Compositions of cellulose esters and polymeric aliphatic polyesters and articles

Abstract

To provide melt-processable cellulose ester compositions that do not exhibit drawbacks even when containing a considerable amount of a monomer plasticizer.SOLUTION: A cellulose ester composition is provided comprising at least one kind of a cellulose ester, and at least one kind of a polymeric aliphatic polyester (PAP), and optionally at least one kind of an impact modifier and / or at least one kind of a monomeric plasticizer. Processes for producing the cellulose ester compositions as well as articles made using these compositions are also provided.SELECTED DRAWING: None

Description

Technical Field

[0001]

[0001] The present invention belongs to the field of cellulose ester chemistry, and in particular, to polymer aliphatic polyesters (PAP), and to cellulose esters optionally containing an impact modifier and / or a monomeric plasticizer. The present invention also belongs to the field of cellulose ester compositions containing at least one PAP, and optionally at least one impact modifier and / or at least one monomeric plasticizer. Also provided are methods for producing these cellulose ester compositions, and plastic articles produced using these compositions, such as spectacle frames, automotive parts, and toys.

Background Art

[0002]

[0002] Cellulose ester compositions typically have a heat deflection temperature (HDT) or glass transition temperature (Tg) of less than 90°C. Commercially available cellulose esters that are melt-processed into articles typically contain a significant amount of monomeric plasticizer in order to enable processing and impart sufficient toughness to the molded article. However, adding a high level of monomeric plasticizer can have drawbacks as it can lower the HDT compared to the base cellulose ester and may limit the use of cellulose ester materials for applications that can accommodate an HDT of less than about 90°C. Also, common monomeric plasticizers used in cellulose ester molded articles can cause exudation of the plasticizer during processing and use.

Summary of the Invention

Problems to be Solved by the Invention

[0003]

[0003] It would be beneficial to be able to provide a melt-processable cellulose ester composition that does not have such drawbacks.

Means for Solving the Problems

[0004]

[0004] Surprisingly, it has been found that compositions of cellulose esters such as cellulose acetate propionate (CAP) having a glass transition temperature (Tg) of about 110 °C or 120 °C or higher can be produced, and they can have good transparency and toughness. In some embodiments of the present invention, this can be achieved by reducing the amount of monomer plasticizer and, in some embodiments, completely eliminating the use of monomer plasticizer in the composition. By eliminating the monomer plasticizer, the common problems associated with the leaching of monomer plasticizer during use can be eliminated. However, reducing or eliminating the monomer plasticizer may reduce the toughness of these high-Tg cellulose compositions. Surprisingly, a specific combination of CAP and a polymer of polybutylene succinates (which may include other polymer aliphatic polyesters such as polyethylene, polypropylene, or succinates, glutarates, or adipates of polybutylene, may include different comonomers or tercomonomers, and are collectively described as PBS polymer or PAP as defined below) can restore the toughness of the high-Tg cellulose composition, is suitable for high-temperature applications, and can provide a cellulose ester composition having good flow characteristics, good transparency, and maintaining long-term dimensional stability.

[0005]

[0005] In some embodiments, the present invention relates to dispersing in a cellulose ester composition an amount of one or more PAPs, such as poly(butylene succinate) (PBS), sufficient to improve the mechanical and physical properties of the cellulose ester composition. The PAP (e.g., PBS) modified cellulose ester according to some embodiments of the present invention is melt processable and has a unique property of having a significantly higher Tg compared to commercially available plasticized cellulose ester thermoplastic resins, and having a high modulus of elasticity, good impact properties, and good load deformation resistance. and has unique properties of having a significantly higher Tg, a high modulus of elasticity, good impact properties, and good load deformation resistance.

[0006]

[0006] In one embodiment of the present invention, a cellulose ester composition comprising at least one type of cellulose ester and at least one type of PAP (for example, PBS) is provided. In one embodiment, the cellulose ester is selected from cellulose acetate propionate containing from about 10 to about 40% by weight of propionyl based on the total weight of the polymer, and the cellulose ester composition has a Tg of at least 120°C. In some embodiments, the cellulose ester composition has a Tg of at least 140°C or at least 150°C.

[0007]

[0007] In another embodiment of the present invention, a cellulose ester composition comprising at least one type of cellulose ester, at least one type of PAP, and at least one type of impact resistance improver is provided. In another embodiment of the present invention, a cellulose ester composition comprising at least one type of cellulose ester, at least one type of PAP, at least one type of impact resistance improver, and a monomer plasticizer of less than 1% to 5% by weight is provided.

[0008]

[0008] In another embodiment of the present invention, a method for producing a cellulose ester composition is provided, which includes contacting at least one type of cellulose ester, at least one type of PAP, and optionally at least one type of impact resistance improver and / or at least one type of monomer plasticizer, and mixing the formulation. In one embodiment, the cellulose ester composition contains a monomer plasticizer present in an amount that does not substantially lower the Tg of the cellulose ester composition compared to a similar composition without the monomer plasticizer. In some embodiments, the Tg does not change (for example, decrease) by more than 10%, or more than 5%, or more than 2% as a result of including the monomer plasticizer.

[0009]

[0009] In some embodiments of the present invention, it does not contain a monomer plasticizer, but contains 1% to 35% by weight, or 2.5% to 30% by weight, or 5 to 20% by weight, or 6 to 18% by weight, or 7 to 15% by weight of PAP based on the total weight of the cellulose ester composition, has a Tg value higher than 120 °C, or at least 140 °C, or at least 150 °C, and has a notched Izod impact strength value higher than 80 J / m, or higher than 100 J / m, or higher than 110 J / m, or higher than 125 J / m, or higher than 150 J / m, or higher than 175 J / m, or higher than 200 J / m at 23 °C. A cellulose ester composition is described.

[0010]

[0010] In other embodiments of the present invention, a cellulose ester composition that does not contain a monomer plasticizer but is melt-processable is provided. In some embodiments, the melt-processable cellulose ester composition contains 1% to 35% by weight, or 2.5% to 30% by weight, or 5 to 20% by weight, or 6 to 18% by weight, or 7 to 15% by weight of PAP based on the total weight of the cellulose ester composition, has a Tg value higher than 120 °C, or at least 140 °C, or at least 150 °C, a notched Izod impact strength value higher than 80 J / m, or higher than 100 J / m, or higher than 110 J / m, or higher than 125 J / m, or higher than 150 J / m, or higher than 175 J / m, or higher than 200 J / m at 23 °C, and has a spiral flow value of at least 38 centimeters (15 inches) when measured at a barrel temperature of 240 °C using the procedure described herein.

[0011]

[0011] In other embodiments, a small amount of monomer plasticizer can be included in the meltable cellulose ester composition described above. In some embodiments, the monomer - The plasticizer is present in an amount that does not substantially lower the Tg of the cellulose ester composition compared to a similar composition without monomeric plasticizer. In some embodiments, the Tg does not change (e.g., decrease) by more than 10%, or more than 5%, or more than 2% as a result of including the monomeric plasticizer.

[0012]

[0012] In one embodiment of the present invention, there is provided a polymer-based resin comprising at least one cellulose ester, at least one PAP, and optionally at least one monomeric plasticizer, wherein the cellulose ester is CAP, the PAP is PBS, and the resin comprises 0 to 5 wt%, 0 wt% to less than 5 wt%, 0 to 4 wt%, 0 to 2 wt%, or 0 to 1 wt% of the monomeric plasticizer. In one embodiment, the cellulose ester is CAP and the resin does not contain a monomeric plasticizer. In one embodiment, the cellulose ester is CAP, the PBS has an MFR (190 °C, 2.16 kg) of less than 10 and an elongation at break of 200% or more, and the resin does not contain a monomeric plasticizer and contains less than 10 wt%, or less than 8 wt% of any other additive. However, in some embodiments, the resin may also include additional pigments or colorants or optical additives, such as titanium dioxide, for opaque / coloring applications.

[0013]

[0013] In some embodiments, the MFR of the PAP measured at 190 °C using a 2.16 kg load in accordance with ASTM test method D1238 is less than 30.

[0014] In some embodiments, the cellulose ester resin is selected from at least one of cellulose propionate (CP), cellulose butyrate (CB), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose acetate isobutyrate (CAIB), cellulose propionate butyrate (CPB), cellulose tripropionate (CTP), or cellulose tributyrate (CTB). In some embodiments, the resin contains, or does not contain, any other one or more polymers that contribute to the continuous binder phase of the resin containing the cellulose ester, which 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%. For example, in some embodiments, PAP (e.g., PBS) exists as a dispersed phase within the cellulose ester resin and does not contribute to the continuous binder phase of the resin containing the cellulose ester.

[0014]

[0015] In some embodiments, the cellulose ester resin is selected from at least one of cellulose propionate (CP), cellulose butyrate (CB), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose acetate isobutyrate (CAIB), cellulose propionate butyrate (CPB), cellulose tripropionate (CTP), or cellulose tributyrate (CTB), and PAP (e.g., PBS) is miscible in the cellulose ester resin or in the same phase as the cellulose ester binder phase. In some embodiments, the cellulose ester resin and PAP (e.g., PBS) are miscible, and the cellulose ester composition further includes an impact modifier. In one embodiment, the impact modifier is a core - shell type impact modifier. In one embodiment, the impact modifier is an acrylic core - shell type impact modifier.

[0015]

[0016] In some embodiments, there is provided a cellulose ester composition comprising at least one type of cellulose ester, and at least one type of PAP, at least one type of impact resistance improver, and a monomer plasticizer of less than 1 wt% to 5 wt%. In some embodiments, the PAP, the impact resistance improver, and the monomer plasticizer are present in an amount sufficient to provide a composition that is moldable and has a balance of a relatively high Tg, good toughness, and creep resistance (i.e., load deformation resistance). In some embodiments, the cellulose ester is CAP, the PAP is PBS, the impact resistance improver is an acrylic core-shell type impact resistance improver, and the monomer plasticizer is an adipate-based monomer plasticizer (e.g., DOA), and the composition comprises 2 to 10 wt%, or 3 to 8 wt% of PBS; 2 to 10 wt%, or 4 to 8 wt% of the impact resistance improver; and a monomer plasticizer of 2 wt% to less than 5 wt%. In one embodiment, the monomer plasticizer is DOA.

[0016]

[0017] In some embodiments, for any of the above embodiments, one or more types of PAPs include PBS, or a copolymer of poly(butylene succinate) and poly(butylene adipate) (PBSA). In some embodiments, for any of the above embodiments, the PAP is PBS or PBSA. In some embodiments, for any of the above embodiments, the PAP is PBS.

[0017]

[0018] In some embodiments, the cellulose ester can be selected from cellulose acetate butyrate containing about 5 to about 55 wt% butyryl based on the total weight of the polymer. In some embodiments, the cellulose ester can be selected from cellulose acetate propionate containing about 5 to about 50 wt% propionyl based on the total weight of the polymer.

[0018]

[0019] In some embodiments, the cellulose ester is cellulose acetate propionate (CAP) having a propionyl content higher than 5% by weight based on the total weight of the polymer. In some embodiments, the cellulose ester is cellulose acetate propionate (CAP) having a propionyl content higher than 40% based on the total weight of the CAP polymer. In some embodiments, the cellulose ester is cellulose acetate propionate (CAP) having a propionyl content less than 40% based on the total weight of the CAP polymer.

[0019]

[0020] In some embodiments, the cellulose ester is cellulose acetate butyrate (CAB) having a butyryl content higher than 5% by weight based on the total weight of the polymer. In some embodiments, the cellulose ester is cellulose acetate butyrate (CAB) having a butyryl content higher than 40% based on the total weight of the CAB polymer. In some embodiments, the cellulose ester is cellulose acetate butyrate (CAB) having a butyryl content less than 32% by weight or a butyryl content in the range of 15 - 32% by weight based on the total weight of the CAB polymer.

Mode for Carrying Out the Invention

[0020]

[0021] In one embodiment of the present invention, there is provided a cellulose ester composition comprising at least one type of cellulose ester, at least one type of PAP, and optionally at least one type of impact modifier and / or at least one type of monomer plasticizer.

[0021]

[0022] In some embodiments, the cellulose ester used in the present invention may be any cellulose ester having a sufficient content of a salt or ester moiety of a C3 - C 10 acid, preferably a propionate and / or butyrate moiety. The cellulose esters that can be used for the present invention generally have the structure:

[0022] [Chem.]

[0023] (wherein, R 1 , R 2 , and R 3 are each independently selected from the group consisting of hydrogen or a linear alkanoyl having 2 to 10 carbon atoms) and contains a repeating unit. For cellulose esters, the substitution level is usually represented by the degree of substitution (DS), which is the average number of non-OH substituents per anhydroglucose unit (AGU). Generally, conventional cellulose contains three hydroxyl groups that can be substituted in each AGU unit; thus, the DS can have a value between 0 and 3. However, low molecular weight cellulose mixed esters can have a total degree of substitution slightly higher than 3 as a result of the contribution of end groups. Natural cellulose is a large polysaccharide having a degree of polymerization of 250 to 5,000 even after pulping and purification; thus, the assumption that the maximum DS is 3.0 is approximately correct. However, in the case of low molecular weight cellulose mixed esters, as the degree of polymerization decreases, the end groups of the polysaccharide backbone become relatively more significant, thereby resulting in a DS that can be in a range higher than 3.0. Low molecular weight cellulose mixed esters will be discussed in more detail later herein. Since the DS is a statistical average value, a value of 1 does not guarantee that all AGUs have a single substituent. In some cases, unsubstituted anhydroglucose units may be present, some may have two substituents, some may have three substituents, and usually this value is non-integer. The total DS is defined as the average number of all substituents per anhydroglucose unit. The degree of substitution per AGU may refer to a specific substituent such as hydroxyl, acetyl, butyryl, or propionyl, for example.

[0024]

[0023] In some embodiments, the cellulose ester used may be a cellulose triester or a secondary cellulose ester. Examples of cellulose triesters include, but are not limited to, cellulose tripropionate or cellulose tributyrate. Examples of secondary cellulose esters include cellulose acetate propionate and cellulose acetate butyrate.

[0025]

[0024] In one embodiment of the present invention, 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 acetate isobutyrate (CAIB), cellulose tripropionate (CTP), or cellulose tributyrate (CTB), or a combination thereof. Examples of some cellulose esters are described in U.S. Patent 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. There is.

[0026]

[0025] In one embodiment of the present invention, the cellulose ester can be selected from cellulose propionate (CP), cellulose butyrate (CB), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose acetate isobutyrate (CAIB), cellulose propionate butyrate (CPB), cellulose tripropionate (CTP), or cellulose tributyrate (CTB), but is not selected from cellulose acetate (CA).

[0027] In some embodiments of the present invention, the cellulose ester has a total weight percentage 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 less than 5% to 50%, or less than 10% to 50%, or less than 15% to 50%, or less than 20% to 50%, or less than 25% to 50%, or less than 30% to 50%, or less than 35% to 50%, or less than 40% to 50%, or less than 45% to 50%, or less than 35% to 50%, or less than 40% to 50%, or less than 45% to 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.

[0028] In some embodiments of the present invention, the cellulose ester has a total weight percentage 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 more than 40% up 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 more than 40% up 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 more than 40% up 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 more than 40% up 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% to less than 32%, or 10% to less than 32%, or 15% to less than 32%, or 20% to less than 32%, or 25% to 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.

[0029]

[0028] In some embodiments, the cellulose ester, as a percentage of the total weight of the polymer, is 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 5 0%, or a cellulose propionate butyrate or cellulose acetate propionate butyrate having a total content of propionate and butyryl in the range of 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%.

[0030]

[0029] The cellulose ester can be produced by any method known in the art. Examples of methods for producing cellulose esters are taught in Kirk-Othmer, Encyclopedia of Chemical Technology, 5th Edition, Vol. 5, Wiley-Interscience, New York (2004), pp. 394-444. The cellulose used as a starting material for producing the cellulose ester can be obtained in different grades and, among others, from cotton linters, softwood pulp, hardwood pulp, corn fibers, and other agricultural sources, as well as from sources such as bacterial cellulose.

[0031]

[0030] One way to produce a cellulose ester is the esterification of cellulose by mixing cellulose with a suitable organic acid, acid anhydride, and catalyst. Next, the cellulose is converted to cellulose triester. Next, ester hydrolysis is carried out by adding a water - acid mixture to the cellulose triester, and then this can be filtered to remove gel particles or fibers. Next, water is added to the mixture to precipitate the cellulose ester. Next, the cellulose ester can be washed with water to remove reaction by - products and subsequently dehydrated and dried.

[0032]

[0031] The cellulose triester to be hydrolyzed can have three substituents independently selected from alkanoyl 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 produced by a number of methods known to those skilled in the art. For example, cellulose esters can be produced by the heterogeneous acylation of cellulose in a mixture of carboxylic acid and anhydride in the presence of a catalyst such as H2SO4. Cellulose triester can also be produced by the homogeneous acylation of cellulose dissolved in a suitable solvent such as LiCl / DMAc or LiCl / NMP.

[0033]

[0032] After esterifying cellulose to a triester, a part of the acyl substituents can be removed by hydrolysis or alcoholysis to obtain a secondary cellulose ester. As described above, depending on the particular method used, the distribution of acyl substituents can be random or non - random. Secondary cellulose esters can also be produced directly without hydrolysis by using a limited amount of acylating agent. This process is particularly useful when the reaction is carried out in a solvent that dissolves cellulose. All of these methods can be used to obtain cellulose esters useful in the present invention.

[0034]

[0033] The most common commercial secondary cellulose esters are produced by first performing acid-catalyzed heterogeneous acylation of cellulose to form a cellulose triester. After obtaining a homogeneous solution of the cellulose triester in the corresponding carboxylic acid, the cellulose triester is then subjected to hydrolysis 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) at each hydroxyl is approximately equal.

[0035]

[0034] Some examples of cellulose esters useful in various embodiments of the present invention can be produced using techniques known in the art and are available from Eastman Chemical Company, Kingsport, TN, USA (e.g., Eastman® cellulose acetate propionate CAP482-20, Eastman® cellulose acetate propionate CAP141-20, Eastman® cellulose acetate butyrate CAB 381-20, and cellulose acetate butyrate CAB 171-15). Some examples of common cellulose esters are listed in Table 1 below along with the indicated ball drop viscosity values.

[0036]

[0035]

[0037]

Table 1

[0038]

[0036] In some embodiments, the cellulose ester used in the present invention may also contain chemical functional groups and is described herein as either a derivatized, modified, or functionalized cellulose ester. The functionalized cellulose ester is produced by reacting the free hydroxyl groups of the cellulose ester with a bifunctional reactant having one linking group for grafting to the cellulose ester and one functional group for imparting a new chemical group to the cellulose ester. Examples of such bifunctional reactants include succinic anhydride, which is linked via an ester bond and imparts an acid functional group; mercaptosilane, which is linked via an alkoxysilane bond and imparts a mercapto functional group; and isocyanotoethyl methacrylate, which is linked via a urethane bond and imparts a methacrylate functional group.

[0039]

[0037] In one embodiment of the present invention, the functionalized cellulose ester is produced by reacting the free hydroxyl 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, acetoacetate, acetoacetate imide, mercapto, melamine, and long-chain alkyl.

[0040]

[0038] The bifunctional reactant for producing a cellulose ester containing a long-chain alkyl functional group is described in U.S. Patent No. 5,750,677, which is incorporated herein by reference to the extent not inconsistent with the description herein. In one embodiment, the cellulose ester containing a long-chain alkyl functional group is produced by reacting cellulose in a carboxamide diluent or a urea-based diluent with an acylating agent using a titanium-containing species. Long-chain alkyl Cellulose esters containing a ru functional group 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.

[0041]

[0039] In some embodiments, the cellulose ester is cellulose acetate propionate (CAP) having a propionyl content higher than 5% based on the total weight of the CAP polymer. In some embodiments, the cellulose ester is cellulose acetate propionate (CAP) having a propionyl content of less than about 40% based on the total weight of the CAP polymer.

[0042]

[0040] In some embodiments of the present invention, the cellulose ester has a propionyl total weight percentage 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 less than 5 to 50%, or less than 10 to 50%, or less than 15 to 50%, or less than 20 to 50%, or less than 25 to 50%, or less than 30 to 50%, or less than 35 to 50%, or less than 40 to 50%, or less than 45 to 50%, or less than 35 to 50%, or less than 40 to 50%, or less than 45 to 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.

[0043]

[0041] In some embodiments, the cellulose ester is cellulose acetate butyrate (CAB) having a butyryl content higher than 5% based on the total weight of the CAB polymer. In some embodiments, the cellulose ester is cellulose acetate butyrate (CAB) having a butyryl content less than 55% based on the total weight of the CAB polymer.

[0044]

[0042] In some embodiments of the present invention, the cellulose ester has a total weight percentage 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 more than 40% up 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 more than 40% up 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 more than 40% up 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 more than 40% up 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% to less than 32%, or 10% to less than 32%, or 15% to less than 32%, or 20% to less than 32%, or 25% to less than 32%, or 5 to 30%, or 10 to 30%, or 15 to 30%, or 20 to 30, or 25 to 30 % by total weight of butyryl.

[0045]

[0043] In some embodiments, the cellulose ester is cellulose propionate butyrate or cellulose acetate propionate butyrate having a total content of propionyl and butyryl 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%, or 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.

[0046]

[0044] Any of the cellulose esters discussed above may also contain residual hydroxyl units of 10% or less, preferably 0.5% to 5%.

[0045] In some embodiments of the present invention, the term "PBS polymer" can be used interchangeably with polymer aliphatic polyester (PAP), where PAP is a polymer aliphatic polyester containing residues of one or more C2-C4 alkanediols and residues of one or more C4-C8 alkyl dicarboxylic acids, or containing residues of ring-opening lactones. In some embodiments, PAP contains residues of C2-C4 alkanediols and residues of C4-C6 alkyl dicarboxylic acids. In some embodiments, PAP contains residues of ethylene glycol or 1,4-butanediol, and residues of succinic acid, glutaric acid, or adipic acid. In some embodiments, PAP contains residues of ethylene glycol or 1,4-butanediol, and residues of succinic acid. In some embodiments, PAP is selected from poly(butylene succinate) or poly(ethylene succinate). In some embodiments, PAP is selected from poly(butylene adipate) or poly(ethylene adipate). In some embodiments, PAP is poly(butylene succinate) (PBS). In other embodiments, the aliphatic polyester contains residues of ring-opening of lactones such as caprolactone (cyclic esters). In some embodiments, PAP can be a copolymer. In some embodiments, 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 some embodiments, PAP has a number average molecular weight (Mn) in the range of 5000-20000, or 8000-20000, or 8000-15000, or 9000-12000. The molecular weight (and Mn) can be determined using gel permeation chromatography (GPC) with a refractive index detector and a polystyrene standard sample using methylene chloride as the solvent. In one embodiment, PAP is poly(butylene succinate) having a Mn in the range of 5000-20000; or 10000-20000; or 15000-20000.

[0047]

[0046] In some embodiments of the present invention, the PBS polymer (or PAP) may be any poly(butylene succinate) material. In some embodiments, the PBS polymer (or PAP) can be selected 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 substituent group, suberic acid, 1,3-propanediol, and other substituted glycols to obtain a PBS random copolymer. 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 PBS polymer (or PAP) is poly(butylene succinate) (PBS).

[0048]

[0047] In some embodiments, the MFR of the PAP measured at 190 °C using a 2.16 kg load in accordance with ASTM test method D1238 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 some embodiments, the PAP has an MFR of at least 0.5, or 1, or 2.

[0049]

[0048] In some embodiments, the PBS polymer (or PAP) has an MFR (190 °C, 2.16 kg) 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 some embodiments, the PBS polymer (or PAP) has an elongation at break of 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 PBS polymer (or PAP) having an MFR (190 °C, 2.16 kg) of 10 or less and an elongation at break of 100% or more. In some embodiments, the amount of such PBS polymer (or PAP) in the cellulose ester composition is 0.5 to 40% by weight, or 1 to 35% by weight, or 2 to 30% by weight, or 2 to 20% by weight, or 2 to 10% by weight, or 2.5 to 30% 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 7 to 18% by weight, or 8 to 12% by weight, based on the total cellulose ester composition. In some embodiments, the composition comprises, in addition to the PBS polymer (or PAP), at least one impact modifier and / or at least one monomer plasticizer, and the amount of the PBS polymer (or PAP) in the cellulose ester composition is 0.5 to 40% by weight, or 1 to 35% by weight, or 2 to 30% by weight, or 2 to 20% by weight, or 2 to 10% by weight, or 3 to 10% by weight, or 3 to 8% by weight, or 3 to 7% by weight, or 4 to 8% by weight, or 4 to 7% by weight, based on the total cellulose ester composition.

[0050]

[0049] In one embodiment, one or more impact modifiers can be included together with the PBS polymer (or PAP). In some embodiments, the impact modifier can be any polymeric material classified as an elastomer having a (Tg) lower than room temperature. The Tg can be measured, for example, in accordance with ASTM-D3418 using a TA-2100 thermal analyzer at a scanning rate of 20 °C / min. Some classes of impact modifiers are compatible with this description.

[0051]

[0050] 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 a further monomer that limits the crystallization of the polymer, increases the amount of chains having a Tg lower than room temperature, and reduces the elastic modulus to below 500 MPa. Examples of modified olefins include ethylene methyl acrylate (EMA) (examples include Elvaloy 4051, Lotader 3410, and Lotader 8900), ethylene butyl acetate (EBA), ethylene vinyl acetate (EVA) (examples include 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 elastomer (EPDM) (example includes Royaltuf 498), and ethylene propylene rubber elastomer (EPR).

[0052]

[0051] In one embodiment, the impact modifier may be a block copolymer in which at least one segment of the chain has a Tg lower than room temperature (referred to as a soft segment), and at least one segment of the chain has a Tg or Tm higher than room temperature (referred to as a hard segment). These block copolymers are also generally referred to as thermoplastic elastomers (TPE). Examples of this class of block copolymers include poly(styrene-butadiene-styrene) (SBS), poly(styrene-ethylene-butylene-styrene) (SEBS), and styrene-isoprene rubber elastomer (SIS) (examples include Kraton G1657MS, Kraton FG1901G, and Kraton FG1924G); thermoplastic urethane (TPU) (examples include Elastolan 1170Z, Estane 2355, Estane ALR CL87A, and Estane ALR 72A); polyester-ether copolymers (examples include Ecdel 9966 and Hytrel 3078), or styrenic materials such as polyamide-ether copolymers ( an example is Pebax 5533).

[0053]

[0052] In one embodiment, the impact modifier can be selected from the class of emulsion preparation materials known as core-shell type impact modifiers. In one embodiment, the impact modifier is an MBS core-shell type impact modifier such as methacrylate-butadiene-styrene having a core formed from a butadiene-styrene copolymer and a shell formed from a methyl methacrylate-styrene copolymer. In other embodiments, the impact modifier is an acrylic core-shell type impact modifier having a core formed from an acrylic polymer such as butyl acrylate or styrene butyl acrylate, and a shell formed from a polymethyl methacrylate or styrene methyl methacrylate copolymer.

[0054] In some embodiments, the MBS impact modifier may include a polymer or copolymer of 10-70% by weight of butadiene, and first, a graft polymer composition including methyl (meth)acrylate and a crosslinking agent, second, styrene, and third, a graft including methyl (meth)acrylate and optionally a crosslinking agent.

[0055]

[0054] Suitable monomers for polymerizing with conjugated diolefins, preferably butadiene, include alkenyl aromatic compounds, preferably vinyl aromatic compounds such as styrene, divinylbenzene, α-methylstyrene, vinyltoluene, hydrogenated styrene; lower (C2-C4) alkyl acrylates such as ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, 3-methylbutyl acrylate, amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate; lower (C2-C4) alkyl (meth)acrylates; acrylonitrile; olefins; etc., or any combination of the above. 12 ) alkyl (meth)acrylate; acrylonitrile; olefins; etc., or any combination of the above; can be mentioned.

[0056]

[0055] Suitable crosslinking agents include divinylbenzene; di(meth)acrylate; diacrylates such as diacrylates 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.

[0057]

[0056] In one embodiment, the MBS core-shell type impact modifier is a copolymer of butadiene and styrene, most preferably of butadiene, styrene, and divinylbenzene. It may contain a terpolymer. The relative amounts of the monomers constituting the copolymer substrate can vary, but based on 100 parts by weight in total of butadiene, styrene, and divinylbenzene, the butadiene component usually constitutes about 30 to 100 parts by weight, the styrene component constitutes 0 to about 70 parts by weight, and the divinylbenzene component constitutes 0 to about 5 parts by weight. In one embodiment, the copolymer substrate may contain, on the same basis, about 50 to about 90 parts by weight of butadiene, about 10 to about 50 parts by weight of styrene, and 0 to about 5 parts by weight of divinylbenzene, most preferably about 65 to about 85 parts by weight of butadiene, about 15 to about 35 parts by weight of styrene, and about 0.5 to about 2.0 parts by weight of divinylbenzene.

[0058]

[0057] Examples of methacrylate - butadiene - styrene core - shell polymers are those described in U.S. Patents US - 4,446,585, US - 5,534,594, and US - 6,331580, but are not limited thereto. MBS core - shell type impact modifiers can be obtained from Kaneka as Kane Ace B564, from Arkema as Clearstrength, from Mitsubishi Chemical as Metablen C and Metablen E, from Dow as Paraloid, and from Evonik as Visiomer.

[0059]

[0058] In one embodiment of the present invention, the core - shell type impact modifier is about 25 to 95% by weight of a first elastomer phase polymerized from a monomer system containing about 75 to 99.8% by weight of (C1 - C6) alkyl acrylate, 0.1 to 5% by weight of a crosslinkable monomer, and 0.1 to 5% by weight of a graft - bonding monomer, and about 75 to 5% by weight of a final hard thermoplastic phase containing no epoxy groups polymerized in the presence of such an elastomer phase, which is an acrylic impact modifier.

[0060]

[0059] Examples of useful acrylates are methyl acrylate, ethyl acrylate, butyl acrylate, 2 - ethylhexyl acrylate, etc. In some embodiments, the acrylate is n - butyl acrylate and ethyl acrylate.

[0061]

[0060] The graft-bonding monomer has both highly reactive double bonds and less reactive double bonds. The highly reactive double bonds tend to polymerize during the first-stage monomer polymerization, leaving double bonds for polymerization during the next-stage polymerization, thereby defining it as a polyethylene unsaturated monomer that graft-bonds the first-stage polymer to the second-stage polymer. 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. Also preferably, generally 0.05 to 3% by weight of a crosslinkable monomer is also present based on the first-stage monomer system, which is defined as a polyethylene unsaturated monomer having at least two double bonds with substantially equal reactivity to cause crosslinking during the first-stage polymerization. Examples of common crosslinkable monomers are 1,3-butylene diacrylate, 1,3-butylene dimethacrylate, divinylbenzene, and the like.

[0062]

[0061] "Epoxy functional group" means an epoxy unit pendant from the final-stage polymer. In some embodiments, the epoxy functional group is introduced into the final-stage polymer by using an epoxy-containing monomer such as glycidyl acrylate or glycidyl methacrylate in the final-stage monomer mixture.

[0063]

[0062] Examples of acrylic core-shell polymers are those described in Patents: US-3,448,173, US-3,655,825, and US-3,853,968, but are not limited thereto. Examples of suitable acrylic impact modifiers are Kane Ace ECO100 and M570 from Kaneka, Durastrength from Arkema, Elvaloy and Elvaloy HP from DuPont, Metablen W from Mitsubishi Chemical, and Paraloid from Dow.

[0064]

[0063] In one class of this embodiment, the impact modifier is an ABS core-shell type impact modifier having a core formed from a butadiene-styrene copolymer and a shell formed from an acrylonitrile-styrene copolymer. Examples of the ABS core-shell type impact modifier include Blendex from Galata Chemicals and Elix from Elix Polymers.

[0065]

[0064] In one class of this embodiment, the impact modifier is a silicone-acrylic type core-shell type impact modifier having a core formed from a silicone-acrylic rubber and a shell formed from a PMMA copolymer or a methyl methacrylate-styrene copolymer. An example of the silicone-acrylic type core-shell type impact modifier is Metablen S from Mitsubishi Chemical Company.

[0066]

[0065] In one embodiment, the impact modifier has a neutral acidity. This is thought to help prevent the cellulose ester from decomposing during melt processing of the composition.

[0066] In one embodiment, the impact modifier may 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.

[0067]

[0067] In one embodiment using a non-reactive impact modifier, the impact modifier comprises a first polymer chain segment that is more chemically or physically compatible with the cellulose ester than another polymer chain segment. In one embodiment, the first segment comprises polar functional groups that impart 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 interaction of the first polymer chain segment, which is preferential to the second segment, with the cellulose ester polymer, and can mean molecular scale or microscale interactions. The first segment can be composed of oligomers or polymers of 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; polyethylene vinyl acetate; polyvinyl acetate; and polyvinyl alcohol. In one embodiment, the first segment is polyethylene vinyl acetate; polyoxyethylene, or polyvinyl alcohol.

[0068]

[0068] In some embodiments, the second segment can be either a saturated or unsaturated hydrocarbon group, or can include both saturated and unsaturated hydrocarbon groups. The second segment can be an oligomer or a polymer. In one embodiment of the present invention, the second segment of the non-reactive impact modifier is selected from the group consisting of polyolefins, polydienes, polyaromatic compounds, and copolymers. An example of a polyaromatic second segment is polystyrene. An example of a copolymer second segment is a styrene / butadiene copolymer.

[0069]

[0069] The first and second segments of the non-reactive impact modifier may have a diblock, triblock, branched, or comb structure. The weight average molecular weight (Mw) of the non-reactive impact modifier may 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 may range from about 15 to about 85% polar first segment / about 15 to about 85% non-polar second segment. It may be within the range.

[0070]

[0070] 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 are C 11 ~C 15 secondary alcohol ethoxylates, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and C 12 ~C 14 natural linear alcohols ethoxylated with ethylene oxide. C 11 ~C 15 alcohol ethoxylates can be obtained from the Dow Chemical Company as Dow Tergitol® 15S. Poly oxyethylene cetyl ether and polyoxyethylene stearyl ether can be obtained from ICI Surfactants as products of the Brij® series. C natural linear alcohols ethoxylated with ethylene oxide can be obtained from Hoechst Celanese as products of the Genapol® series. Ethoxylated alkyl 12 ~C 14 phenols can be obtained from ICI Surfactants as products of the Nonidet® series. Examples of phenols include octylphenoxypoly(ethyleneoxy)ethanol and nonylphenoxypoly(ethyleneoxy)ethanol. Octylphenoxypoly(ethyleneoxy)ethanol can be obtained from Rhodia as products of the Igepal® CA series, and nonylphenoxypoly(ethyleneoxy)ethanol can be obtained from Rhodia as products of the Igepal CO series or from Dow Chemical Company as Tergitol® ® NP. Examples of ethoxylated fatty acids include polyethylene glycol monostearate or monolaurate, which can be obtained from Henkel as products of the Nopalcol® series. Block polymers of propylene oxide and ethylene oxide can be obtained from BASF as products of the Pluronic® series. Polyglycerol esters can be obtained from Stepan as products of the Drewpol® series. Polysaccharide esters can be obtained from Henkel as products of the Glucopon® series (which are alkyl polyglucosides). Sorbitan esters can be obtained from ICI as products of the Tween® series.

[0071]

[0071] In another embodiment of the present invention, the non-reactive impact modifier can be synthesized in situ in the cellulose ester composition by reacting a cellulose ester-compatible compound. These compounds can be, for example, telechelic oligomers defined as prepolymers that can initiate further polymerization or other reactions by their reactive end groups. In one embodiment of the present invention, these in situ impact modifiers can have a higher weight average molecular weight (Mw) of about 10,000 to about 1,000,000.

[0072]

[0072] In other embodiments of the present invention, the impact modifier may be reactive. The reactive impact modifier can include a polymer or oligomer compatible with one component of the composition and a functional group capable of reacting with other components of the composition. In some embodiments, there are two types of reactive impact modifiers that can be used. The first reactive impact modifier has a hydrocarbon chain compatible with the cellulose ester and also has a functional group capable of reacting with the cellulose ester. Such functional groups include, but are not limited to, carboxylic acid, anhydride, acid chloride, epoxide, and isocyanate. 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 oil esters; styrene maleic anhydride copolymers; maleic anhydride grafted polypropylene; copolymers of maleic anhydride and olefins and / or acrylic acid esters, such as terpolymers of ethylene, acrylic acid esters, and maleic anhydride ; and copolymers of glycidyl methacrylate and olefins and / or acrylic acid esters, such as terpolymers of ethylene, acrylic acid esters, and glycidyl methacrylate, but are not limited thereto.

[0073]

[0073] Reactive impact modifiers are available from Sartomer / Cray Valley as SMA® 3000 styrene maleic anhydride copolymer, from Eastman Chemical Company as Eastman G-3015® maleic anhydride grafted polypropylene, from Westlake Chemical as Epolene® E-43 maleic anhydride grafted polypropylene, from Arkema as Lotader® MAH 8200 random ter polymer of ethylene, acrylic acid esters, and maleic anhydride, Lotader® of ethylene, acrylic acid esters, and glycidyl methacrylate Registered Trademark) GMA AX8900 random terpolymer and Lotarder (registered trademark) GMA AX8840 random terpolymer of ethylene, acrylic ester, and glycidyl methacrylate can be obtained.

[0074]

[0074] The reactive polyolefin impact modifier can be obtained as Lotader, Fusabond, Elvloy PTW, Lotryl, Elvaloy AC, InterLoy.

[0075] The second type of reactive impact modifier has a polar chain compatible with the cellulose ester and also has a functional group capable of reacting with the cellulose ester. Examples of these types of reactive impact modifiers include cellulose esters or polyethylene glycols having an olefin functional group or a thiol functional group. Examples of 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 functional group is polyethylene glycol thiol. An example of a reactive cellulose ester impact modifier is mercaptoacetate cellulose ester.

[0075]

[0076] In some embodiments of the present invention, the amount of the impact modifier in the cellulose ester composition is about 1 wt% to about 15 wt%, or about 2 wt% to about 10 wt%, or about 4 wt% to about 10 wt%, or about 4 wt% to about 8 wt%, or about 5 wt% to about 10 wt% based on the weight of the cellulose ester composition. In some embodiments, the cellulose ester composition comprises 55 to 98 wt% of at least one cellulose ester, preferably CAP; 1 to 30 wt% of at least one PBS polymer (or PAP), preferably PBS having an MFR (190 °C, 2.16 kg) of less than 25 and an elongation at break of 100% or more; and 1 to 15 wt% of at least one impact modifier, preferably an acrylic core-shell type impact modifier. In some embodiments containing an impact modifier, CAP contains more than 10 wt%, or more than 20 wt%, or more than 30 wt%, or more than 40 wt%, or more than 45 wt% propionyl.

[0076]

[0077] 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% as measured using a 3.2 mm plaque after injection molding at a barrel set point of 249 °C and a residence time of 5 minutes in accordance with ASTM-D1003. In some embodiments, the polymer-based resin has a transmittance 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% as measured using a 3.2 mm plaque after injection molding at a barrel set point of 249 °C and a residence time of 5 minutes in accordance with ASTM-D1003. In one class of this embodiment, the cellulose ester composition containing the PBS polymer (or PAP) has a haze percentage of less than 10%. In some embodiments, the cellulose ester composition containing the PBS polymer (or PAP) has a haze percentage of less than 8%, or less than 6%, or less than 5%.

[0077]

[0078] In other embodiments, the refractive index (RI) of the PBS polymer (or PAP) is close to the refractive index (RI) of one or more cellulose esters sufficient to provide a composition having high transmittance and low haze. In one embodiment, the PBS polymer (or PAP) has an RI close to that of a cellulose ester of about 1.46 to 1.48, providing a transparent composition. In some embodiments, the PBS polymer (or PAP) and the cellulose ester component have a refractive index difference of about 0.006 to about -0.0006: RI (second component) - RI (first component) (e.g., RI of CE - RI of PBS), and the blend has at least 75% transmittance and a haze of 10% or less, more preferably 5% or less.

[0078]

[0079] In some embodiments of the present invention, the amount of the PBS polymer (or PAP) in the cellulose ester composition is about 0.5 wt% to about 40 wt%, or about 1 wt% to about 35 wt%, or 2 to 30 wt%, or 2 to 20 wt%, or 2 to 10 wt%, or about 2.5 wt% to about 30 wt%, or about 5 wt% to about 25 wt%, or about 5 wt% to about 20 wt%, or about 5 wt% to about 15 wt%, or about 5 wt% to about 10 wt%, or about 10 wt% to about 30 wt%, or about 10 wt% to about 25 wt%, or about 10 wt% to about 20 wt%, or about 10 wt% to about 15 wt%, or more than 10 wt% to up to about 30 wt%, or more than 10 wt% to up to about 25 wt%, or more than 10 wt% to up to about 20 wt%, or more than 10 wt% to up to about 15 wt%, based on the weight of the cellulose ester composition. In some embodiments, the composition includes at least one impact modifier and / or at least one monomer plasticizer in addition to the PBS polymer (or PAP), and the amount of the PBS polymer (or PAP) in the cellulose ester composition is 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 total cellulose ester composition.

[0079]

[0080] In other embodiments of the present invention, the cellulose ester composition further comprises at least one additional polymer component as a blend (with the cellulose ester) in an amount of 5 to 95% by weight, 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 above polymers; but are not limited thereto. The blend can be produced by conventional processing techniques known in the art, such as melt blending or solution blending. In some embodiments, the total amount of additional polymer compounds (excluding PBS polymer (or PAP)) is less than 25% by weight, or less than 20% by weight, or less than 15% by weight, or less than 10% by weight, or less than 5% by weight, or 0, based on the total weight of the cellulose ester composition.

[0080]

[0081] In one embodiment of the present invention, in addition to the PBS polymer (or PAP) (and optionally an impact modifier), the composition may contain a monomeric plasticizer. In some embodiments, the monomeric plasticizer used in the present invention can be any one known in the art that can lower the glass transition temperature and / or melt viscosity of the cellulose ester to improve the melt processing characteristics. The monomeric plasticizer is a cellulose ester Any monomer plasticizer suitable for use with (in addition to the PBS polymer (or PAP) and impact modifier included in the composition) may be used. The monomer plasticizer level must be lower than the standard (or normal) monomer plasticizer level used in conventional / commercial cellulose esters such that the composition has a higher Tg, good toughness, and good fluidity than a fully plasticized cellulose ester composition. In some embodiments, the monomer plasticizer is present in an amount that does not substantially lower the Tg of the cellulose ester composition compared to a similar composition without the monomer plasticizer. In some embodiments, the Tg does not change (e.g., decrease) by more than 20%, or more than 15%, or more than 10%, or more than 5%, or more than 2% as a result of including the monomer plasticizer.

[0081]

[0082] The monomer plasticizer may have a structure that is either a monomer or a polymer. In one embodiment, the monomer plasticizer is at least one selected from the group consisting of aromatic phosphate ester plasticizers, alkyl phosphate ester plasticizers, dialkyl ether diester plasticizers, tricarboxylic acid ester plasticizers, polymeric 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, benzoate plasticizers, polyol benzoate plasticizers, adipate plasticizers, phthalate plasticizers, glycolic acid ester plasticizers, citrate plasticizers, hydroxyl-functional plasticizers, or solid amorphous resin plasticizers.

[0082]

[0083] In one embodiment of the present invention, the monomer plasticizer can be selected from at least one of triphenyl phosphate, cresyl 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.

[0083]

[0084] In another embodiment of the present invention, the monomer plasticizer can be selected from at least one of esters containing (i) an acid residue containing 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) an alcohol residue containing one or more residues of an aliphatic, alicyclic, or aromatic alcohol containing about 20 or fewer carbon atoms.

[0084]

[0085] In another embodiment of the present invention, the monomer plasticizer can be selected from at least one of esters containing (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, or phosphoric acid; and (ii) at least one alcohol residue selected from the group consisting of aliphatic, alicyclic, or aromatic alcohols containing about 20 or fewer carbon atoms.

[0085]

[0086] In other embodiments of the present invention, the monomer plasticizer may contain an alcohol residue, and the alcohol residue may be stearyl alcohol, lauryl alcohol, phenol, benzyl alcohol, hydroquinone, catechol, resorcinol, ethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, and diethylene gly col, at least one selected therefrom.

[0086]

[0087] In other embodiments of the present invention, the monomer plasticizer can be selected from at least one of benzoate, phthalate, phosphate, arylene-bis(diaryl phosphate), and isophthalate. In other embodiments, the monomer plasticizer contains diethylene glycol dibenzoate (hereinafter abbreviated as "DEGDB").

[0087]

[0088] In other embodiments of the present invention, the monomer plasticizer is a C2-C 10 dicarboxylic acid residue, such as residues of malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid; and a C2-C 10 diol residue; and can be selected from aliphatic compounds containing the same.

[0088]

[0089] In other embodiments, the monomer plasticizer may contain a diol residue which may 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.

[0089]

[0090] In other embodiments of the present invention, the monomer plasticizer includes at least one of 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).

[0090]

[0091] In other embodiments of the present invention, the monomer plasticizer includes (A) about 5 to about 95% by weight of a C2-C 12 carbohydrate organic ester (the carbohydrate contains about 1 to about 3 monosaccharide units); and (B) about 5 to about 95% by weight of one or more of a C2-C 12 polyol ester (the polyol is derived from a C5 or C6 carbohydrate). In one embodiment, the polyol ester does not contain or comprises no one or more polyol acetates.

[0091]

[0092] In other embodiments, the monomer 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.

[0092]

[0093] In other embodiments of the present invention, the monomer plasticizer includes at least one carbohydrate ester, and the carbohydrate portion of the carbohydrate ester includes one or more of α-glucose pentaacetate, β-glucose pentaacetate, α-glucose pentapropionate, β-glucose pentapropionate, α-glucose pentabutyrate, and β-glucose pentabutyrate.

[0093]

[0094] In other embodiments, the monomer plasticizer includes at least one carbohydrate ester, and the carbohydrate portion of the carbohydrate ester includes an α-anomer, a β-anomer, or a mixture thereof.

[0094]

[0095] In other embodiments, the monomer plasticizer is selected from at least one of propylene glycol dibenzoate, glyceryl tribenzoate, diethylene glycol dibenzoate, triethylene glycol dibenzoate, dipropylene glycol dibenzoate, and polyethylene glycol dibenzoate.

[0095]

[0096] In other embodiments of the present invention, the monomer plasticizer may be a solid amorphous resin. These resins may contain a small amount of aromatic or polar functional groups and can reduce the melt viscosity of the cellulose ester. In one embodiment of the present invention, the monomer plasticizer is, for example, rosin; hydrogenated rosin; stabilized rosin, and their monofunctional alcohol esters or polyol esters; modified rosins such as maleic acid and phenol-modified rosin and their esters (but not limited thereto); terpene resins; phenol-modified terpene resins; coumarin-indene resins; phenol resins; alkylphenol-acetylene resins; and phenol-formaldehyde resins; and may be solid amorphous compounds (resins) such as these.

[0096]

[0097] In other embodiments of the present invention, the monomer plasticizer is triacetin, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, triethyl citrate, acetyltrimethyl citrate, acetyltriethyl citrate, acetyltributyl citrate, tributyl-o-acetyl citrate, dibutyl phthalate, diaryl phthalate, diethyl phthalate, dimethyl phthalate, di-2-methoxyethyl phthalate, dioctyl phthalate, dioctyl adipate, dibutyl tartrate, ethyl o-benzoylbenzoate, ethyl phthalylethyl glycolate, methyl phthalylethyl glycolate, n-ethyltoluene sulfonamide, 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 to C 20At least one monomer plasticizer selected from the group consisting of dicarboxylic acid esters, dimethyl adipate, dibutyl maleate, dioctyl maleate, resorcinol monoacetate, catechol, catechol esters, phenols, epoxidized soybean oil, castor oil, linseed oil, epoxidized linseed oil, other vegetable oils, other seed oils, polyethylene glycol-based difunctional glycidyl ethers, γ-butyrolactone, alkyl phosphate esters, aryl phosphate esters, phospholipids, eugenol, cinnamyl alcohol, camphor, methoxyhydroxyacetophenone, vanillin, ethyl vanillin, 2-phenoxyethanol, glycol ethers, glycol esters, glycol ester ethers, polyglycol ethers, polyglycol esters, ethylene glycol ethers, propylene glycol ethers, ethylene glycol esters, propylene glycol esters, polypropylene glycol esters, acetylsalicylic acid, acetaminophen, naproxen, imidazole, triethanolamine, benzoic acid, benzyl benzoate, salicylic acid, 4-hydroxybenzoic acid, propyl-4-hydroxybenzoate, methyl-4-hydroxybenzoate, ethyl-4-hydroxybenzoate, benzyl-4-hydroxybenzoate, 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.

[0097]

[0098] The amount of monomer plasticizer in the cellulose ester composition is, for example, the cellulose used Depending on the type of the suber ester, it may range from 0 to about 15% by weight based on the weight of the cellulose ester composition. In one embodiment, this amount may range from about 0% to about 15% by weight based on the weight of the cellulose ester composition. In other embodiments, this amount may range from about 10% by weight or less based on the weight of the cellulose ester composition. In other embodiments, this amount may be about 5% by weight or less, or less than 5% by weight, or about 4% by weight or less, or less than about 3% by weight based on the weight of the cellulose ester composition.

[0098]

[0099] In one embodiment of the present invention, the cellulose ester composition may further contain a plasticizer selected from one or more polyglycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol (in addition to or instead of the monomer plasticizer). These may range from low molecular weight dimers and trimers to high molecular weight oligomers and polymers. In one embodiment, the weight average molecular weight (Mw) of the polyglycol may range from about 200 to about 2000.

[0099]

[0100] In other embodiments of the present invention, the composition does not contain a monomer plasticizer. In some embodiments, the cellulose ester composition may contain materials that are generally known or within the category of materials described herein as monomer plasticizers, but are not considered monomer plasticizers for the purposes of the present invention, provided that this material is of a particular type or provides (or contributes to) other functional groups (other than plasticizer functional groups) and has a minimal effect on reducing Tg or melt flow viscosity, for example, an amount that causes a change of less than 1% or less than 0.5% of such properties. For example, epoxidized soybean oil (e.g., Vikoflex 7170) is added in a small amount (e.g., 1% by weight or less based on the composition) to stabilize the composition Although epoxidized oil or epoxidized soybean oil may generally be in the category of monomeric plasticizers, such materials are not considered to be monomeric plasticizers (when they do not contain other materials that act as plasticizers) and are excluded from the specific range of monomeric plasticizers (according to various embodiments disclosed herein), and a composition may contain such materials but be considered to be free of monomeric plasticizers (when they do not contain other materials that act as monomeric plasticizers).

[0100]

[0101] In some embodiments, the composition does not include a polyetherester compound. In some embodiments, the composition does not include an adipic acid compound. In some embodiments, the composition does not include a tall oil fatty acid ester. In some embodiments, the composition does not include an aromatic fatty acid ester. In some embodiments, the composition does not include an acylated phenolic fatty acid ester or diester. In some embodiments, the composition does not include triethyl citrate.

[0101]

[0102] In some embodiments, the composition comprises 0 to 2 wt. %, or 0 to 1.5 wt. %, or alternatively 0-1 wt. % of a fatty acid ester. In some embodiments, the composition comprises 0-2 wt. %, or alternatively 0-1.5 wt. %, or alternatively 0-1 wt. % of an epoxidized fatty acid ester, such as epoxidized soybean oil. In some embodiments, the composition comprises 0.1-2 wt. %, or alternatively 0.1-1.5 wt. %, or alternatively 0.1-1 wt. % of an epoxidized fatty acid ester. In some embodiments, the composition comprises 0.1-2 wt. %, or alternatively 0.1-1.5 wt. %, or alternatively 0.1-1 wt. % of an epoxidized soybean oil. In some embodiments, the composition comprises 0.1-2 wt. %, or alternatively 0.1-1.5 wt. %, or alternatively 0.1-1 wt. % of an epoxidized fatty acid ester and no other monomeric plasticizers. In some embodiments, the composition comprises 0.1-2 wt. %, or alternatively 0.1-1.5 wt. %, or alternatively 0.1-1 wt. % of an epoxidized soybean oil and no other monomeric plasticizers.

[0102]

[0103] In some embodiments, the cellulose ester composition is a cellulose ester. Based on the total weight of the cellulose ester composition, the cellulose ester composition contains 65-99 wt% of one or more cellulose esters, 1-35 wt% of one or more PBS polymers (or PAP), and less than 10 wt% in total of other components. In some embodiments, such other components do not include monomeric plasticizers, polyetherester compounds, or adipic acid compounds. In some embodiments, the cellulose ester composition does not include polyetherester compounds or camphor plasticizers.

[0103]

[0104] In another embodiment of the present invention, the cellulose ester composition comprises at least The composition includes a cellulose ester, at least one PBS polymer (or PAP), at least one impact modifier, and at least one monomeric plasticizer. In some embodiments, the cellulose ester is CAP (e.g., Eastman Co., Ltd.). (CAP482-20 from Kaneka), the impact modifier is an acrylic core-shell type impact modifier (e.g. Kane Ace M570 impact modifier from Kaneka), and the PBS polymer (or P The (AP) is poly(butylene succinate) (e.g., PBS grade C or D from Table 2), the monomer plasticizer is dioctyl adipate (DOA), where the total amount of the monomer plasticizer is 5 wt% or less, or less than 5 wt% (e.g., 2 wt% to less than 5 wt%, or 2 - 4 wt%) based on the total cellulose ester composition. In some embodiments, the PBS polymer (or PAP), the impact modifier, and the monomer plasticizer are present in an amount sufficient to provide a cellulose ester composition having a Tg of at least 110°C, or at least 120°C, good impact strength properties, and good creep (resistance to deflection under load). In some embodiments, based on the total weight of the entire cellulose composition, the PBS polymer (or PAP) is present in an amount of 2 - 10 wt%, or 3 - 8 wt%, or 3 - 7 wt%; the impact modifier is present in an amount of 2 - 10 wt%, or 4 - 8 wt%; and the monomer plasticizer is present in an amount of 1 - 5 wt%, or 1 wt% to less than 5 wt%, or 2 - 4 wt%. In some embodiments, the total combined amount of the PBS polymer (or PAP), the impact modifier, and the monomer plasticizer is 10 - 18 wt%, or 12 - 17 wt%, or 13 - 16 wt% based on the total cellulose ester composition.

[0104]

[0105] In other embodiments of the present invention, the composition is melt processable. Melt processability generally refers to the ability to thermally process materials at temperatures below their decomposition temperatures to obtain uniform pellets or plastic articles. For example, the described compositions can be melt extruded at a throughput of 35 pounds per hour using a screw speed of 250 rpm and a barrel temperature of 240°C in a Werner & Pflerderer 30 mm twin screw extruder, and injection molded in a Toyo 110 injection molding machine using a barrel temperature of 240°C and a mold temperature of 160°F with a minimal decrease in molecular weight (e.g., less than 5% decrease from the initial MW in MW) or discoloration (e.g., less than 5% increase in haze or less than 5% decrease in transmittance based on a 0 - 100% scale).

[0105]

[0106] In one embodiment of the present invention, it contains 1% to 35% by weight, or 2.5% to 30% by weight, 5% to 15% by weight of PBS polymer (or PAP), does not contain a monomer plasticizer, has a glass transition temperature (Tg) of at least 120 ° C (measured at 20 ° C / min according to ASTM-D3418 as further described herein), and a notched Izod impact strength value higher than 80 J / m, or higher than 100 J / m, or higher than 125 J / m, or higher than 150 J / m (measured for a bar with a thickness of 3.2 mm at 23 ° C according to ASTM-D256), and when measured at a barrel temperature of 240 ° C using the procedure described herein, a melt-processable cellulose ester composition having a spiral flow value of at least 38 centimeters (15 inches) is provided Unless otherwise indicated, the notched Izod impact strength was performed at 23 ° C for a bar with a thickness of 3.2 mm on a molded bar after notching according to ASTM method D256 after conditioning at 23 ° C and 50% RH for 48 hours.

[0106]

[0107] The spiral flow was determined as follows: width 0.50 inches × depth 0.030 in A reciprocating screw injection molding machine with a screw diameter of 32 mm and a clamping force of 110 tons, equipped with a water-cooled cold runner mold having a helical cavity with dimensions of 2.0 inches in diameter × 60.00 inches in length, was used. The cavity was supplied through a cold sprue 3.5 inches in length with an apparent diameter of 0.400 inches and a taper of 3°, followed by a cold runner 1.0 inches in length with an apparent diameter of 0.30 inches, and then a rectangular gate with a width of 0.25 inches × a thickness of 0.030 inches × a length of 0.10 inches. The variables controlled for the scope of the experiment included resin drying, injection unit barrel temperature, mold temperature, initial injection speed, injection pressure limit, screw rotation speed, and back pressure regarding screw recovery, injection time, and cycle time. For each combination of variables, the responses included the actual melt temperature and the melt movement distance (excluding runners and gates) within the helical cavity. The injection process could be stabilized for each set of conditions (usually 10 - 15 shots), and then 10 molded test specimens were recovered regarding the reported average flow length. All materials were molded using pressure control, a mold temperature of 120°F, an initial injection speed of 1 inch / second, an injection unit pressure limit of 2000 psi, an injection time of 5 seconds, a cycle time of 32 seconds, a maximum cushion of 0.2 inches, a screw recovery rotation speed of 150 rpm, and a screw recovery back pressure of 100 psi.

[0107]

[0108] In one embodiment, in addition to the PBS polymer (or PAP), melt processable The capable cellulose ester composition contains 0 to 15% by weight of an impact resistance improver and 0 to 15% by weight of a monomer plasticizer, and has a Tg higher than 120°C. In one embodiment, in addition to the PBS polymer (or PAP), the melt-processable cellulose ester composition contains 1 to 8% by weight, or 1 to 5% by weight, or less than 1 to 5% by weight of a monomer plasticizer, and has a Tg higher than 110°C. In other embodiments, the melt-processable cellulose ester composition contains 0 to 15% by weight of an impact resistance improver, 0 to 10% by weight of a monomer plasticizer, and has a Tg higher than 130°C. In still other embodiments, the melt-processable cellulose ester composition contains 0 to 10% by weight of an impact resistance improver, 0 to 10% by weight of a monomer plasticizer, and has a Tg higher than 140°C. In other embodiments, the melt-processable cellulose ester composition contains 0 to 10% by weight of an impact resistance improver, 0 to 5% by weight of a monomer plasticizer, and has a Tg higher than 140°C. In one embodiment, the impact resistance improver is a core-shell type impact resistance improver. In one embodiment, the impact resistance improver is an acrylic core-shell type impact resistance improver.

[0108]

[0109] In some embodiments of the present invention, the polymer-based resin is at It has a Tg that is higher than, or higher than 110 °C, or higher than 120 °C. In some embodiments, the polymer-based resin has a Tg of at least 120 °C, or at least 125 °C, or at least 130 °C, or at least 135 °C, or at least 140 °C, or at least 145 °C, or at least 150 °C, or at least 155 °C, or at least 160 °C. In some embodiments, the polymer-based resin has a Tg in the range of 100 °C to 190 °C, 100 °C to 185 °C, 100 °C to 180 °C, 100 °C to 175 °C, 100 °C to 170 °C, 110 °C to 190 °C, 110 °C to 185 °C, 115 °C to 190 °C, 115 °C to 185 °C, 120 °C to 190 °C, 120 °C to 185 °C, 125 °C to 190 °C, 125 °C to 185 °C, 130 °C to 190 °C, 130 °C to 185 °C, 135 °C to 190 °C, 135 °C to 185 °C, 140 °C to 190 °C, 140 °C to 185 °C, or 145 °C to 190 °C.

[0109]

[0110] In some embodiments of the present invention, the polymer-based resin is ASTM- Measured using a 3.2 mm thick bar exposed to 50% relative humidity at 23°C for 48 hours in accordance with ASTM-D256, it has a notched Izod impact strength of 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 some embodiments, the polymer-based resin has a notched Izod impact strength in the range of about 80 J / m to about 500 J / m, about 80 J / m to about 400 J / m, about 80 J / m to about 300 J / m, about 80 J / m to about 200 J / m, about 100 J / m to about 500 J / m, about 100 J / m to about 400 J / m, about 100 J / m to about 300 J / m, about 100 J / m to about 200 J / m, about 120 J / m to about 500 J / m, about 120 J / m to about 400 J / m, about 120 J / m to about 300 J / m, about 120 J / m to about 200 J / m, about 150 J / m to about 500 J / m, about 150 J / m to about 400 J / m, about 150 J / m to about 300 J / m, about 150 J / m to about 200 J / m, about 170 J / m to about 500 J / m, about 170 J / m to about 400 J / m, about 170 J / m to about 300 J / m, about 170 J / m to about 200 J / m, about 180 J / m to about 500 J / m, about 180 J / m to about 400 J / m, about 180 J / m to about 300 J / m, about 180 J / m to about 200 J / m, about 190 J / m to about 500 J / m, about 190 J / m to about 400 J / m, about 190 J / m to about 300 J / m, about 190 J / m to about 200 J / m, about 200 J / m to about 500 J / m, about 200 J / m to about 400 J / m, or about 200 J / m to about 300 J / m, measured using a 3.2 mm thick bar exposed to 50% relative humidity at 23°C for 48 hours in accordance with ASTM-D256.

[0110]

[0111] In some embodiments of the present invention, the thickness of the polymer-based resin is 3.2 m The plaque of m exhibits ductile fracture as defined in Section X1.8 of ASTM-D3763 when tested by instrumented impact according to ASTM-D3763.

[0111]

[0112] In some embodiments of the present invention, the polymer-based resin has a flexural modulus of greater than 1600 MPa as measured using a 3.2 mm thick bar exposed to 50% relative humidity at 23 °C for 48 hours in accordance with ASTM- D790. In some embodiments, the polymer-based resin has a flexural modulus of at least 1700 MPa, at least 1800 MPa, 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 as measured using a 3.2 mm thick bar exposed to 50% relative humidity at 23 °C for 48 hours in accordance with ASTM-D790. In some embodiments, the polymer-based resin has a flexural modulus in the range of about 1600 to about 3000 MPa, about 1700 to about 3000 MPa, about 1800 to about 3000 MPa, about 1900 to about 3000 MPa, about 2000 to about 3000 MPa, about 2100 to about 3000 MPa, about 2200 to about 3000 MPa, about 2300 to about 3000 MPa, about 2400 to about 3000 MPa, or about 2500 to about 3000 MPa as measured using a 3.2 mm thick bar exposed to 50% relative humidity at 23 °C for 48 hours in accordance with ASTM-D790. In some embodiments, the polymer-based resin has a flexural modulus in the range of about 1600 to about 2500 MPa, about 1700 to about 2500 MPa, about 1700 to about 2500 MPa, about 1900 to about 2500 MPa, about 1900 to about 2800 MPa, or about 1900 to about 3000 MPa as measured using a 3.2 mm thick bar exposed to 50% relative humidity at 23 °C for 48 hours in accordance with ASTM-D790.

[0112]

[0113] In some embodiments of the present invention, the cellulose ester composition is cellulose Containing 2.5 wt% to 30 wt% of PBS polymer (or PAP) based on the total weight of the cellulose ester composition, having a Tg value higher than 120 °C, a notched Izod impact strength value higher than 80 J / m, or higher than 100 J / m, or higher than 125 J / m, or higher than 150 J / m, or higher than 175 J / m, or higher than 200 J / m, and having a light transmittance value higher than 80%, or at least 85%, or at least 90% as measured using a 3.2 mm plaque after injection molding at a barrel set point of 249 °C and a residence time of 5 minutes in accordance with ASTM-D1003.

[0113]

[0114] Cellulose esters containing no monomer plasticizer or containing a low level of monomer plasticizer One problem that can occur when melt-processing cellulose esters containing no monomer plasticizer or containing a low level of monomer plasticizer in a screw plasticizing injection molding machine is that it is difficult to smoothly recover the screw, which can cause poor material supply and a "screeching" sound. Surprisingly, it has been found that by adding a PBS polymer (or PAP) according to some embodiments of the present invention, these problems during injection molding can be eliminated.

[0114]

[0115] In some embodiments of the present invention, the cellulose ester composition contains 2.5 wt% to 30 wt% of PBS polymer (or PAP) based on the total weight of the cellulose ester composition, has a notched Izod impact strength value higher than 120 °C, higher than 80 J / m, or higher than 100 J / m, or higher than 125 J / m, or higher than 150 J / m, or higher than 175 J / m, or higher than 200 J / m, and does not produce screeching or have screw recovery problems during injection molding at a barrel set point of 249 °C.

[0115]

[0116] In some embodiments of the present invention, the cellulose ester composition contains It contains 2.5 wt% to 30 wt% of PBS polymer (or PAP) based on the total weight of the cellulose ester composition, has a Tg value higher than 120 °C, a notched Izod impact strength value higher than 150 J / m or higher than 200 J / m, and has a light transmittance value higher than 80%, or at least 85%, or at least 90% when measured using a 3.2 mm plaque after injection molding at a barrel set point of 249 °C and a residence time of 5 minutes according to ASTM-D1003.

[0116]

[0117] In some embodiments of the present invention, the total weight of the cellulose ester composition The 3.2 mm thick plaque of the cellulose ester composition containing 2.5 wt% to 30 wt% of PBS polymer (or PAP) based on the total weight shows ductile fracture as defined in Section X1.8 of ASTM-D3763 when tested by instrumented impact according to ASTM-D3763 and has a Tg value higher than 120 °C.

[0117]

[0118] In other embodiments of the present invention, the cellulose ester composition further contains at least one additive selected from the group consisting of antioxidants , heat stabilizers, release agents, antistatic agents, brightening agents, colorants, flow aids, processing aids, anti-fogging additives, minerals, UV stabilizers, lubricants, chain extenders, nucleating agents, reinforcing fillers, wood or wood flour fillers, glass fibers, carbon fibers, flame retardants, dyes, pigments, colorants, further resins, and combinations thereof.

[0118]

[0119] In some embodiments, PAP, such as PBS, and optionally impact resistance In addition to the impact modifier and / or monomer plasticizer (discussed herein), the cellulose ester composition comprises a stabilizer selected from the group consisting of a secondary antioxidant, an acid scavenger, or a combination thereof. In some embodiments, in addition to PAP, such as PBS, and optionally an impact modifier and / or monomer plasticizer (discussed herein), the cellulose ester composition comprises a secondary antioxidant in the range of about 0.1 to about 0.8 weight percent, based on the total weight of the composition. In some embodiments, in addition to PAP, such as P BS, and optionally an impact modifier and / or monomer plasticizer (discussed herein), the cellulose ester composition comprises an acid scavenger in the range of about 0.2 to about 2.0 weight percent, based on the total weight of the composition. In one embodiment, in addition to PAP, such as PBS, and optionally an impact modifier and / or monomer plasticizer (discussed herein), the cellulose ester composition comprises a secondary antioxidant in the range of about 0.1 to about 0.8 weight percent and an acid scavenger in the range of about 0.2 to about 2.0 weight percent, based on the total weight of the composition. 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. In one embodiment, the cellulose ester composition further comprises a salt stabilizer, for example, in the range of about 0.1 to about 0.5 weight percent, based on the total weight of the composition. In one embodiment, in addition to the cellulose ester, PAP, such as PBS, and the stabilizer (discussed herein), the cellulose ester composition comprises any other components in a total amount of less than 10 weight percent, or less than 8 weight percent, or less than 5 weight percent, or less than 2 weight percent, based on the total weight of the composition.

[0119]

[0120] In other embodiments of the present invention, a method for manufacturing a cellulose ester composition is provided is provided. This method involves contacting at least one type of cellulose ester, at least one type of PBS polymer (or PAP), and optionally at least one impact modifier and / or monomer plasticizer. The cellulose ester, impact modifier, monomer plasticizer, and PBS polymer (or PAP) have been discussed earlier herein. In one embodiment, the cellulose ester, PBS polymer (or PAP), and optionally the impact modifier and / or monomer plasticizer can be mixed in any order of addition.

[0120]

[0121] In other embodiments of the present invention, (a) at least one type of PBS polymer (or PAP), at least one type of cellulose ester, and optionally at least one impact modifier and / or monomer plasticizer are mixed at a time and temperature sufficient to disperse the PBS polymer (or PAP) to produce a cellulose ester composition. The sufficient temperature is generally defined as the flow temperature of the cellulose ester which is about 50 °C higher than the Tg of the cellulose ester. In other embodiments, this temperature is about 80 °C higher than the Tg of the cellulose ester. In some embodiments, the temperature during mixing is limited by the processing temperature of the PBS polymer (or PAP) in the higher range and by the maximum use temperature of the cellulose ester composition in the lower range.

[0121]

[0122] The efficiency of mixing two or more viscoelastic materials can be determined by the ratio of the viscosities of the viscoelastic materials. In one embodiment, for a given mixing device and shear rate range, the viscosity ratio of the dispersed phase (PBS polymer (or PAP)) to the continuous phase (cellulose ester) must be within defined limits in order to obtain an appropriate particle size.

[0122]

[0123] In some embodiments, the PBS polymer (or PAP), cellulose ester The mixing of starch, and optionally an impact modifier and / or a monomer plasticizer, and any additives, can be achieved by any method known in the art suitable for dispersing the PBS polymer (or PAP), impact modifier, monomer plasticizer, and additives in the cellulose ester. Examples of mixing devices include, but are not limited to, a Banbury mixer, a Brabender mixer, a roll mill, and an extruder (single-screw or twin-screw). The shear energy during mixing is determined by the combination of the device, blade design, rotational speed (rpm), and mixing time. The shear energy must be sufficient to disperse the PBS polymer (or PAP) and optional impact modifier throughout the cellulose ester but not excessive. excessive.

[0123]

[0124] In some embodiments, the cellulose ester, PBS polymer (or PAP), impact modifier, monomer plasticizer, and additives can be mixed in any order during the process. In one embodiment, the cellulose ester is premixed with the PBS polymer (or PAP), impact modifier and / or monomer plasticizer. Next, the cellulose ester containing the PBS polymer (or PAP), impact modifier and / or monomer plasticizer is mixed with the additives. In other embodiments of the present invention, when using a reactive impact modifier, the reactive impact modifier can first be mixed with the cellulose ester, and then the other components are added. excessive.

[0124]

[0125] The composition of the present invention can be used as a molded plastic part or as a solid plastic article. It is useful as a product. This composition is suitable for use in any application where a hard and transparent plastic is required. Examples of such parts include disposable knives, forks, spoons, plates, cups, straws, as well as spectacle frames, toothbrush handles, toys, automotive trims, tool handles, camera parts, electronic device parts, razor parts, ink pen barrels, disposable syringes, bottles, etc. In one embodiment, the composition of the present invention is useful as plastics, films, fibers (including melt-spun fibers and solution-spun fibers), and sheets. In one embodiment, the present composition is useful as plastics for manufacturing bottles, bottle caps, cosmetic packaging, spectacle frames, cutlery, disposable cutlery, cutlery handles, shelves, shelf partition boards, electronic device housings, electronic device cases, computer monitors, printers, keyboards, pipes, automotive parts, automotive interior parts, automotive trims, signboards, thermoformed letters, siding, toys, thermally conductive plastics, ophthalmic lenses, tools, tool handles, and household items. In other embodiments, the composition of the present invention is suitable for use as films, seatings, fibers, molded articles, medical instruments, packaging materials, bottles, bottle caps, spectacle frames, cutlery, disposable cutlery, cutlery handles, shelves, shelf partition boards, furniture parts, electronic device housings, electronic device cases, computer monitors, printers, keyboards, pipes, toothbrush handles, automotive parts, automotive interior parts, automotive trims, signboards, outdoor signboards, skylights, multilayer films, thermoformed letters, siding, toys, toy parts, thermally conductive plastics, ophthalmic lenses and frames, tools, tool handles, and household items, healthcare items, commercial food service products, boxes, films for graphic art applications, and plastic films for plastic-glass laminates.

[0125]

[0126] This cellulose ester composition is fibers, films, molded articles, and sheetings It is useful for forming G. The method of forming the cellulose ester composition into fibers, films, molded articles, and seatings can follow the methods known in the art. Examples of possible molded articles include, without limitation, medical devices, medical packaging materials, healthcare products, products for commercial food and beverage services such as food pans, tumblers, and storage boxes, bottles, food processors, blenders, and mixing bowls, household items, water cylinders, crisper trays, the front part of washing machines, parts of vacuum cleaners, and toys. Other possible molded articles can include ophthalmic lenses and frames.

[0126]

[0127] The present invention further relates to a manufactured article comprising one or a plurality of films and / or sheets containing the cellulose ester composition described herein. In some embodiments, the films and / or sheets of the present invention can be of any thickness apparent to those skilled in the art.

[0127]

[0128] The present invention further relates to one or more films and / or sheets described herein. Examples of methods for forming the cellulose ester composition into one or more films and / or sheets can include methods known in the art. Examples of one or more films and / or sheets of the present invention include, but are not limited to, one or more extruded films and / or sheets, one or more calendered films and / or sheets, one or more compression-molded films and / or sheets, and one or more 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.

[0128]

[0129] The present invention further relates to the molded articles described herein. The cellulose ester composition Examples of methods for shaping a composition into a shaped article include methods known in the art. Examples of the shaped articles of the present invention include, but are not limited to, injection-molded articles, extruded articles, injection blow-molded articles, injection stretch blow-molded articles, and extrusion blow-molded articles. Examples of methods for manufacturing a shaped article include, but are not limited to, injection molding, extrusion, injection blow molding, injection stretch blow molding, and extrusion blow molding. Examples of the methods of the present invention include any blow molding process known in the art such as extrusion blow molding, extrusion stretch blow molding, injection blow molding, and injection stretch blow molding (but not limited thereto).

[0129]

[0130] The present invention encompasses any injection blow molding manufacturing process known in the art including, but not limited to, a representative description of an injection blow molding (IBM) manufacturing process involves: (1) melting the composition in a reciprocating screw extruder; (2) injecting the molten composition into an injection mold to form a partially cooled tube (i.e., a preform) closed at one end; (3) transferring 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 stretch and expand the preform to fill the mold; (5) cooling the shaped article; (6) removing the article from the mold.

[0130]

[0131] The present invention encompasses any injection stretch blow molding manufacturing process known in the art includes. Representative descriptions of the injection stretch blow molding (ISBM) manufacturing process include, but are not limited to: (1) melting the composition in a reciprocating screw extruder; (2) injecting the melted composition into an injection mold to form a partially cooled tube (i.e., preform) closed at one end; (3) transferring the preform into a blow mold having the desired final shape around the preform and closing the blow mold around the preform; (4) stretching the preform using an internal stretching rod and blowing air into the preform to stretch and expand the preform to fill the mold; (5) cooling the molded article; and (6) removing the article from the mold.

[0131]

[0132] The present invention encompasses any extrusion blow molding manufacturing process known in the art including. Representative descriptions of the extrusion blow molding manufacturing process include, but are not limited to: (1) melting the composition in an extruder; (2) extruding the melted composition through a die to form a tube of molten polymer (i.e., parison); (3) clamping a mold having the desired final 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 article from the mold; and (7) removing excess plastic (usually called flash) from the article.

[0132]

[0133] In some aspects, articles useful for acoustic applications are provided that may include any cellulose ester composition disclosed herein. In some embodiments, the acoustic article includes a cellulose ester composition comprising at least one cellulose ester and at least one PBS polymer (or PAP). In some embodiments, the cellulose ester is selected from CAP or CAB, and the PBS polymer (or PAP) is present in an amount of about 1 to 25 wt%, or about 2 to 20 wt%, or about 2 to 15 wt%, or about 2 to 10 wt% based on the total composition.

[0133]

[0134] In some embodiments, the acoustic article comprises a cellulose ester composition comprising at least one type of cellulose ester, at least one type of PBS polymer (or PAP), and at least one impact modifier (as described herein). In some embodiments, the cellulose ester is selected from CAP or CAB; the PBS polymer (or PAP) (e.g., PBS) is present in an amount of about 1 to 25 wt%, or about 2 to 20 wt%, or about 2 to 15 wt%, or about 2 to 10 wt% based on the total composition; and the impact modifier is present in an amount of about 1 to 25 wt%, or about 2 to 20 wt%, or about 2 to 15 wt%, or about 2 to 10 wt% based on the total composition. In some embodiments, the impact modifier is a core-shell type impact modifier, such as an acrylic core-shell type impact modifier like M-570.

[0134]

[0135] In some embodiments, the acoustic article comprises a cellulose ester composition comprising at least one type of cellulose ester, at least one type of PBS polymer (or PAP), and at least one monomeric plasticizer (as described herein). In some embodiments, the cellulose ester is selected from CAP or CAB; the PBS polymer (or PAP) (e.g., PBS) is present in an amount of about 1 to 25 wt%, or about 2 to 20 wt%, or about 2 to 15 wt%, or about 2 to 10 wt% based on the total composition; and the monomeric plasticizer is present in an amount of about 0.1 to 8 wt%, or about 1 to 6 wt%, or about 1 to 5 wt%, or less than 5 wt% to 1 wt%, or about 2 to 4 wt% based on the total composition. In some embodiments, the monomeric plasticizer is an adipate monomeric plasticizer, such as DOA.

[0135]

[0136] In some embodiments, the acoustic article comprises a cellulose ester ​​​A cellulose ester composition comprising a stele, at least one PBS polymer (or PAP), at least one impact modifier (as described herein), and at least one monomer plasticizer (as described herein). In some embodiments, the cellulose ester is selected from CAP or CAB; the PBS polymer (or PAP) (e.g., PBS) is present in an amount of about 1 to 25 wt%, or about 2 to 20 wt%, or about 2 to 15 wt%, or about 2 to 10 wt% based on the total composition; the impact modifier is present in an amount of about 1 to 25 wt%, or about 2 to 20 wt%, or about 2 to 15 wt%, or about 2 to 10 wt% based on the total composition; and the monomer plasticizer is present in the range of about 0.1 to 8 wt%, or about 1 to 6 wt%, or about 1 to 5 wt%, or less than 1 wt% to 5 wt%, or about 2 to 4 wt% based on the total composition. In some embodiments, the impact modifier is a core-shell type impact modifier, such as an acrylic core-shell type impact modifier, such as M-570, and the monomer plasticizer is an adipate plasticizer, such as DOA is.

[0136]

[0137] In some embodiments, the cellulose ester composition provides an acoustic article having improved vibration (and / or acoustic) damping compared to similar articles formed from other thermoformable plastics such as ABS, PC, polyester, or nylon (having one or more other equivalent physical properties). In some embodiments, the article has a lower total harmonic distortion (THD) compared to similar articles formed from other such thermoformable plastics. In some embodiments, the lower THD may be in the form of a lower average THD compared to similar articles formed from other such thermoformable plastics over a frequency range of 20 Hz to 20 kHz, or 20 Hz to 10 kHz, or 100 Hz to 10 kHz, or 20 Hz to 500 Hz, or 3000 Hz to 20 kHz, or 3000 Hz to 10 kHz. In some embodiments, the lower The THD may be in the form of a lower THD peak for the cellulose ester composition article compared to similar articles formed from other such thermoformable plastics, when comparing the highest THD peak in a plot of THD as a function of frequency over a frequency range of 20 Hz to 20 KHz, or 20 Hz to 10 KHz, or 20 Hz to 500 Hz, or 3000 Hz to 20 KHz, or 3000 Hz to 10 KHz.

[0137]

[0138] In some embodiments, the cellulose ester composition (as described herein) is The article (formed from the composition) has a total harmonic distortion (THD) of less than 0.3% over the frequency range of 20 to 500 Hz, or less than 0.2% over frequencies of 3 to 10 KHz, or less than 0.6% over frequencies of 100 Hz to 10 KHz, or 100 Hz to 20 KHz, as measured by known methods.

[0138]

[0139] In some embodiments, 2 to 15% by weight, or 3 to 10% by weight, or 4 to 8 weight percent of an impact modifier (as described herein), e.g., an amine such as M-570 Cellulose ester compositions having high vibration damping properties are provided that include a krylic-based core-shell impact modifier and also include 2-15 wt. %, or 3-10 wt. %, or 4-8 wt. % of a PBS polymer (or PAP) (as described herein), such as CAP, e.g., CAP482-20 (from Eastman Chemical Company), and a combination of the impact modifier and the PBS polymer (or PAP).

[0139]

[0140] In some embodiments, 2 to 15% by weight, or 3 to 10% by weight, or 4 to 8 weight percent of an impact modifier (as described herein), e.g., an amine such as M-570 Containing a krill-based core-shell type impact modifier; also containing 2 to 15 wt%, or 3 to 10 wt%, or 4 to 8 wt% of a PBS polymer (or PAP) as described herein; also containing 2 to 6 wt%, or 2 to 5 wt%, or less than 2 to 5 wt%, or 2 to 4 wt% of a monomer plasticizer as described herein, such as a DOA plasticizer, CAP, such as CAP482-20 (from Eastman Chemical Company), and a combination of an impact modifier, a PBS polymer (or PAP), and a monomer plasticizer, a cellulose ester composition having high vibration damping characteristics is provided. In some embodiments, the cellulose ester composition contains 4 to 8 wt% of an impact modifier as described herein, such as an acrylic core-shell type impact modifier like M-570, and also contains 4 to 8 wt% of a PBS polymer (or PAP) as described herein; also contains 2 to less than 5 wt%, or 2 to 4 wt% of a monomer plasticizer as described herein, such as a DOA plasticizer.

[0140]

[0141] In some embodiments, the cellulose ester composition having high (or improved) vibration (or acoustic) damping may also have one or more other physical properties described herein. In some embodiments, the one or more other physical properties are selected from a relatively high Tg (e.g., a Tg of 110 °C or 120 °C or higher), a high modulus of elasticity, good impact properties, and good load deformation resistance (such properties are described in more detail herein).

[0141]

[0142] In some embodiments, the cellulose ester composition has excellent vibration damping It has characteristics, a high flexural modulus, and excellent impact resistance, and can be suitably used for manufactured articles such as audio equipment, electrical appliances, construction / building materials, and industrial equipment, or their parts or housings by using various molding methods such as injection molding, extrusion molding, or thermoforming. Furthermore, since the cellulose ester composition of the present invention has a relatively high flexural modulus, excellent vibration damping characteristics, and the ability to sufficiently maintain its shape, this cellulose ester composition is for transportation vehicles such as automobiles, railway vehicles, and airplanes, or their parts or housings, manufacturing articles for which weight reduction is desirable can be used.

[0142]

[0143] The application of the cellulose ester composition of the present invention to manufactured articles such as audio equipment, electrical appliances, transportation vehicles, construction / building materials, and industrial equipment, or their parts or housings can be appropriately set according to the manufacturing methods of parts, housings, devices, and equipment, the parts to be applied, and the intended purpose, and this composition can be used according to the usual methods in the art. In other words, by molding the cellulose ester resin composition of the present invention according to a known method, manufactured articles such as audio equipment, electrical equipment, transportation vehicles, construction / building materials, and industrial equipment, or their parts or housings can be obtained.

[0143]

[0144] In some embodiments, the cellulose ester resin composition of the present invention is As a material for audio equipment housings, for speakers, TVs, cassette players, headphones, audio components, microphones, etc.; further, as a material for parts and housings of electrical equipment having an electric motor, for power tools such as electric drills and electric drivers, computers, projectors, servers, and electrical equipment having a cooling fan such as a POS system, washing machines, clothes dryers, air conditioner indoor units, sewing machines, dishwashers, fan heaters, multifunction copiers, printers, scanners, hard disk drives, video cameras, etc.; as a material for parts and housings of electrical equipment including a vibration source, for electric toothbrushes, electric shavers, massagers, etc.; as a material for parts and housings of electrical equipment having a motor, for generators, gas generators, etc.; as a material for parts and housings of electrical equipment having a compressor, for refrigerators, vending machines, air conditioner outdoor units, dehumidifiers, and home generators; as a material for automotive parts, for materials for interior materials such as dashboards, instrument panels, floors, doors, and roofs, and engine-related materials such as oil pans, front covers, and rocker covers; as a material for railway vehicle parts, for interior materials such as floors, walls, side panels, ceilings, doors, seats, and tables, housings or parts in areas related to electric motors, various protective covers, etc.; as a material for aircraft parts, for interior materials such as floors, walls, side panels, side panels, ceilings, seats, and tables, housings or parts in parts related to engines, etc.; as a material for ship parts, for housings or wall materials for engine rooms, housings or wall materials for measurement rooms; as construction materials, for walls, ceilings, floors, partition boards, soundproof walls, shutters, curtain rails, pipe ducts, stairs, doors, etc.; as a material for industrial equipment parts, for shooters, elevators, escalators, conveyors, tractors, bulldozers, lawn mowers, etc.; can be used.

[0144]

[0145] In some embodiments, acoustic articles (e.g., high vibration damping or low T An article having HD can be selected from integrated audio devices such as speakers in automobiles, televisions, and smartphones; home theater systems including stand-alone speakers (wired or wireless), soundbars, subwoofers, and under-TV speakers; smart speakers including WiFi streaming and virtual personal assistants; and headphones, earphones, and other wearable speakers. In some embodiments, the acoustic article can also be a part or component of any of these devices such as a housing, enclosure, speaker component, microphone component, headband, wristband, clip, handle, etc.

[0145]

[0146] In some embodiments, an article comprising a cellulose ester composition can be a wearable article that generates sound or is subjected to vibration, or an article that contacts the body, and can be selected from eyeglass frames, eyeglass lenses, sunglass frames, sunglass lenses, goggles, wearable electronic devices, headphones, earphones, wristwatches, personal devices, personal electronic devices, medical devices, medical packaging materials, healthcare supplies, personal protective equipment, safety devices, water sports items or their components. In one embodiment, an article comprising a cellulose ester composition is an ophthalmic article, such as glasses or eye protectors. In some embodiments, the ophthalmic article can be selected from eyeglass frames, eyeglass lenses, sunglass frames, sunglass lenses, safety glasses and / or lenses, goggles, or face shields.

[0146]

[0146]

[0147] In some embodiments, an article comprising a cellulose ester composition can be a wearable article that generates sound or is subjected to vibration, or an article that contacts the body, and can be selected from eyeglass frames, eyeglass lenses, sunglass frames, sunglass lenses, goggles, wearable electronic devices, headphones, earphones, wristwatches, personal devices, personal electronic devices, medical devices, medical packaging materials, healthcare supplies, personal protective equipment, safety devices, water sports items Household or general consumer goods that may generate or be subject to vibrations, which may include kitchenware, bar supplies, outdoor furniture, indoor furniture, furniture parts, shelves, shelf dividers, slat walls, toys, sports equipment, travel bags, electrical appliances, small electrical appliances, storage containers, office supplies, bathroom fixtures or accessories, tools, household electronics, commercial food service products such as hood pans, tumblers and storage boxes, bottles, food processors, blenders and mixing bowls, household items, water barrels, crisper trays, the front part of a washing machine, vacuum cleaner parts, or can be selected from these parts.

[0147]

[0148] The present invention can be further illustrated by the following examples of its preferred embodiments However, these examples are included for illustrative purposes only and are not intended to limit the scope of the present invention unless specifically stated otherwise.

Examples

[0148]

[0149] A selected cellulose ester was compounded with a PBS polymer, an impact modifier, and / or or a monomer plasticizer to prepare a cellulose ester composition. Unless otherwise specified, the compounding of the cellulose ester composition was carried out using a Leistritz 18mm (50:1 L / D ratio) twin-screw extruder at a throughput of 18 pounds per hour, a screw speed of 250 rpm, and a barrel temperature of 220°C. For the compounding of CA and CAP141-20 based compositions, the barrel temperature was 230°C. The grades of cellulose esters used in the following examples are shown in Table 1 above.

[0149]

[0150] The PBS polymers used in the examples are shown in Table 2 below.

[0151]

[0150]

Table 2

[0151]

[0152] The examples include tests on injection molded plaques and bars. Unless otherwise specified, molding was carried out on a Toyo injection molding machine using a barrel temperature of 240 °C (460 °F) and a mold temperature of 70 °C (160 °F). Unless otherwise specified, Tg, haze, light transmittance, transparency, melt viscosity, and notched Izod impact strength were measured / obtained as discussed below.

[0152]

[0153] The glass transition temperature (Tg) was measured according to ASTM standard method D3418 by heating the sample from -100 °C at a heating rate of 20 °C / min. DSC scans of blends of multiple materials may show multiple Tg transitions. If more than one Tg transition is found during the scan, the glass transition of the matrix is defined as the highest Tg measured during the scan.

[0153]

[0153]

[0154] Haze % and light transmittance were measured according to ASTM-D1003 on injection molded plaques 102 mm × 102 mm × 3.2 mm. In the examples, when a transparency grading was given, the grading was determined by visual inspection. A transparent grading corresponds to a haze % of less than about 10%, a slightly hazy grading is higher than about 10%, or higher than about 15% and less than about 25% haze %, and a hazy or cloudy grading corresponds to a haze % higher than about 25%.

[0154]

[0155] Notched Izod impact strength was carried out at 23 °C on a 3.2 mm thick molded bar after notching according to ASTM method D256, after conditioning the bar at 23 °C and 50% RH for 48 hours.

[0155] Example 1: CAP with and without monomer plasticizer:

[0156] CAP grade from Table 1: without monomer plasticizer (Example 1-1) And those having 10% DOA plasticizer (Examples 1-2) were each injection molded into bars with a thickness of 3.2 mm × width of 12.8 mm using a Toyo 110-ton injection molding machine at a barrel temperature of 240 °C and a mold temperature of 70 °C.

[0156]

[0157] For each sample, transparency, melt viscosity, Tg, and Izod impact strength were determined. The compositions and properties of the materials for Examples 1-1 and 1-2 are shown in Table 3 below.

[0158]

[0157]

Table 3

[0158]

[0159] Table 3 shows the properties of CAP482-20 that was not blended with monomer plasticizer (Example 1 -1) and that was blended with monomer plasticizer (Example 1-2), and CAP141-20 without monomer plasticizer (Example 1-3). Examining the table, it can be seen that the plastic was maintained in a transparent state. CAP plastic without monomer plasticizer had a relatively high glass transition temperature but had a lower level of impact resistance. In contrast, the plasticized CAP compound had a higher level of impact strength but had a lower Tg. It would be desirable to provide a cellulose ester composition having both the advantages of a high Tg and good impact resistance.

[0159] Example 2: Blend of CE and PBS:

[0160] Different grades of cellulose ester (from Table 1) were blended with different grades and different amounts of PBS polymer and injection molded into bars with a thickness of 3.2 mm × width of 12.8 mm using a Toyo 110-ton injection molding machine at a barrel temperature of 240 °C and a mold temperature of 70 °C.

[0160]

[0161] For each sample, the transparency, flexural modulus, Tg, and Izod impact strength with notch were determined. The composition and properties of the materials for Example 2 are shown in Table 4 below. The composition and properties of the materials for Example 2 are shown in Table 4 below.

[0162]

[0161]

Table 4

[0162]

[0163] Examining Table 4, it can be seen that the CE / PBS compound had a higher Tg compared to Examples 1 - 2 from Table 3. Furthermore, for CAP141 - 20 when the PBS polymer was added, formulations with both a high Tg and increased toughness (i.e., impact strength higher than 96 J / m) were obtained, and it was shown that the FD92 grade of PBS gave the highest impact strength. Examining Table 4, it can be seen that the CE / PBS compound had a higher Tg compared to Examples 1 - 2 from Table 3. Furthermore, for CAP141 - 20 when the PBS polymer was added, formulations with both a high Tg and increased toughness (i.e., impact strength higher than 96 J / m) were obtained, and it was shown that the FD92 grade of PBS gave the highest impact strength.

[0163] Example 3: Blend of CE, PBS polymer, and impact modifier:

[0164] The CAP482 - 20 cellulose ester grade was blended with different grades of PBS polymer and an impact modifier, and injection molded into bars with a thickness of 3.2 mm × width of 12.8 mm at a barrel temperature of 240 °C and a mold temperature of 70 °C using a Toyo 110 - ton injection molding machine. The CAP482 - 20 cellulose ester grade was blended with different grades of PBS polymer and an impact modifier, and injection molded into bars with a thickness of 3.2 mm × width of 12.8 mm at a barrel temperature of 240 °C and a mold temperature of 70 °C using a Toyo 110 - ton injection molding machine.

[0164]

[0165] For each sample, the transparency, flexural modulus, and Izod impact strength were determined. The composition and properties of the materials for Example 3 are shown in Table 5 below. For each sample, the transparency, flexural modulus, and Izod impact strength were determined. The composition and properties of the materials for Example 3 are shown in Table 5 below.

[0166]

[0165]

Table 5

[0166]

[0167] Examining Table 5, it can be seen that the acrylic core - shell type impact modifier and PBS in C When blended with the AP, higher toughness was achieved compared to using only an equivalent amount of the acrylic core-shell type impact modifier or only PBS (Example 2-2), and it was also found to have good transparency. Also, the selected materials were injection molded into plaques with a thickness of 3.2 mm × 102 mm × width 102 mm using a Toyo 110-ton injection molding machine at a barrel temperature of 240°C and a mold temperature of 70°C for the instrumented impact test according to ASTM-D3763. The ductile fracture mode is given when the test piece plastically deforms without forming cracks that radially spread more than 10 mm from the center of the impact point before fracture. The brittle fracture mode is given when the test area of the test piece decomposes into two or more pieces with sharp edges and shows little plastic flow. In Table 5, tough impact fracture refers to ductile fracture.

[0167]

[0168] The above detailed description of the multiple embodiments of the present invention is intended to describe the various aspects of the present invention in sufficient detail to enable those skilled in the art to practice the present invention to that extent. Other embodiments can be used and modifications can be made without departing from the scope of the invention. Accordingly, the above detailed description should not be construed in a limiting sense. The scope of the present invention is defined only by the claims in the following regular utility model application, together with the full scope of equivalents to which the claims are entitled.

[0168]

[0169] As used herein, the description "one embodiment", "an embodiment", or "some embodiments" means that one or more related features are included in at least one embodiment of the present technology. Separate descriptions of "one embodiment", "an embodiment", or "some embodiments" herein do not necessarily refer to the same embodiment, and are not mutually exclusive unless so stated and / or apparent to those skilled in the art from the description. For example, features, steps, etc. described in one embodiment may or may not also be included in other embodiments. Thus, the present invention can encompass various combinations and / or integrations of the multiple embodiments described herein. The present invention includes the following embodiments. [1] A cellulose ester composition comprising at least one type of cellulose ester, at least one type of polymer aliphatic polyester (PAP), and optionally at least one type of impact modifier and / or at least one type of monomer plasticizer, wherein the at least one type of cellulose ester is 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); the PAP is a polyester 2 ~C 4 containing residues of C 4 ~C 8 alkanediol and residues of C alkyl dicarboxylic acid, or residues of ring-opening lactone; the cellulose ester composition has a Tg of at least 120 °C and, using a 3.2 mm bar, after conditioning the bar at 23 °C and 50% RH for 48 hours, has a notched Izod impact strength of at least 80 J / m when measured at 23 °C according to ASTM method D256. [2] The cellulose ester composition according to [1], wherein the at least one type of PAP is selected from poly(ethylene succinate) (PES), poly(butylene succinate) (PBS), poly(ethylene adipate) (PEA), poly(butylene adipate) (PBA), or a mixture thereof. [3] The cellulose ester composition according to [1], wherein the at least one type of PAP is poly(butylene succinate) (PBS), or a copolymer of poly(butylene succinate) and poly(butylene adipate) (PBSA). [4] The cellulose ester composition according to any one of [1] to [3], wherein the composition contains at least one type of impact modifier. [5] The cellulose ester composition according to any one of [1] to [4], wherein the composition contains at least one type of monomer plasticizer. [6] The cellulose ester composition according to any one of [1] to [5], wherein the composition contains at least one type of impact modifier and at least one type of monomer plasticizer. [7] The cellulose ester composition according to any one of [1] to [6], wherein the composition contains 65 to 95% by weight of the cellulose ester, 2 to 15% by weight of the PAP, and 2 to 15% by weight of the impact resistance improver. [8] The cellulose ester composition according to any one of [1] to [7], wherein the cellulose ester is selected from cellulose acetate propionate (CAP) or cellulose acetate butyrate (CAB). [9] The cellulose ester composition according to any one of [1] to [8], wherein the PAP is PBS or PBSA having an MFR (190 °C, 2.16 kg) of less than 25.

[10] The cellulose ester composition according to any one of [1] to [9], wherein the PAP is PBS or PBSA having an elongation at break of 250% or more.

[11] The cellulose ester composition according to any one of [1] to

[10] , wherein the PAP is PBS or PBSA having a polystyrene (PS) reduced number average molecular weight (Mn) higher than 15,000.

[12] The cellulose ester composition according to any one of [1] to

[11] , wherein the cellulose ester is cellulose acetate propionate (CAP) containing about 10 to about 40% by weight of propionyl.

[13] The cellulose ester composition according to any one of [1] to

[12] , wherein the cellulose ester composition uses a 3.2 mm bar, the bar is conditioned at 23 °C and 50% RH for 48 hours, and then measured at 23 °C according to ASTM method D256 to have a notched Izod impact strength of at least 200 J / m.

[14] The cellulose ester composition according to any one of [1] to

[13] , wherein the composition further contains at least one additive selected from the group consisting of antioxidants, heat stabilizers, release agents, antistatic agents, brightening agents, colorants, minerals, UV stabilizers, lubricants, nucleating agents, reinforcing fillers, glass fibers, carbon fibers, flame retardants, dyes, pigments, colorants, further resins, and combinations thereof.

[15] Further comprising at least one polymer component as a blend, wherein the polymer is selected from the group consisting of 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; polybutylene succinate; polysulfone ether; and poly(ether-ketone) of aromatic dihydroxy compounds; and combinations thereof; the cellulose ester composition according to any one of [1] to

[14] .

[16] A manufactured article comprising the cellulose ester composition according to any one of [1] to

[15] .

[17] The manufactured article according to

[16] , wherein the article is selected from an injection molded article, an extrusion molded article, an injection blow molded article, an injection stretch blow molded article, an extrusion blow molded article, or a compression molded article.

[18] The manufactured article according to

[16] , wherein the article is an injection molded article.

[19] The manufactured article according to

[16] , wherein the article is selected from an acoustic article, a wearable article, a vehicle part, an electric device, a toy, or a component thereof.

[20] A film or sheet comprising the cellulose ester composition according to any one of [1] to

[15] .

Claims

【Claim 1】 A cellulose ester composition comprising at least one type of cellulose ester, at least one type of polymer aliphatic polyester (PAP), at least one type of impact modifier, and optionally at least one type of monomer plasticizer, wherein the at least one type of cellulose ester is 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); The PAP is C ２ to C ４ a residue of an alkanediol and C ４ to C ８ an aliphatic polyester containing a residue of an alkyl dicarboxylic acid; the cellulose ester composition has a Tg of at least 120 °C and a notched Izod impact strength of at least 80 J / m measured at 23 °C according to ASTM method D256 after conditioning the bar with a diameter of 3.2 mm at 23 °C and 50% RH for 48 hours; the impact modifier is selected from the group consisting of acrylic core - shell type impact modifiers, MBS core - shell type impact modifiers, and ABS core - shell type impact modifiers; the amount of the PAP in the cellulose ester composition is 5 to 15% by weight based on the total cellulose ester composition; the amount of the impact modifier in the cellulose ester composition is 4 to 8% by weight based on the total cellulose ester composition. The above cellulose ester composition.

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