the residue of a lipophilic monocarboxylic acid and / or the residue of a hydrophilic monocarboxylic acid. In yet another embodiment, a cellulose ester having carboxylic acid functionality is cellulose acetate phthalate, which can be prepared by reacting cellulose acetate with phthalic anhydride.

[0054] Bifunctional reactants for producing cellulose esters having acetoacetic acid functionality are described in U.S. Patent No. 5,292,877 and are incorporated by reference to the extent not inconsistent with the description herein. In one embodiment, a cellulose ester having acetoacetic acid functionality is produced by contacting (i) cellulose, (ii) diketene, alkyl acetoacetate, 2,2,6-trimethyl-4H 1,3-dioxin-4-one, or mixtures thereof, and (iii) lithium chloride with a solubilizing amount of a solvent system comprising a carboxamide selected from the group consisting of 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, or mixtures thereof.

[0055] Bifunctional reactants for producing cellulose esters having acetoacetic imide functionality are described in U.S. Patent No. 6,369,214, which is incorporated herein by reference to the extent not inconsistent with the description herein. Cellulose esters containing acetoacetic imide functionality are reaction products of a cellulose ester, at least one acetoacetyl group, and an amine-functional compound containing at least one primary amine.

[0056] Bifunctional reactants for producing cellulose esters having mercapto functionality are described in U.S. Patent No. 5,082,914, which is incorporated herein by reference to the extent not inconsistent with the description herein. In one embodiment, the cellulose ester is grafted with a silicon-containing thiol component that is commercially available or can be prepared by procedures known in the art. Examples of silicon-containing thiol compounds include, but are not limited to, (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)-dimethyl-methoxysilane, (3-mercaptopropyl)dimethoxymethylsilane, (3-mercaptopropyl)dimethylchlorosilane, (3-mercaptopropyl)dimethylethoxysilane, (3-mercaptopropyl)diethoxymethylsilane, and (3-mercaptopropyl)triethoxysilane.

[0057] Bifunctional reactants for producing cellulose esters having melamine functionality are described in U.S. Patent No. 5,182,379, which is incorporated herein by reference to the extent not inconsistent with the description herein. In one embodiment, a cellulose ester having melamine functionality is prepared by reacting a cellulose ester with a melamine compound to form a grafted cellulose ester having a melamine moiety grafted to the anhydroglucose ring backbone of the cellulose ester. In one embodiment, the melamine compound is selected from the group consisting of methylol ethers of melamine and aminoplast resins.

[0058] Bifunctional reactants for producing cellulose esters having long-chain alkyl chain functionality are described in U.S. Patent No. 5,750,677 and are incorporated herein by reference to the extent not inconsistent with the description herein. In one embodiment, a cellulose ester having long-chain alkyl chain functionality is produced by the reaction of cellulose with an acylating reagent using a titanium-containing specific substance in a carboxamide diluent or a urea-based diluent. The cellulose ester having long-chain alkyl chain functionality can be selected from the group consisting of cellulose acetate hexanoate, cellulose acetate nonanoate, cellulose acetate laurate, cellulose palmitate, cellulose acetate stearate, cellulose nonanoate, cellulose hexanoate, cellulose hexanoate propionate, and cellulose nonanoate propionate.

[0059] Impact modifier In an embodiment, the impact modifier can be any material that has been found to increase the impact strength of the cellulose ester composition. In one embodiment, the impact modifier can be any polymeric material classified as an elastomer having a glass transition temperature (Tg) below room temperature. The Tg can be measured, for example, at a scanning rate of 20 °C / min using a TA 2100 Thermal Analyst Instrument in accordance with ASTM D3418. Some classes of impact modifiers apply to this description.

[0060] In one embodiment, the impact modifier can be selected from the class of materials known as modified polyolefins (or olefin copolymers). In this class, the olefin is copolymerized with additional monomers that limit the crystallization of the polymer, increase the amount of chains with a Tg below room temperature, and lower the modulus of elasticity to less than 500 MPa. Examples of modified olefins include ethylene methyl acrylate (EMA) or ethylene glycidyl methyl acrylate (EGMA) (including, for example, Elvaloy 4051, Lotader 3410, and Lotader 8900), ethylene butyl acetate (EBA), ethylene vinyl acetate (EVA) (including, for example, Levamelt 500, Levamelt 600, Levamelt 700, Levamelt 800, Elvax 40W, Evatane 28-40, Evatane 40-55, Evatane 18-150, Bynel E418, and Bynel 3101), ethylene ethyl acetate (EEA), ethylene propylene diene monomer-based elastomers (EPDM) (including, for example, Royaltuf 498), and ethylene propylene rubber elastomers (EPR).

[0061] In one embodiment, the impact modifier may be a block copolymer, where the Tg of at least one segment of the chain is lower than room temperature, which is called the soft segment, and the Tg or Tm of at least one segment of the chain is higher than room temperature, which is called the hard segment. These block copolymers are generally also called thermoplastic elastomers (TPE). Examples of this class of block copolymers include styrenic materials such as poly(styrene-butadiene-styrene) (SBS), poly(styrene-ethylene-butylene-styrene) (SEBS), and styrene-isoprene rubber elastomers (SIS) (including, for example, Kraton G1657MS, Kraton FG1901 G, and Kraton FG1924 G); thermoplastic urethanes (TPU) (including, for example, Elastolan 1170Z, Estane 2355, Estane ALR CL87A, and Estane ALR 72A); polyester ether copolymers (including, for example, Ecdel 9966 and Hytrel 3078) or polyamide ether copolymers (including, for example, Pebax 5533).

[0062] In one embodiment, the impact modifier can be selected from the class of emulsion preparation materials known as core-shell impact modifiers. In one embodiment, the impact modifier is an MBS core-shell impact modifier such as methacrylate-butadiene-styrene having a core made from a butadiene-styrene copolymer and a shell made from a methyl methacrylate-styrene copolymer. In another embodiment, the impact modifier is an acrylic core-shell impact modifier having a core made from an acrylic polymer such as butyl acrylate or styrene butyl acrylate and a shell made from a polymethyl methacrylate or styrene methyl methacrylate copolymer.

[0063] In an embodiment, the MBS impact modifier can include a graft polymer composition including a polymer or copolymer of butadiene in an amount of 10 to 70% by weight, and a graft of methyl (meth) acrylate and a crosslinking agent, styrene, and optionally a crosslinking agent with methyl (meth) acrylate.

[0064] Monomers suitable for polymerization with conjugated diolefins and preferably butadiene include alkenyl aromatic compounds and preferably vinyl aromatic compounds such as styrene, divinylbenzene, α-methylstyrene, vinyltoluene, hydrogenated styrene; lower (C2-C12) alkyl acrylates such as ethyl acrylate, n-propyl acrylate, n-butyl acrylate, Z-methylbutyl acrylate, 3-methylbutyl acrylate, amyl acrylate, n-hexyl acrylate, Z-ethylhexyl acrylate; lower (C2-C12) alkyl (meth) acrylates; acrylonitrile; olefins; or any combination of the foregoing.

[0065] Suitable crosslinking agents include divinylbenzene; di(meth)acrylate; diacrylates such as diacrylate of mono, di or polyethylene glycol; their (meth)acrylates; divinyl sulfide; divinyl ether; vinyl acrylate; vinyl (meth)acrylate; trivinylbenzene; trimethylolpropane; tri(meth)acrylate; triallyl cyanurate and triallyl isocyanurate.

[0066] In one embodiment, the MBS core-shell impact modifier can include a copolymer of butadiene and styrene, most preferably a terpolymer of butadiene, styrene and divinylbenzene. The relative amounts of the monomers that make up the copolymer substrate can vary, but the butadiene component will typically be from about 30 to 100 parts by weight, the styrene component from 0 to about 70 parts by weight, and the divinylbenzene component from 0 to about 5 parts by weight, based on a total of 100 parts by weight of butadiene, styrene, and divinylbenzene. In one embodiment, the copolymer substrate can include, on the same basis, from about 50 to about 90 parts by weight of butadiene, from about 10 to about 50 parts by weight of styrene, and from 0 to about 5 parts by weight of divinylbenzene, and most preferably, on the same basis, from about 65 to about 85 parts by weight of butadiene, from about 15 to about 35 parts by weight of styrene, and from about 0.5 to about 2.0 parts by weight of divinylbenzene.

[0067] Examples of methacrylate-butadiene-styrene core-shell polymers are described in U.S. Pat. Nos. 4,446,585, 5,534,594, and 6,331,580, but are not limited thereto. MBS core-shell impact modifiers are available as Kane Ace B564 from Kaneka, Clearstrength from Arkema, Metablen C and Metablen E from Mitsubishi Chemical, Paraloid from Dow, and Visiomer from Evonik.

[0068] In one embodiment, the core-shell impact modifier is an acrylic impact modifier that includes from about 25 to 95 weight percent of a first elastomeric phase polymerized from a monomer system that includes from about 75 to 99.8 weight percent (C1 to C6) alkyl acrylate, from 0.1 to 5 weight percent crosslinking monomer, and from 0.1 to 5 weight percent graft bonding monomer, and from about 75 to 5 weight percent of a final rigid thermoplastic phase that does not contain epoxy groups and is polymerized in the presence of the elastomeric phase.

[0069] Examples of useful acrylates include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc. In some embodiments, the acrylate is n-butyl acrylate and ethyl acrylate. The graft-bonding monomer is defined as a polyethylene unsaturated monomer having both a highly reactive double bond and a low-reactive double bond. The highly reactive double bond tends to polymerize during the first-stage monomer polymerization, and the remaining double bonds are polymerized during the next-stage polymerization, whereby the first-stage polymer and the second-stage polymer tend to be graft-bonded. In some embodiments, the graft-bonding monomer is allyl methacrylate, allyl acrylate, and diallyl maleate. In one embodiment, 0.05 to 3% of the graft-bonding monomer is present based on the first-stage monomer system. The crosslinking monomer is also preferably present in an amount of about 0.05 to 3% by weight, generally based on the first-stage monomer system, and is defined as a polyethylene unsaturated monomer having at least two double bonds with substantially equal reactivity so as to cause crosslinking in the first-stage polymerization. Examples of typical crosslinking monomers include 1,3-butylene diacrylate, 1,3-butylene dimethacrylate, divinylbenzene, etc.

[0070] "Epoxy functionality" means an epoxy unit pendant from the final-stage polymer. In some embodiments, epoxy functionality is incorporated into the final-stage polymer by using an epoxy-containing monomer such as glycidyl acrylate or glycidyl methacrylate in the final-stage monomer mixture.

[0071] Examples of acrylic core-shell polymers include, but are not limited to, those described in U.S. Patent Nos. 3,448,173, 3,655,825, and 3,853,968. Examples of suitable acrylic impact modifiers include Kane Ace ECO 100 and M570 from Kaneka, Durastrength from Arkema, Elvaloy and Elvaloy HP from DuPont, Metablen W from Mitsubishi Chemical, and Paraloid from Dow.

[0072] In one class of this embodiment, the impact modifier is an ABS core-shell impact modifier having a core made from a butadiene-styrene copolymer and a shell made from an acrylonitrile-styrene copolymer. Examples of ABS core-shell impact modifiers include Blendex from Galata Chemicals and Elix from Elix Polymers.

[0073] In one class of this embodiment, the impact modifier is a silicone-acrylic core-shell impact modifier having a core made from a silicone-acrylic rubber and a shell made from a PMMA copolymer or a methyl methacrylate-styrene copolymer. An example of a silicone-acrylic core-shell impact modifier includes Metablen S from Mitsubishi Chemical.

[0074] In one embodiment, the impact modifier has a neutral acidity. This is thought to help prevent the cellulose ester from decomposing during the melt processing of the composition.

[0075] In one embodiment, the impact modifier can be either a non-reactive impact modifier or a reactive impact modifier, or a combination of both. The impact modifier used can also improve the mechanical and physical properties of the cellulose ester composition.

[0076] In one embodiment where a non-reactive impact modifier is used, the impact modifier comprises a first polymer chain segment that is more chemically or physically compatible with the cellulose ester than other polymer chain segments. In one embodiment, the first segment comprises polar functional groups that provide compatibility with the cellulose ester, including but not limited to polar functional groups such as ethers, esters, amides, alcohols, amines, ketones, and acetals. Compatibility is defined by the preferential interaction of the first polymer chain segment with the cellulose ester polymer over the second segment and can mean molecular-scale or microscale interactions. The first segment can be composed of the following oligomers or polymers: cellulose esters; cellulose ethers; polyoxyalkylenes such as polyoxyethylene, polyoxypropylene, polyoxybutylene; polyglycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol; polyesters such as polycaprolactone, polylactic acid, aliphatic polyesters, aliphatic-aromatic copolyesters; polyacrylates and polymethacrylates; polyacetals; polyvinylpyrrolidone; ethylene vinyl acetate; polyvinyl acetate; and polyvinyl alcohol. In one embodiment, the first segment is ethylene vinyl acetate; polyoxyethylene or polyvinyl alcohol.

[0077] In an embodiment, the second segment can be either a saturated hydrocarbon group or an unsaturated hydrocarbon group, or can include both a saturated hydrocarbon group and an unsaturated hydrocarbon group. The second segment can be an oligomer or a polymer. In one embodiment, the second segment of the non-reactive impact modifier is selected from the group consisting of polyolefins, polydienes, polyaromatics, and copolymers. An example of a polyaromatic second segment is polystyrene. An example of a copolymer second segment is styrene / butadiene copolymer.

[0078] The first and second segments of the non-reactive impact modifier can be in a diblock, triblock, branched or comb structure. The molecular weight, weight average (Mw), of the non-reactive impact modifier can range from about 300 to about 20,000, or from about 500 to about 10,000, or from about 1,000 to about 5,000. The segment ratio of the non-reactive impact modifier can range such that the polar first segment is from about 15 to about 85% and the non-polar second segment is from about 15 to about 85%.

[0079] Examples of non-reactive impact modifiers include, but are not limited to, ethoxylated alcohols, ethoxylated alkylphenols, ethoxylated fatty acids, polyethylene vinyl acetate, block polymers of propylene oxide and ethylene oxide, ethylene / propylene terpolymers, functionalized polyolefins, polyglycerol esters, polysaccharide esters, and sorbitan esters. Examples of ethoxylated alcohols include C 11 -C 15 secondary alcohol ethoxylates, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and C ethoxylated with ethylene oxide 12 -C 14 natural straight-chain alcohols, etc. C 11 -C 15 The secondary ethoxylate is available from the Dow Chemical Company as Dow Tergitol® 15S. Polyoxyethylene cetyl ether and polyoxyethylene stearyl ether are available from Imperial Chemical Industries (ICI Surfactants) as products of the Brij® series. C ethoxylated with ethylene oxide 12 -C 14Natural straight-chain alcohols are available from the Genapol® product series of Hoechst Celanese. Examples of ethoxylated alkylphenols include octylphenoxypoly(ethyleneoxy)ethanol and nonylphenoxypoly(ethyleneoxy)ethanol. Octylphenoxypoly(ethyleneoxy)ethanol is available from Rhodia as products of the Igepal® CA series, and nonylphenoxypoly(ethyleneoxy)ethanol is available as products of the Igepal CO series of Rhodia or Tergitol® NP of Dow Chemical Company. Ethoxylated fatty acids include polyethylene glycol monostearate or monolaurate, which are available from the Nopalcol® series of products of Henkel. Block polymers of propylene oxide and ethylene oxide are available from the Pluronic® series of products of BASF. Polyglycerol esters are available from the Drewpol™ series of products of Stepan. Polysaccharide esters are available from Henkel as products of the Glucopon® series, which are alkyl polyglucosides. Sorbitan esters are available from ICI as products of the Tween® series.

[0080] In another embodiment, the non-reactive impact modifier can be synthesized in situ in the cellulose ester composition by reacting a compound compatible with the cellulose ester. These compounds are, for example, telechelic oligomers and are defined as prepolymers that can further polymerize or enter into other reactions via reactive end groups. In one embodiment, these in situ impact modifiers can have a higher molecular weight, weight average (Mw), of from about 10,000 to about 1,000,000.

[0081] In another embodiment, the impact modifier may be reactive. A reactive impact modifier may include a polymer or oligomer that is compatible with one component of the composition and functionality that can react with another component of the composition. In embodiments, there are two types of reactive impact modifiers that can be used. The first reactive impact modifier has a hydrocarbon chain that is compatible with the cellulose ester and also has functionality that can react with the cellulose ester. Such functional groups include, but are not limited to, carboxylic acids, anhydrides, acid chlorides, epoxides, and isocyanates. Specific examples of this type of reactive impact modifier include long-chain fatty acids such as stearic acid (octadecanoic acid); long-chain fatty acid chlorides such as stearoyl chloride (octadecanoyl chloride); long-chain fatty acid anhydrides such as stearic anhydride (octadecanoic anhydride); epoxidized oils and fatty acid esters; styrene maleic anhydride copolymers; maleic anhydride grafted polypropylene; copolymers of maleic anhydride with olefins and / or acrylic acid esters such as terpolymers of ethylene, acrylic acid esters, and maleic anhydride; and copolymers of glycidyl methacrylate with olefins and / or acrylic acid esters such as terpolymers of ethylene, acrylic acid esters, and glycidyl methacrylate, but are not limited thereto.

[0082] Reactive impact modifiers are available as Sartomer / Cray Valley's SMA (trademark) 3000 styrene maleic anhydride copolymer, Eastman Chemical Company's Eastman G-3015 (registered trademark) maleic anhydride grafted polypropylene, Westlake Chemical's Epolene (registered trademark) E-43 maleic anhydride grafted polypropylene, Arkema's Lotader (registered trademark) MAH 8200 random terpolymer of ethylene, acrylic ester, and maleic anhydride, Lotader (registered trademark) GMA AX 8900 random terpolymer of ethylene, acrylic ester, and glycidyl methacrylate, and Lotader (registered trademark) GMA AX 8840 random terpolymer of ethylene, acrylic ester, and glycidyl methacrylate.

[0083] Reactive polyolefin impact modifiers are available as Lotader, Fusabond, Elvaloy PTW, Lotryl, Elvaloy AC, and InterLoy.

[0084] The second type of reactive impact modifier has a polar chain compatible with the cellulose ester and also has functionality capable of reacting with the cellulose ester. Examples of these types of reactive impact modifiers include cellulose esters or polyethylene glycols having an olefin or thiol functional group. Reactive polyethylene glycol impact modifiers having an olefin functional group include, but are not limited to, polyethylene glycol allyl ether and polyethylene glycol acrylate. An example of a reactive polyethylene glycol impact modifier having a thiol functionality is polyethylene glycol thiol. An example of a reactive cellulose ester impact modifier is mercaptoacetate cellulose ester.

[0085] In embodiments, the amount of the impact modifier in the cellulose ester composition can range from about 1 wt% to about 15 wt%, or from about 2 wt% to about 10 wt%, or from about 4 wt% to about 10 wt%, or from about 4 wt% to about 8 wt%, or from about 5 wt% to about 10 wt% based on the weight of the cellulose ester composition.

[0086] Friction modifier In embodiments, the friction modifier can be any material that has been found to lower the static and / or dynamic coefficient of friction of the cellulose ester composition compared to the base resin (i.e., the composition without the friction modifier). In embodiments, the friction modifier can lower the static and / or dynamic coefficient of friction of the cellulose ester composition while maintaining or substantially not decreasing the physical properties of the base resin.

[0087] In embodiments, one or more friction modifiers can be selected from a wide range of waxes and siloxanes. Waxes useful in the cellulose ester composition can include higher alkanes and lipids that are lipophilic malleable solids at room temperature (i.e., 23 °C). Natural waxes are found in plants and animals and also in petroleum products. In one embodiment, the wax is a mixture of saturated alkanes, naphthenes, and alkyl- and naphthene-substituted aromatic compounds. In another embodiment, the wax is montan wax, which is extracted from certain coal and lignite sources. In another embodiment, the wax can be rice bran wax (RBW), such as RBW obtained from crude rice bran such as LICOCARE® RBW Vita additive (manufactured by Clariant). In another embodiment, the wax can be a polyolefin wax. In some embodiments, naturally occurring waxes such as beeswax, which is mainly myricyl palmitate, cetyl palmitate, lanolin, carnauba wax, can be used.

[0088] In an embodiment, the one or more friction modifiers may include one or more siloxanes. A siloxane is a compound containing Si-O-Si bonds. Examples include compounds having the structures of H(OSiH2)nOH and (OSiH2)n. In other embodiments, the siloxane is a silicon or polysiloxane having the structure of (-RSi-O-SiR-), where R is an organic group such as an alkyl or aryl group. Examples of such polysiloxanes include polydimethylsiloxane or "PDMS" and polyphenylsiloxane. Examples of commercially available such waxes and siloxanes include Genioplast S, a pelletized silicone gum formulation from Wacker Chemie AG; Tegomer H-Si, a polyester-modified siloxane from Evonik Industries AG (e.g., H-Si 6441 P); Dowsil™ Si powder resin modifier from Dow Chemical Company (e.g., DowSil 4-7081); and Loxiol P (e.g., P861), a polyol ester available from Emery Oleochemicals GmbH.

[0089] In embodiments, the wax and / or siloxane utilized as the friction modifier component may be present in an amount of from about 0.1 to about 15, or from about 0.1 to about 12, or from about 0.1 to about 10, or from about 0.1 to about 8, or from about 0.1 to about 6, or from about 0.1 to about 5, or from about 0.1 to about 4, or from about 0.1 to about 3, or from about 0.1 to about 2, or from about 0.1 to about 1, or from about 0.2 to about 5, or from about 0.2 to about 4, or from about 0.2 to about 3, or from about 0.2 to about 2, or from about 0.2 to about 1, or from about 0.3 to about 5, or from about 0.3 to about 4, or from about 0.3 to about 3, or from about 0.3 to about 2, or from about 0.3 to about 1.5, or from about 0.4 to about 2, or from about 0.4 to about 1.5, or from about 0.5 to about 5, or from about 0.5 to about 4, or from about 0.5 to about 3, or from about 0.5 to about 2, or from about 0.5 to about 1.5, or from about 0.5 to about 1 weight percent of the weight of the cellulose ester composition.

[0090] In embodiments, the friction modifier component comprises one or more siloxanes, which are present in an amount of from about 0.1 to about 10, or from about 0.1 to about 8, or from about 0.1 to about 6, or from about 0.1 to about 5, or from about 0.1 to about 4, or from about 0.1 to about 3, or from about 0.1 to about 2, or from about 0.1 to about 1, or from about 0.2 to about 5, or from about 0.2 to about 4, or from about 0.2 to about 3, or from about 0.2 to about 2, or from about 0.2 to about 1, or from about 0.3 to about 5, or from about 0.3 to about 4, or from about 0.3 to about 3, or from about 0.3 to about 2, or from about 0.3 to about 1.5, or from about 0.4 to about 2, or from about 0.4 to about 1.5, or from about 0.5 to about 5, or from about 0.5 to about 4, or from about 0.5 to about 3, or from about 0.5 to about 2, or from about 0.5 to about 1.5, or from about 0.5 to about 1 weight percent of the weight of the cellulose ester composition.

[0091] Plasticizer In one embodiment, the composition can include a plasticizer. The plasticizer used can be any plasticizer known in the art that can reduce the glass transition temperature and / or the melt viscosity of the cellulose ester to improve the melt processing characteristics. The plasticizer can be any plasticizer suitable for use with the cellulose ester. The plasticizer level should be lower than the normal (or typical) plasticizer level of the cellulose ester, and as a result, the composition has a higher Tg (or HDT), good toughness, and good fluidity than a fully plasticized cellulose ester composition. In an embodiment, the plasticizer is present in an amount that does not substantially reduce the Tg (or HDT) of the cellulose ester composition compared to a similar composition without the plasticizer. In an embodiment, as a result of including the plasticizer, the Tg (or HDT) does not change (e.g., decrease) by more than 20%, 15%, 10%, 5%, or 2%.

[0092] The plasticizer can be either of monomeric structure or polymeric structure. In one embodiment, the plasticizer is at least one selected from the group consisting of aromatic phosphate plasticizers, alkyl phosphate plasticizers, dialkyl ether diester plasticizers, tricarboxylic acid ester plasticizers, high molecular weight polyester plasticizers, polyglycol diester plasticizers, polyester resin plasticizers, aromatic diester plasticizers, aromatic triester plasticizers, aliphatic diester plasticizers, carbonate plasticizers, epoxidized ester plasticizers, epoxidized oil plasticizers, benzoic acid plasticizers, polyol benzoic acid plasticizers adipic acid plasticizers, phthalic acid plasticizers, glycolic acid ester plasticizers, citric acid ester plasticizers, hydroxy-functional plasticizers, or solid amorphous resin plasticizers.

[0093] In one embodiment, the plasticizer can be selected from at least one of the following: triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, dibenzyl phthalate, butyl phthalyl butyl glycolate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl-tri-n-butyl citrate, and acetyl-tri-n-(2-ethylhexyl) citrate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, or triethylene glycol dibenzoate.

[0094] In another embodiment, the plasticizer can be selected from at least one of the following: esters comprising: (i) acid residues comprising one or more residues of phthalic acid, adipic acid, trimellitic acid, succinic acid, benzoic acid, azelaic acid, terephthalic acid, isophthalic acid, butyric acid, glutaric acid, citric acid or phosphoric acid; and (ii) alcohol residues comprising one or more residues of an aliphatic, alicyclic or aromatic alcohol having up to about 20 carbon atoms.

[0095] In another embodiment, the plasticizer can be selected from at least one of the following: esters comprising: (i) at least one acid residue selected from the group consisting of phthalic acid, adipic acid, trimellitic acid, succinic acid, benzoic acid, azelaic acid, terephthalic acid, isophthalic acid, butyric acid, glutaric acid, citric acid and phosphoric acid; and (ii) at least one alcohol residue selected from the group consisting of aliphatic, alicyclic, and aromatic alcohols having up to about 20 carbon atoms.

[0096] In another embodiment, the plasticizer can contain an alcohol residue, and the alcohol residue is at least one selected from the following: stearyl alcohol, lauryl alcohol, phenol, benzyl alcohol, hydroquinone, catechol, resorcinol, ethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, and diethylene glycol.

[0097] In another embodiment, the plasticizer can be selected from at least one of the following: benzoate, phthalate, phosphate, arylene-bis(diaryl phosphate), and isophthalate. In another embodiment, the plasticizer contains diethylene glycol dibenzoate, which is abbreviated as "DEGDB" herein.

[0098] In another embodiment, the plasticizer can be selected from at least one of the following: C 2~10 dicarboxylic acid residues such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid; and C 2~10 aliphatic polyesters containing diol residues.

[0099] In another embodiment, the plasticizer can contain a diol residue that can be a residue of at least one of the following C2-C 10 diols: ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,5-pentylene glycol, triethylene glycol, and tetraethylene glycol.

[0100] In another embodiment, the plasticizer can include polyglycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol. These can range from low molecular weight dimers and trimers to high molecular weight oligomers and polymers. In one embodiment, the molecular weight of the polyglycol can range from about 200 to about 2000.

[0101] In another embodiment, the plasticizer includes at least one of the following: Resoflex® R296 plasticizer, Resoflex™ 804 plasticizer, SHP (sorbitol hexapropionate), XPP (xylitol pentapropionate), XPA (xylitol pentaacetate), GPP (glucose pentaacetate), GPA (glucose pentapropionate), and APP (arabitol pentapropionate).

[0102] In another embodiment, the plasticizer includes one or more of the following: A) from about 5 to about 95 wt% of a C2-C 12 carbohydrate organic ester (where the carbohydrate contains from about 1 to about 3 monosaccharide units); and B) from about 5 to about 95 wt% of a C2-C 12 polyol ester (where the polyol is derived from a C5 or C6 carbohydrate). In one embodiment, the polyol ester does not include polyol acetates or polyol acetates.

[0103] In another embodiment, the plasticizer includes at least one carbohydrate ester, and the carbohydrate portion of the carbohydrate ester is derived from one or more compounds selected from the group consisting of glucose, galactose, mannose, xylose, arabinose, lactose, fructose, sorbose, sucrose, cellobiose, cellotriose, and raffinose.

[0104] In another embodiment, the plasticizer comprises at least one carbohydrate ester, and the carbohydrate portion of the carbohydrate ester comprises one or more of α-glucose pentaacetate, β-glucose pentaacetate, α-glucose pentapropionate, β-glucose pentapropionate, α-glucose pentabutyrate, and β-glucose pentabutyrate.

[0105] In another embodiment, the plasticizer comprises at least one carbohydrate ester, and the carbohydrate portion of the carbohydrate ester comprises an α-anomer, a β-anomer, or a mixture thereof.

[0106] In another embodiment, the plasticizer can be selected from at least one of the following: propylene glycol dibenzoate, glyceryl tribenzoate, diethylene glycol dibenzoate, triethylene glycol dibenzoate, dipropylene glycol dibenzoate, and polyethylene glycol dibenzoate.

[0107] In another embodiment, the plasticizer can be a solid amorphous resin. These resins can contain a certain degree of aromatic or polar functionality and can reduce the melt viscosity of the cellulose ester. In one embodiment, the plasticizer can be, for example, rosin; hydrogenated rosin; stabilized rosin, and their monofunctional alcohol esters or polyol esters; modified rosins including, but not limited to, maleic acid and phenol-modified rosins and their esters; terpene resins; phenol-modified terpene resins; coumarin indene resins; phenolic resins; alkylphenol acetylene resins; and phenolic formaldehyde resins, etc., which can be solid amorphous compounds (resins).

[0108] In another embodiment, the plasticizer is at least one plasticizer selected from the group consisting of: triacetin, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, triethyl citrate, acetyltrimethyl citrate, acetyltriethyl citrate, acetyltributyl citrate, tributyl-o-acetyl citrate, dibutyl phthalate, diallyl phthalate, diethyl phthalate, dimethyl phthalate, di-2-methoxyethyl phthalate, di-octyl phthalate, di-octyl adipate, dibutyl tartrate, ethyl o-benzoylbenzoate, ethyl phthalylethyl glycolate, methyl phthalylethyl glycolate, n-ethyltoluenesulfonamide, o-cresyl p-toluenesulfonate, aromatic diol, substituted aromatic diol, aromatic ether, tripropionin, tribenzoin, polycaprolactone, glycerin, glycerin ester, diacetin, glycerol acetate benzoate, polyethylene glycol, polyethylene glycol ester, polyethylene glycol diester, di-2-ethylhexyl polyethylene glycol ester, triethylene glycol bis-2-ethylhexanoate, glycerol ester, diethylene glycol, polypropylene glycol, polyglycol diglycidyl ether, dimethyl sulfoxide, N-methylpyrrolidinone, C1-C20 dicarboxylic acid ester, dimethyl adipate, dibutyl maleate, dioctyl maleate, resorcinol monoacetate, catechol, catechol ester, phenol, epoxidized soybean oil, castor oil, linseed oil, epoxidized linseed oil, other vegetable oils, other seed oils, bifunctional glycidyl ether based on polyethylene glycol, γ-butyrolactone, alkyl phosphate ester, aryl phosphate ester, phospholipid, eugenol, cinnamyl alcohol, camphor, methoxyhydroxyacetophenone, vanillin, ethyl vanillin, 2-phenoxyethanol, glycol ether, glycol ester, glycol ester ether, polyglycol ether, polyglycol ester, ethylene glycol ether, propylene glycol ether, ethylene glycol ester, propylene glycol ester, polypropylene glycol ester, acetylsalicylic acid,Acetaminophen, naproxen, imidazole, triethanolamine, benzoic acid, benzyl benzoate, salicylic acid, 4-hydroxybenzoic acid, propyl-4-hydroxybenzoic acid, methyl-4-hydroxybenzoic acid, ethyl-4-hydroxybenzoic acid, benzyl-4-hydroxybenzoic acid, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, butylated hydroxytoluene, butylated hydroxyanisole, sorbitol, xylitol, ethylenediamine, piperidine, piperazine, hexamethylenediamine, triazine, triazole, pyrrole, and any combination thereof.,

[0109] In embodiments, the amount of plasticizer in the cellulose ester composition can range from 0 to about 15 wt% based on the weight of the cellulose ester composition. In one embodiment, the amount can range up to about 15 wt% based on the weight of the cellulose ester composition. In another embodiment, the amount can range up to about 10 wt% based on the weight of the cellulose ester composition. In another embodiment, the amount can range up to about 5 wt%, or up to about 3 wt%, or less than 2 wt% based on the weight of the cellulose ester composition. In embodiments, the cellulose ester composition comprises a cellulose ester that is CA and comprises a plasticizer as described herein, for example, in an amount ranging from 1 to 15 wt%, or 1 to 10 wt%, or 1 to 8 wt%, or 2 to 15 wt%, or 2 to 10 wt%, or 2 to 8 wt%, or 2 to 6 wt%, or 2 to 5 wt%, or 3 to 15 wt%, or 3 to 10 wt%, or 3 to 8 wt%, or 3 to 6 wt% based on the total weight of the composition. In another embodiment, the cellulose ester composition does not contain a plasticizer. In one embodiment, the cellulose ester composition comprises a cellulose ester that is CAP and does not contain a plasticizer. In one embodiment, the cellulose ester composition comprises a cellulose ester that is CAB and does not contain a plasticizer.

[0110] Embodiment of a specific cellulose ester composition In certain embodiments, the cellulose ester composition comprises from 75 to 98 wt%, or from about 80 to 98 wt%, of at least one cellulose ester (in one embodiment, CAP); from 1 to 15 wt%, or from 1 to 10 wt%, of at least one impact modifier (in one embodiment, an acrylic core-shell impact modifier); and from 0.1 to 10 wt%, or from 0.2 to 5 wt%, of at least one friction modifier. In embodiments, the friction modifier comprises a siloxane friction modifier or is a siloxane friction modifier.

[0111] In certain embodiments, the cellulose ester composition comprises from 55 to 98 wt%, or from about 77 to 98 wt%, of at least one cellulose ester (in one embodiment, CAP); from 1 to 15 wt%, or from 1 to 10 wt%, of at least one impact modifier (in one embodiment, an acrylic core-shell impact modifier); from 1 to 30 wt%, or from 1 to 20 wt%, or from 1 to 10 wt%, of at least one PAP (in one embodiment, PBS having an MFR (190 °C, 2.16 kg) of less than 25 and an elongation at break of 100% or more); and from 0.1 to 10 wt%, or from 0.2 to 5 wt%, of at least one friction modifier, such as a siloxane friction modifier. In embodiments, the CAP comprises more than 10%, or more than 20%, or more than 30%, or more than 40%, or more than 45% propionyl on a weight basis.

[0112] In one embodiment, the cellulose ester composition is transparent and has a light transmittance of at least 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90% when measured using a 3.2 mm plaque in accordance with ASTM D1003 after injection molding at a barrel set temperature of 249 °C and a residence time of 5 minutes. In certain embodiments, the polymer-based resin has a transmittance in the range of 70% to 95%, or 75% to 95%, or 80% to 95%, or 85% to 95%, or 90% to 95%, or 70% to 90%, or 75% to 90%, or 80% to 90%, or 85% to 90% when measured using a 3.2 mm plaque in accordance with ASTM D1003 after injection molding at a barrel set temperature of 249 °C and a residence time of 5 minutes. In one class of this embodiment, the haze ratio of the cellulose ester composition containing PAP (e.g., PBS), an impact modifier (e.g., an acrylic core-shell impact modifier), and a friction modifier is less than 10%. In embodiments, the cellulose ester composition containing PAP, an impact modifier, and a friction modifier has a haze ratio of less than 8%, or less than 6%, or less than 5%.

[0113] In another embodiment, the refractive indices (RIs) of PAP and the impact modifier are each sufficiently close to the refractive index of the cellulose ester, so that a composition with high transmittance and low haze values can be obtained. In one embodiment, PAP, the impact modifier, and the friction modifier each have an RI close to the RI of the cellulose ester of about 1.46 to 1.48, and a transparent composition can be obtained. In embodiments, PAP, the impact modifier, and the friction modifier each have a difference in refractive index of RI (second component) - RI (first component) (e.g., RI of CE - RI of PBS) of about 0.006 to about -0.0006 with respect to the cellulose ester component, and the blend has a transmittance of at least 75% and a haze value of 10% or less, more preferably 5% or less.

[0114] In an embodiment, the amount of PAP, such as PBS, in the cellulose ester composition can range from about 0.5 wt% to about 40 wt%, or from about 1 wt% to about 35 wt%, or from 2 to 30 wt%, or from 2 to 20 wt%, or from 2 to 10 wt%, or from about 2.5 wt% to about 30 wt%, or from about 5 wt% to about 25 wt%, or from about 5 wt% to about 20 wt%, or from about 5 wt% to about 15 wt%, or from about 5 wt% to about 10 wt%, or from about 10 wt% to about 30 wt%, or from about 10 wt% to about 25 wt%, or from about 10 wt% to about 20 wt%, or from about 10 wt% to about 15 wt%, or more than 10 wt% to about 30 wt%, or more than 10 wt% to about 25 wt%, or more than 10 wt% to about 20 wt%, or more than 10 wt% to about 15 wt% based on the weight of the cellulose ester composition. In an embodiment, the composition contains at least one PAP in an amount of 0.5 to 40 wt%, or 1 to 35 wt%, or 2 to 30 wt%, or 2 to 20 wt%, or 2 to 10 wt%, or 3 to 10 wt%, or 3 to 8 wt%, or 3 to 7 wt%, or 4 to 8 wt%, or 4 to 7 wt% based on the whole cellulose ester composition, in addition to at least one impact modifier, at least one friction modifier, and optionally at least one monomer plasticizer.

[0115] In another embodiment, the cellulose ester composition further comprises, as a blend (with the cellulose ester), at least one additional polymer component in an amount of 5 to 95 wt% based on the total cellulose ester composition. Suitable examples of additional polymer components include nylon; polyester; polyamide; polystyrene; other cellulose esters, cellulose ethers; polystyrene copolymers; styrene acrylonitrile copolymers; polyolefins; polyurethanes; acrylonitrile butadiene styrene copolymers; poly(methyl methacrylate); acrylic copolymers; poly(ether imide); polyphenylene oxide; polyvinyl chloride; polyphenylene sulfide; polyphenylene sulfide / sulfone; poly(ester carbonate); polycarbonate; polysulfone; polylactic acid; polysulfone ether; and poly(ether ketone) of aromatic dihydroxy compounds; or mixtures of any of the foregoing polymers, but are not limited thereto. The blend can be prepared by conventional processing techniques known in the art, such as melt blending or solution blending. In certain embodiments, the total amount of additional polymer compounds (excluding PAP) is less than 25 wt%, or less than 20 wt%, or less than 15 wt%, or less than 10 wt%, or less than 5 wt%, or none, based on the total weight of the cellulose ester composition.

[0116] In another embodiment, the composition is melt processable. Melt processability generally refers to the ability of a material to be heat treated at a temperature lower than its degradation temperature to obtain homogeneous pellets or plastic products. For example, the described composition can be melt extruded at a throughput of 35 pounds per hour on a Werner & Pfleiderer 30 mm twin screw extruder at a screw speed of 250 rpm and a barrel temperature of 240 °C, and injection molded on a Toyo 110 injection molding machine at a barrel temperature of 240 °C and a mold temperature of 160 °F with minimal degradation of molecular weight or color.

[0117] In one embodiment, a melt-processable cellulose ester composition is provided that contains from 1 to 30 wt%, or from 1 to 15 wt%, or from 2 to 10 wt% of an impact modifier and no plasticizer, and the cellulose ester composition has an HDT value above 85 °C, a notched Izod impact strength value above 80 J / m (measured on a 3.2 mm thick bar at 23 °C according to ASTM D256), and a spiral flow value of at least 15 inches at 240 °C when measured using the procedure described herein. In one embodiment, the cellulose ester composition has a Tg value above 120 °C as measured at 20 °C / min according to ASTM D3418. Unless otherwise specified, the notched Izod impact strength value was performed on a molded bar at 23 °C on a 3.2 mm thick bar after notching according to the ASTM D256 procedure after conditioning at 23 °C, 50% RH for 48 hours.

[0118] In another embodiment, the composition has a melt viscosity at 240 °C and 400 rad / sec of 10,000 P or less as measured with a plate - in - melt rheometer, such as a Rheometrics Dynamic Analyzer (RDA II), with parallel plates 25 mm in diameter, and has a 1 mm gap and 10% strain as measured using a frequency scan from 1 rad / sec to 400 rad / sec according to ASTM D4440.

[0119] In one embodiment, the melt-processable cellulose ester composition comprises 1 to 30 wt%, or 1 to 15 wt% of an impact modifier, 0 to 15 wt% of a plasticizer, and has a Tg above 90 °C. In another embodiment, the melt-processable cellulose ester composition comprises 1 to 30 wt%, or 1 to 15 wt% of an impact modifier, 0 to 10 wt% of a plasticizer, and has a Tg above 100 °C. In yet another embodiment, the melt-processable cellulose ester composition comprises 1 to 10 wt% of an impact modifier, 0 to 10 wt% of a plasticizer, and has a Tg above 100 °C. In another embodiment, the melt-processable cellulose ester composition comprises 1 to 10 wt% of an impact modifier, 0 to 5 wt% of a plasticizer, and has a Tg above 115 °C.

[0120] In one embodiment, the melt-processable cellulose ester composition comprises 1 to 30 wt%, or 1 to 15 wt% of an impact modifier, 1 to 20 wt%, or 1 to 15 wt% of PAP, 0 to 15 wt% of a plasticizer, and has a Tg above 90 °C. In another embodiment, the melt-processable cellulose ester composition comprises 1 to 30 wt%, or 1 to 15 wt% of an impact modifier, 1 to 20 wt%, or 1 to 15 wt% of PAP, 0 to 10 wt% of a plasticizer, and has a Tg above 100 °C. In yet another embodiment, the melt-processable cellulose ester composition comprises 1 to 10 wt% of an impact modifier, 1 to 15 wt% of PAP, 0 to 10 wt% of a plasticizer, and has a Tg above 100 °C. In another embodiment, the melt-processable cellulose ester composition comprises 1 to 10 wt% of an impact modifier, 1 to 10 wt% of PAP, 0 to 5 wt% of a plasticizer, and has a Tg above 115 °C.

[0121] In another embodiment, when the cellulose ester composition contains an impact modifier and no plasticizer, it has a Tg or HDT similar to the base cellulose ester polymer with a decrease of only a few degrees Celsius (e.g., less than 5 °C, or less than 2 °C). The impact properties of these compositions can also exceed 80 J / m (notched Izod impact strength value at 23 °C).

[0122] In an embodiment, the cellulose ester composition has a heat deflection temperature (HDT) measured according to ASTM D648 at 1.82 MPa using a 3.2 mm thick bar exposed at 70 °C for 4 hours that exceeds 80 °C or exceeds 85 °C. In certain embodiments, the polymer-based resin has an HDT of at least 85 °C, at least 90 °C, or at least 95 °C at 0.455 MPa. In certain embodiments, the cellulose ester composition has an HDT in the range of 85 °C to 140 °C, 85 °C to 130 °C, 85 °C to 120 °C, 85 °C to 110 °C, 85 °C to 105 °C, 85 °C to 100 °C, 85 °C to 95 °C, 90 °C to 140 °C, 90 °C to 130 °C, 90 °C to 120 °C, 90 °C to 110 °C, 90 °C to 105 °C, 90 °C to 100 °C, 95 °C to 140 °C, 95 °C to 130 °C, 95 °C to 120 °C, 95 °C to 110 °C, 95 °C to 105 °C, 95 °C to 100 °C.

[0123] In an embodiment, when the polymer-based resin is measured according to ASTM D256 using a 3.2 mm thick bar exposed to 50% relative humidity at 23 °C for 48 hours, the notched Izod impact strength value is at least 80 J / m, or at least 90 J / m, or at least 100 J / m, or at least 110 J / m, or at least 120 J / m, or at least 130 J / m, or at least 140 J / m, or at least 150 J / m, or at least 160 J / m, or at least 170 J / m, or at least 180 J / m, or at least 190 J / m, or at least 200 J / m. In a particular embodiment, when the polymer-based resin is measured according to ASTM D256 using a 3.2 mm thick bar exposed to 50% relative humidity at 23 °C for 48 hours, the range of the notched Izod impact strength value is from about 80 J / m to about 500 J / m, from about 80 J / m to about 400 J / m, from about 80 J / m to about 300 J / m, from about 80 J / m to about 200 J / m, from about 100 J / m to about 500 J / m, from about 100 J / m to about 400 J / m, from about 100 J / m to about 300 J / m, from about 100 J / m to about 200 J / m, from about 120 J / m to about 500 J / m, from about 120 J / m to about 400 J / m, from about 120 J / m to about 300 J / m, from about 120 J / m to about 200 J / m, from about 150 J / m to about 500 J / m, from about 150 J / m to about 400 J / m, from about 150 J / m to about 300 J / m, from about 150 J / m to about 200 J / m, from about 170 J / m to about 500 J / m, from about 170 J / m to about 400 J / m, from about 170 J / m to about 300 J / m, from about 170 J / m to about 200 J / m, from about 180 J / m to about 500 J / m, from about 180 J / m to about 400 J / m, from about 180 J / m to about 300 J / m, from about 180 J / m to about 200 J / m, from about 190 J / m to about 500 J / m, from about 190 J / m to about 400 J / m, from about 190 J / m to about 300 J / m, from about 190 J / m to about 200 J / m, from about 200 J / m to about 500 J / m, from about 200 J / m to about 400 J / m, or from about 200 J / m to about 300 J / m.

[0124] In an embodiment, the polymer-based resin has a flexural modulus exceeding 1800 MPa when measured in accordance with ASTM D790 using a 3.2 mm thick bar exposed to 50% relative humidity at 23°C for 48 hours. In certain embodiments, the polymer-based resin has a flexural modulus of at least 1900 MPa, at least 2000 MPa, at least 2100 MPa, at least 2200 MPa, at least 2300 MPa, or at least 2400 MPa when measured in accordance with ASTM D790 using a 3.2 mm thick bar exposed to 50% relative humidity at 23°C for 48 hours. In certain embodiments, the polymer-based resin has a flexural modulus in the range of about 1800 to about 3500 MPa, about 1900 to about 3500 MPa, about 2000 to about 3500 MPa, about 2100 to about 3500 MPa, about 2200 to about 3500 MPa, about 2300 to about 3500 MPa, about 2400 to about 3500 MPa, or about 2500 to about 3500 MPa when measured in accordance with ASTM D790 using a 3.2 mm thick bar exposed to 50% relative humidity at 23°C for 48 hours. In certain embodiments, the polymer-based resin has a flexural modulus in the range of about 1900 to about 2500 MPa, about 1900 to about 2800 MPa, or about 1900 to about 3000 MPa when measured in accordance with ASTM D790 using a 3.2 mm thick bar exposed to 50% relative humidity at 23°C for 48 hours.

[0125] In certain embodiments, the cellulose ester composition contains 1 wt% to 30 wt%, or 2 wt% to 15 wt% of an impact modifier based on the total weight of the cellulose ester composition, has an HDT value exceeding 85°C, or 90°C, and a notched Izod impact strength value exceeding 80, or 100, or 120 J / m, and has a viscosity of less than 10,000 P at 240°C and 400 rad / sec.

[0126] In certain embodiments, the cellulose ester composition comprises 1 wt% to 30 wt%, or 2 wt% to 15 wt% of an impact modifier, based on the total weight of the cellulose ester composition, and has an HDT value exceeding 85 °C, or 90 °C, and a notched Izod impact strength value exceeding 80, or 100, or 120 J / m, and a light transmittance value of 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%. This was measured in accordance with ASTM D1003 using a 3.2 mm plaque after injection molding at a barrel set temperature of 249 °C for a residence time of 5 minutes.

[0127] In certain embodiments, the cellulose ester composition comprises 1 wt% to 30 wt%, or 2 wt% to 15 wt% of an impact modifier, based on the total weight of the cellulose ester composition, and has an HDT value exceeding 85 °C, or 90 °C, and a notched Izod impact strength value exceeding 80, or 100, or 120 J / m, and no problems of squeaking or screw recovery occur during injection molding at a barrel set temperature of 249 °C.

[0128] In certain embodiments, the cellulose ester composition comprises 1 wt% to 30 wt%, or 2 wt% to 15 wt% of an acrylic core-shell impact modifier, based on the total weight of the cellulose ester composition, and has an HDT value exceeding 85 °C, or 90 °C, and a notched Izod impact strength value exceeding 150 J / m, and no problems of squeaking or screw recovery occur during injection molding at a barrel set temperature of 249 °C.

[0129] In another embodiment, the cellulose ester composition further comprises at least one additive selected from the group consisting of antioxidants, heat stabilizers, release agents, antistatic agents, whitening agents, colorants, flow aids, processing aids, plasticizers, anti-fogging additives, minerals, UV stabilizers, lubricants, chain extenders, nucleating agents, reinforcing fillers, wood or wheat flour fillers, glass fibers, carbon fibers, flame retardants, dyes, pigments, colorants, additional resins, and combinations thereof.

[0130] In an embodiment, the reinforcing material may be useful in the composition. The reinforcing material may include, but is not limited to, carbon filaments, silicates, mica, clay, talc, titanium dioxide, wollastonite, glass flakes, glass beads and fibers, and polymer fibers and combinations thereof. In one embodiment, the reinforcing material is, for example, glass such as fibrous glass filaments, mixtures of glass and talc, glass and mica, and glass and polymer fibers.

[0131] In certain embodiments, in addition to the impact modifier and friction modifier, and optionally the monomer plasticizer and / or PAP (as described herein), the cellulose ester composition includes a stabilizer selected from the group consisting of a secondary antioxidant, an acid scavenger, or a combination thereof. In certain embodiments, in addition to the impact modifier and friction modifier, and optionally the monomer plasticizer and / or PAP (as described herein), the cellulose ester composition includes, based on the total weight of the composition, from about 0.01 to about 0.8 wt%, or from about 0.05 to about 0.5 wt%, or from about 0.08 to about 0.4 wt%, or from about 0.1 to about 0.3 wt% of a secondary antioxidant. In certain embodiments, in addition to the impact modifier and friction modifier, and optionally the monomer plasticizer and / or PAP (as described herein), the cellulose ester composition includes, based on the total weight of the composition, from about 0.2 to about 5 wt%, or from about 0.5 to about 4 wt%, or from about 0.5 to about 3 wt%, or from about 0.75 to about 3.5 wt%, or from about 1 to about 3 wt%, or from about 1 to about 2 wt%, or from about 1.5 to about 2.5 wt% of an acid scavenger. In one embodiment, in addition to the impact modifier and friction modifier, and optionally the monomer plasticizer and / or PAP (as described herein), the cellulose ester composition includes, based on the total weight of the composition, from about 0.01 to about 0.8 wt%, or from about 0.05 to about 0.5 wt%, or from about 0.08 to about 0.4 wt%, or from about 0.1 to about 0.3 wt% of a secondary antioxidant, and from about 0.2 to about 5 wt%, or from about 0.5 to about 4 wt%, or from about 0.5 to about 3 wt%, or from about 0.75 to about 3.5 wt%, or from about 1 to about 3 wt%, or from about 1 to about 2 wt%, or from about 1.5 to about 2.5 wt% of an acid scavenger.In the embodiment, the weight ratio of the acid scavenger to the secondary antioxidant is in the range of 4:1 to 25:1, or 5:1 to 20:1, or 6:1 to 18:1, or 7:1 to 15:1, or 8:1 to 15:1, or 9:1 to 15:1, or 10:1 to 15:1, or 9:1 to 14:1, or 9:1 to 13:1, or 9:1 to 12:1, or 10:1 to 14:1, or 10:1 to 13:1, or 10:1 to 12:1.

[0132] In an embodiment, the secondary antioxidant is a pentaerythritol diphosphite compound having a melting point of 200 °C or lower, or 190 °C or lower, or 180 °C or lower. In an embodiment, the secondary antioxidant is bis(dialkylphenyl)pentaerythritol diphosphite. In one embodiment, the secondary antioxidant is 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane. In one embodiment, the acid scavenger is an epoxidized fatty acid ester, such as epoxidized soybean oil. In one embodiment, the cellulose ester composition further comprises a salt stabilizer in the range of about 0.1 to about 0.5 wt% based on the total weight of the composition. In one embodiment, in addition to the cellulose ester, impact modifier, friction modifier, and optionally monomeric plasticizer and / or PAP and / or stabilizer (as described herein), the cellulose ester composition comprises other components in a total amount of less than 5 wt%, or less than 2 wt%, or less than 1 wt%, or less than 0.5 wt% based on the total weight of the composition. It should be noted that an additive / component may perform multiple functions in the cellulose ester composition. The different (or specific) functionality of a particular additive (or component) with respect to the cellulose ester composition may depend on its physical properties (e.g., molecular weight, solubility, melting temperature, Tg, etc.) and / or the amount of such additive / component in the overall composition. For example, an epoxidized oil such as epoxidized soybean oil can function as a plasticizer in one form (e.g., a certain molecular weight, number of reactive groups, or wt% in the composition), or as an acid scavenger (with little or no plasticizing effect) at another molecular weight, number of reactive groups, or wt% in the composition.

[0133] In certain embodiments, the cellulose ester composition does not contain maleic anhydride modified EVA. In certain embodiments, the cellulose ester composition does not contain a polyether ester compound. In certain embodiments, the cellulose ester composition does not contain an adipic acid compound. In certain embodiments, the cellulose ester composition comprises, based on the total weight of the cellulose ester composition, 60 to 99 wt% of one or more cellulose esters, 1 to 30 wt% of one or more impact modifiers, 0.1 to 10 wt% of a friction modifier component, and less than 5 wt% in total of other components. In certain embodiments, such other components do not include a plasticizer, a polyether ester compound, or an adipic acid compound. In certain embodiments, the cellulose ester composition contains dioctyl adipate (DOA) plasticizer and does not contain other adipic acid compounds.

[0134] In another embodiment, a method of manufacturing a cellulose ester composition is provided. The method includes combining at least one cellulose ester, at least one impact modifier, a friction modifier component, and optionally at least one plasticizer and / or PAP and / or stabilizer. The cellulose ester, impact modifier, friction modifier component, plasticizer, PAP, and stabilizer have been described hereinbefore. In one embodiment, the cellulose ester and other components can be mixed in any order of addition.

[0135] In another embodiment, a method for manufacturing a cellulose ester composition is provided, the method comprising: a) mixing at least one impact modifier, at least one cellulose ester, a friction modifier component, and optionally at least one plasticizer and / or PAP and / or stabilizer at a temperature and for a time sufficient to disperse the component containing the impact modifier to produce a cellulose ester composition. The sufficient temperature is defined as the flow temperature of the cellulose ester, which is generally about 50 °C higher than the Tg of the cellulose ester. In another embodiment, the temperature is about 80 °C higher than the Tg of the cellulose ester. In an embodiment, the temperature during mixing is limited at the upper end by the treatment temperature of the impact modifier and at the lower end by the maximum use temperature of the cellulose ester composition.

[0136] The efficiency of mixing multiple viscoelastic materials can depend on the ratio of the viscosities of the viscoelastic materials. In one embodiment, in a given mixing apparatus and shear rate range, the viscosity ratio of the dispersed phase (including the impact modifier) to the continuous phase (cellulose ester) should be within the limits specified to obtain an appropriate particle size.

[0137] In an embodiment, the mixing of the impact modifier, cellulose ester, friction modifier, and other additives can be achieved by any method known in the art suitable for dispersing the additives in the cellulose ester. Examples of mixing apparatuses include, but are not limited to, Banbury mixers, Brabender mixers, roll mills, and extruders (single-screw or twin-screw). The shear energy during mixing depends on the combination of the apparatus, blade design, rotational speed (rpm), and mixing time. The shear energy must be sufficient to disperse the impact modifier (and, if present, other dispersed phase components) throughout the cellulose ester.

[0138] In an embodiment, the cellulose ester, impact modifier, friction modifier, plasticizer, and other additives can be combined in any order during the process. In one embodiment, the cellulose ester is premixed with the impact modifier and / or plasticizer. Next, the cellulose ester containing the impact modifier and / or plasticizer is mixed with the other additives. In another embodiment, when using a reactive impact modifier, the reactive impact modifier can first be mixed with the cellulose ester, and then the other components can be added.

[0139] The composition can be useful as a molded plastic product or part (or solid plastic object). The composition is suitable for use in any application where a rigid plastic is required. Examples of such parts include disposable knives, forks, spoons, dishes, cups, straws, as well as eyeglass frames, toothbrush handles, toys, automotive trim, tool handles, camera parts, electronic device parts, razor parts, ink pen barrels, disposable syringes, bottles, and the like. In one embodiment, the composition can be useful as a plastic, film, fiber, and sheet. In one embodiment, the composition is for manufacturing bottles, bottle caps, eyeglass frames, cutlery, disposable cutlery, cutlery handles, shelves, shelf dividers, electronic device housings, electronic device cases, computer monitors, printers, keyboards, pipes, automotive parts, automotive interior parts, automotive trim, signs, thermoformed letters, siding, toys, thermally conductive plastics, ophthalmic lenses, tools, tool handles, appliances, or hard trims for clothing items (such as snaps, buckles, buttons, zippers, etc.) and can be useful as a plastic. In another embodiment, the composition is suitable for use as a film, sheet, fiber, molded article, medical device, packaging, bottle, bottle cap, eyeglass frame, cutlery, disposable cutlery, cutlery handle, shelf, shelf divider, furniture parts, electronic device housing, electronic device case, computer monitor, printer, keyboard, pipe, toothbrush handle, automotive parts, automotive interior parts, automotive trim, signs, outdoor signs, skylights, multilayer films, thermoformed letters, siding, toys, toy parts, thermally conductive plastics, ophthalmic lenses and frames, tools, tool handles, and appliances, healthcare supplies, commercial food service products, boxes, films for graphic art applications, and plastic films for plastic glass laminates. In an embodiment, the product can be an acoustic product.For example, it can be an audio product such as an integrated audio device including speakers for automobiles, televisions, and smartphones; a stand-alone speaker (wired or wireless), a soundbar, a subwoofer, a home theater system including under the TV; a smart speaker including WiFi streaming, a virtual personal assistant; and an article selected from headphones, earphones, and other wearable speakers. In an embodiment, the acoustic article can also be a component or part of any of these devices, such as a housing, an enclosure, a speaker component, a microphone component, a headband, a wristband, a clip, a handle, etc.

[0140] The composition is also useful for forming injection-molded toys. In particular, the composition is useful for forming injection-molded assembled toys or parts thereof. As used herein, the term "assembled toy" includes conventional toy assembly elements in the form of box-shaped assembly blocks having a knob on the upper side and a complementary tube on the lower side. Conventional box-shaped toy assembly blocks are shown in FIGS. 1 and 2. Conventional box-shaped toy assembly blocks were first disclosed in U.S. Patent No. 3,005,282 and are widely sold under the trademark names LEGO® and LEGO® DUPLO®. This term also includes other similar box-shaped assembly blocks manufactured by companies other than the LEGO Group and sold under trademark names other than the LEGO trademark.

[0141] The term "construction toy" also includes other types of toy construction elements having knobs on the upper side and / or complementary tubes on the lower side, which are usually part of a toy construction set including a plurality of construction elements that are mutually compatible and thus connectable to each other. Such toy construction sets are also sold under trademarks of LEGO, such as LEGO (registered trademark) bricks, LEGO (registered trademark) Technic, and LEGO (registered trademark) DUPLO (registered trademark). Some of these toy construction sets include toy construction figures, such as LEGO (registered trademark) minifigures (see, for example, U.S. Patent Application 05 / 877,800), having complementary tubes on the lower side (see FIG. 2) that allow this element to be connected to other toy construction elements within the toy construction set. Such toy construction figures are also encompassed by the term "toy construction element". The term also includes other similar toy construction elements manufactured by companies other than the LEGO Group and thus sold under trade names other than LEGO trademarks.

[0142] Toy construction elements are available in a wide variety of shapes, sizes, and colors. One difference between LEGO (registered trademark) bricks and LEGO (registered trademark) DUPLO (registered trademark) bricks is that LEGO (registered trademark) DUPLO (registered trademark) bricks are twice as large as LEGO (registered trademark) bricks in all dimensions. The size of a conventional box-shaped LEGO (registered trademark) toy construction brick having 4x2 knobs on the upper surface is approximately 3.2 cm in length, 1.6 cm in width, and 0.96 cm in height (excluding the knobs), and the diameter of each knob is approximately 0.48 cm. In contrast, the size of a LEGO (registered trademark) DUPLO (registered trademark) brick having 4x2 knobs on the upper surface is approximately 6.4 cm in length, 3.2 cm in width, and 1.92 cm in height (excluding the knobs), and the diameter of each knob is approximately 0.96 cm.

[0143] The cellulose ester composition of the present invention is useful for forming fibers, films, molded articles, and sheets. The method of forming the cellulose ester composition into fibers, films, molded articles, and sheets can follow methods known in the art. Examples of potential molded articles include medical devices, medical packaging, healthcare products, commercial food service products such as food pans, tumblers, and storage boxes, bottles, food processors, blender and mixer bowls, kitchen utensils, water pitchers, vegetable crisper trays, the front of washing machines, vacuum cleaner parts, and toys, but are not limited thereto. Other potential molded articles include ophthalmic lenses and frames.

[0144] The present invention further relates to a manufactured product comprising a film and / or a sheet comprising the cellulose ester composition described herein. In embodiments, the film and / or the sheet can be of any thickness apparent to those skilled in the art.

[0145] The present invention further relates to the film and / or the sheet described herein. The method of forming the cellulose ester composition into a film and / or a sheet can include methods known in the art. Examples of films and / or sheets include, but are not limited to, extruded films and / or sheets, calendered films and / or sheets, compression molded films and / or sheets, solution cast films and / or sheets. Methods for manufacturing films and / or sheets include, but are not limited to, extrusion, calendering, compression molding, wet block processing, dry block processing, and solution casting.

[0146] The present invention further relates to a molded article described herein. Methods for molding a cellulose ester composition into a molded article may include methods known in the art. Examples of molded articles include, but are not limited to, injection molded articles, overmolded articles, 2k (or 2-shot) molded articles, extruded articles, injection blow molded articles, injection stretch blow molded articles, and extrusion blow molded articles. Methods for manufacturing molded articles include, but are not limited to, injection molding, injection overmolding, 2k (or 2-shot) injection molding, extrusion molding, injection blow molding, injection stretch blow molding, and extrusion blow molding. The process may include any blow molding process known in the art, including, but not limited to, extrusion blow molding, extrusion stretch blow molding, injection blow molding, and injection stretch blow molding.

[0147] The present invention includes any injection blow molding manufacturing process known in the art. A typical description of an injection blow molding (IBM) manufacturing process includes, but is not limited to: 1) melting the composition with a reciprocating screw extruder; 2) injecting the molten composition into an injection mold to form a partially cooled tube (i.e., a preform) with one end closed; 3) moving the preform into a blow mold having a desired final shape around the preform and closing the blow mold around the preform; 4) blowing air into the preform to expand and inflate the preform to fill the mold; 5) cooling the molded article; 6) removing the molded article from the mold.

[0148] The present invention includes any injection stretch blow molding manufacturing process known in the art. A typical description of an injection stretch blow molding (ISBM) manufacturing process includes, but is not limited to, the following: 1) melting the composition with a reciprocating screw extruder; 2) injecting the molten composition into an injection mold to form a partially cooled tube (i.e., a preform) with one end closed; 3) moving the preform into a blow mold having a desired finished shape around the preform and closing the blow mold around the preform; 4) using an internal stretch rod to stretch the preform, blowing air into the preform, and expanding and inflating the preform to fill the mold; 5) cooling the molded article; 6) removing the molded article from the mold.

[0149] The present invention includes any extrusion blow molding manufacturing process known in the art. A typical description of an extrusion blow molding manufacturing process includes, but is not limited to, the following: 1) melting the composition with an extruder; 2) extruding the molten composition through a die to form a tube of molten polymer (i.e., a parison); 3) clamping a mold having a desired finished shape around the parison; 4) blowing air into the parison to stretch and expand the extrudate to fill the mold; 5) cooling the molded article; 6) removing the molded article from the mold; 7) removing excess plastic (commonly referred to as flash) from the molded article.

[0150] The present invention can be further illustrated by the following examples of preferred embodiments, which are included for illustrative purposes only and are not intended to limit the scope of the present invention in the absence of specific recitation.

Examples

[0151] Section 1. Base resin test Cellulose ester CAP482-20 (manufactured by Eastman) was compounded with PBS polymer and impact modifier (IM) to prepare a cellulose ester composition. The PBS polymer was FD92 grade PBS (manufactured by PTT MCC Biochem), and the IM was Kane Ace M570 acrylic core-shell impact modifier (manufactured by Kaneka). The compounding was carried out using a Leistritz 18 mm (L / D ratio 50:1) twin-screw extruder at a throughput of 18 pounds per hour, a screw speed of 250 rpm, and a barrel temperature of 220 °C. The resulting CE composition (C-04) consisted of 86 wt% CAP, 8 wt% PBS, and 6 wt% IM.

[0152] C-04 resin and several other commercially available resins were subjected to a series of tests. This test was designed to set performance criteria in terms of the physical properties and frictional performance of the cellulose ester composition.

[0153] The physical properties normally described in the technical data sheet (TDS) were evaluated using injection-molded tensile or flexure bars with established test methods defined by ASTM (American Society for Testing and Materials). For commercially available resins, the drying and processing conditions described in the technical data sheet were used for molding. For the modified resin, the processing conditions used were selected from those of the base resin.

[0154] Multiple tests were completed on all samples, including not only existing commercially available resins but also the modified resins under development detailed in Section 3 below. These test methods are classified as follows: · Specific physical properties normally described in the technical data sheet. Specific tests include tensile properties (ASTM D638), flexural properties (ASTM D790), notched Izod impact properties (ASTM D256), and heat distortion properties (ASTM D648). In all cases, both commercially available resins and modified resins under development were subject to standard conditioning and test protocols. · Friction profile of the base resin. Measured as the static coefficient of friction and the dynamic coefficient of friction (μ s and μ k ), respectively, using an in-house test method equivalent to that of the conventional standardized friction and slip thread test (ASTM D1894). These values were measured by intentionally contacting the surfaces of a pair of 4-inch x 4-inch x 1 / 8-inch plaques manufactured by injection molding using a Bruker tribometer. To prevent degradation of the quality of friction data measurement, gloves were always worn to avoid direct contact with the test samples. After molding, the coefficient of friction was measured using a pair of plaques according to the following definitions:

[0155] Static COF (μ s ). Measured at the limit where both the contact force (F z ) between the two plaques and the relative velocity (vx) between the two contacting plaques approach zero. Example: F z = 0.05 N, v x = 0.01 mm / sec Dynamic COF (μ k ). Defined as the friction measured at a constant force and the relative velocity between the two contacting plaques. Example: F z = 3.00 N, v x = 10.0 mm / sec

[0156] Table 1 shows an overview of commercially available resins evaluated as "control" or "counter" examples.

[0157]

Table 1

[0158] Table 2 shows an overview of the physical properties of the control / counter materials.

[0159]

Table 2

[0160] Considering the physical property data in Table 2, Resins C-01 and C-02 (ABS and polycarbonate (PC), respectively) exhibit higher rigidity than all other evaluated materials in both tensile modulus and flexural modulus. Resins C-03 and C-04 (cellulose-based materials) show tensile properties similar to C-01 except for the modulus, and similarly show similar impact toughness measured by the notched Izod test. The toughness of Resins C-06 and C-07 is significantly lower than that of C-01, while the rigidity of Resin C-05 is the lowest among all the commercial resins evaluated.

[0161] The frictional performance of the materials in Table 1 was evaluated, and the static friction coefficient and dynamic friction coefficient (μ s and μ k ), respectively) were quantified. The values of the coefficient of friction (COF) are shown in Table 3 below.

[0162]

Table 3

[0163] Considering Table 3, it can be seen that C-01 (ABS) and C-02 (PC) have similar friction profiles with respect to the static friction coefficient and dynamic friction coefficient when measured according to the sliding thread type test (Table 3). Furthermore, Resin C-01 has lower frictional performance compared to all the resins evaluated. Thus, in order to enable the functionality of applications that originally use ABS materials and require similar frictional behavior, it is necessary to modify the frictional performance of other resins (e.g., C-03 to C-07) to match the performance of C-01 in the friction test, while maintaining (or not significantly reducing) the physical properties, especially rigidity and impact toughness, compared to the unmodified base resin.

[0164] Section 2. Modification The modified samples were produced using twin screw compounding and various additives, resulting in a change in performance, most notably a change in the friction profile by incorporating various additives. The additives tested were chemically diverse and ranged from short chain molecules (such as waxes) to high molecular weight or ultra-high molecular weight organosiloxanes (such as PDMS). In the compounded formulations, it was found that the additives could function as internal and / or external lubricants depending on the chemical nature, molecular weight, loading level, and functionality of the specific additive. The friction modifiers used are shown in Table 4 below.

[0165]

Table 4

[0166] Section 3. Examples Multiple samples of the cellulose ester composition were generated by modifying with different friction modifiers and varying amounts of additives. The samples were prepared by compounding at 25 pounds per hour with a 2-hole die head or 150 pounds per hour with a 5-hole die head using a 30 mm or 40 mm twin screw extruder, respectively. All solids were pre-mixed and fed to the first loss-in-weight (gravimetric) feeder at the feed port of the extruder. Liquids were fed using a liquid loss-in-weight feeder at the first injector port downstream of the feed port of the extruder. The temperature of the extruder barrel was raised from the feed port to the die head. The profiles used were as follows: 100 °C at the feed port, 175 °C, 200 °C, and 225 °C at the die head. The melt temperature was measured to be between 218 °C and 224 °C. The extruded polymer strands were cooled using a water bath and an air knife and pelletized with a pellet chopper system to produce 2 x 3 mm cylindrical pellets.

[0167] The physical properties were measured before and after the thermal degradation protocol. The friction performance of each formulation was also evaluated using a functionality test under the same conditions for a specific application. The results are reported in the following table summarizing the performance of the modified formulations compared to the control example.

[0168] Table 5 summarizes the formulations evaluated in this study, CE-01 to CE-12, compared to control or counter examples, including specific compositions of friction modifiers. Note: The "base resin" used for all friction-modified cellulose ester samples was C-04.

[0169]

Table 5

[0170] In accordance with the aforementioned procedures and test methods, the physical properties and performance were measured for all controls, counters, and / or modified resins in Table 5. An overview of the physical properties, including tensile properties, notched Izod impact toughness, flexural modulus, and heat distortion temperature, is shown in Table 6 below.

[0171]

Table 6

[0172] Considering Table 6, it can be seen that the tensile performance (yield force, yield strain, breaking strength, breaking strain) is maintained even in formulations with different types and load levels of friction modifiers, compared to C-01 and unmodified cellulose materials (C-03 and C-04). Specifically, in some examples such as TR-04, TR-10, and TR-11, similar tensile modulus and / or flexural modulus were maintained compared to the unmodified cellulose formulations of C-03 and / or C-04; in some examples such as TR-02, TR-09, and TR-12, it was shown that the tensile modulus and / or flexural modulus were improved compared to the unmodified cellulose formulations of C-03 and / or C-04; and in some examples such as TR-07, TR-11, and TR-12, it was shown that the notched Izod performance and / or heat distortion performance were similar compared to the unmodified cellulose formulation C-04.

[0173] For some examples, the physical properties were also evaluated after the accelerated degradation protocol. This was accomplished by subjecting the samples to a thermal degradation protocol and then performing physical property tests on the thermally degraded test bars according to the standard ASTM test methods outlined above. Tests were conducted both before and after thermal exposure to investigate whether significant changes occurred in performance and physical properties due to friction modification and additives. Table 7 shows the tensile properties measured after standard conditioning (72 hours at 23°C and 50% RH) and after the thermal degradation protocol (200 hours at 60°C).

[0174]

Table 7

[0175] Considering Table 7, it can be seen that there were slight changes in the measured properties compared to Example C-01.

[0176] Finally, the friction performance of specific modified samples was compared to control samples C-03 and C-04. The results are shown in Table 8 below.

[0177]

Table 8

[0178] Considering Table 8, it can be seen that the static COF and dynamic COF of the modified examples are decreased compared to the C-03 and C-04 samples, and TR-07 and TR-08 show the greatest decrease in COF at lower load levels than TR-03 and TR-12. It was also noted that the COF value of the bio-based example TR-08 is approaching that of the fossil fuel-based resin C-01. For the samples in Table 8, the optical transparency, i.e., the haze ratio, was evaluated. The haze ratio was measured using a Datacolor 650 device equipped with a haze add-on under a C2 light source with a medium area field of view and a UV400 filter. The measurement was performed twice, once under total transmission and once under diffuse transmission. The resulting haze values are shown in Table 9 below.

[0179]

Table 9

[0180] Considering Table 9, it can be seen that the TR-12 formulation had a significantly lower haze ratio compared to the formulations modified with other COF modifiers tested.

[0181] Section 3. Injection molded toy assembly blocks The toy assembly blocks shown in Figure 1 are injection molded. The blocks were manufactured by injection molding with both Lego (registered trademark) size and Lego (registered trademark) Duplo (registered trademark) size, using C-04 resin and TR-03, TR-07, TR-08, and TR-09 modified resins, respectively. The injection molding parameters in the manufacture of toy assembly blocks are as follows.

[0182]

Table 10

[0183] Resin C-03, i.e., a commercially available TREVA grade, has low impact strength and breaks in a brittle mode (when tested as a requirement for toy assembly elements), so it is not suitable for the manufacture of toy assembly elements. Furthermore, resin C-03 has very high friction and the elements stick together and cannot be easily separated, so it is not suitable for toy assembly elements.

[0184] Resin C-04 has an appropriate level of impact strength and is a suitable material for toy assembly elements, but as shown in Table 5 above, it is necessary to add a COF modifier to modify the friction characteristics.

[0185] Accordingly, toy assembly elements made from modified resin TR-03 containing 1% Dowsil 4-7081 additive and modified resin TR-07 containing 0.5% Genioplast-S additive were tested. However, these resins did not function well with Lego 2x4 blocks due to their very high friction levels, and the blocks could not be separated (attached-detached), resulting in poor playability. It appears that more of these COF modifiers are needed to obtain an appropriate level of friction.

[0186] Toy assembly elements with modified resins TR-08 and TR-09 containing 0.75% and 1.0% Genioplast-S additive were also manufactured and tested. As a result, it was revealed that these toy assembly elements had an appropriate level of friction.

[0187] Although the present invention has been described in detail with particular reference to certain embodiments, it will be understood that changes and modifications are possible within the spirit and scope of the invention.

Claims

1. A cellulose ester composition comprising: (a) at least one cellulose ester, (b) At least one impact modifier in an amount of about 1 to about 15% by weight, (c) At least one friction modifier selected from waxes and siloxanes in an amount of about 0.1 to about 15% by weight, and (d) Optionally, one or more plasticizers in an amount of 0 to about 15% by weight, Here, the composition has an HDT value exceeding 85°C at 0.455 MPa, and a notched Izod impact strength value exceeding 80 J / m measured in accordance with ASTM D256 for a 3.2 mm thick bar at 23°C, after the bar has been conditioned at 23°C and 50% RH for 48 hours.

2. The composition according to claim 1, wherein the friction modifier is a wax.

3. The composition according to claim 1, wherein the friction modifier is a siloxane.

4. The composition according to claim 1, wherein the friction modifier is present in an amount of about 0.1 to about 4% by weight.

5. The composition according to claim 1, wherein the impact-resistant modifier is present in an amount of about 2 to about 10% by weight.

6. The composition according to claim 1, wherein the impact-resistant modifier is a core-shell impact-resistant modifier.

7. The composition according to claim 6, wherein the impact-resistant modifier is selected from an acrylic core-shell impact-resistant modifier, an ABS core-shell impact-resistant modifier, or an MBS core-shell impact-resistant modifier.

8. The composition according to claim 7, wherein the impact-resistant modifier is an acrylic core shell impact-resistant modifier.

9. The composition according to claim 8, wherein the impact modifier has a refractive index of 1.46 to 1.50 and a particle size of 0.01 to 2.0 μm.

10. The cellulose ester composition further comprises at least one polymer aliphatic polyester (PAP) in an amount of about 4 to about 12% by weight, wherein the PAP is C ２ From C ４ Alkanediol residues and C ４ ~C ８ The composition according to claim 1, which is an aliphatic polyester containing an alkyldicarboxylic acid residue or a ring-opened lactone residue.

11. The composition according to claim 10, wherein the at least one PAP is selected from poly(ethylene succinate) (PES), poly(butylene succinate) (PBS), poly(ethylene adipate) (PEA), poly(butylene adipate) (PBA), or a mixture thereof.

12. The composition according to claim 10, wherein the at least one PAP is poly(butylene succinate) (PBS) or a copolymer of poly(butylene succinate) and poly(butylene adipate) (PBSA).

13. The composition according to claim 12, wherein the PAP is PBS or PBSA with an MFR (190°C, 2.16 kg) of less than 25.

14. The composition according to claim 12, wherein the PAP is PBS or PBSA having an elongation at break of 250% or more.

15. The cellulose ester composition according to claim 1, wherein the cellulose ester is selected from one or more of cellulose propionate (CP), cellulose butyrate (CB), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose propionate butyrate (CPB), cellulose trippropionate (CTP), or cellulose tripylate (CTB).

16. The composition according to claim 1, wherein the cellulose ester is selected from cellulose acetate propionate (CAP) or cellulose acetate butyrate (CAB), and the composition contains 0 to 5% by weight of a plasticizer.

17. The composition according to claim 1, wherein the composition further comprises at least one additive selected from the group consisting of antioxidants, heat stabilizers, mold release agents, antistatic agents, whitening agents, colorants, plasticizers, minerals, ultraviolet stabilizers, lubricants, nucleating agents, reinforcing fillers, glass fibers, carbon fibers, flame retardants, dyes, pigments, colorants, additional resins, and combinations thereof.

18. The composition according to claim 17, wherein the total amount of the additive is less than 2% by weight of the total weight of the cellulose ester composition.

19. The composition according to claim 17, wherein the total amount of the additive is less than 1% by weight of the total weight of the cellulose ester composition.

20. The composition according to claim 18, wherein the total amount of the additives other than the impact modifier, friction modifier, plasticizer, and PAP is less than 2% by weight of the total weight of the cellulose ester composition.

21. The composition according to claim 19, wherein the total amount of the additives other than the impact modifier, friction modifier, plasticizer, and PAP is less than 1% by weight of the total weight of the cellulose ester composition.

22. The composition according to claim 1, wherein the composition comprises a secondary antioxidant in an amount ranging from about 0.05 to about 0.5% by weight and an acid scavenger in an amount ranging from about 0.5 to about 3% by weight, based on the total weight of the composition.

23. The composition according to claim 22, wherein the weight ratio of the acid scavenger to the secondary antioxidant is in the range of 5:1 to 20:

1.

24. The composition according to claim 1, wherein the static COF of the composition is 0.6 or less and the dynamic COF is 0.5 or less.

25. A molded or formed article comprising the polymer composition according to any one of claims 1 to 24.

26. The article according to claim 25, wherein the article is an assembly toy or a part thereof.

27. The article according to claim 25, wherein the article is an injection-molded assembly toy or a part thereof.

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