Compositions of cellulose ester and ethylene vinyl acetate, and articles manufactured using these compositions.

Abstract

A melt-processable cellulose ester composition is provided. Cellulose ester compositions are provided that include at least one cellulose ester, at least one ethylene-vinyl acetate copolymer, and, optionally, at least one plasticizer. Methods for making the cellulose ester compositions and articles made with these compositions, such as eyeglass frames, automotive parts, and toys, are also provided.

Description

[Technical Field]

[0001]

[0001] The present invention belongs to the field of cellulose ester chemistry, and more particularly to the field of cellulose esters comprising ethylene vinyl acetate (EVA) copolymers and optionally plasticizers. The present invention also belongs to the field of cellulose ester compositions comprising at least one EVA copolymer and optionally at least one plasticizer. Methods for producing these cellulose ester compositions are also provided, as well as plastic articles produced using these compositions, such as eyeglass frames, automotive parts, and toys. [Background technology]

[0002]

[0002] Cellulose ester compositions typically have a heat distortion temperature (HDT) or glass transition temperature (Tg) below 90°C. Commercially available cellulose esters that are melt-processed into articles usually contain a considerable amount of plasticizer to enable processing and give the molded articles sufficient toughness. However, the addition of plasticizer has the disadvantage that this lowers the HDT compared to the base cellulose ester, limiting the use of cellulose ester materials to applications where an HDT lower than about 90°C can be accepted. In addition, cellulose ester molded articles may leach plasticizer during use.

[0003]

[0003] To eliminate the need for low molecular weight plasticizers, it has been proposed to mix certain EVA copolymers with certain cellulose esters. However, the combinations proposed so far have been limited to certain relatively low molecular weight cellulose esters in order to provide acceptable processability and melt flowability for molding applications. As a result, the use of such materials has been limited for higher temperature end applications and applications requiring higher impact toughness. [Overview of the project] [Problems that the invention aims to solve]

[0004]

[0004] It would be beneficial to provide a melt-processable cellulose ester composition that does not have the aforementioned drawbacks. [Means for solving the problem]

[0005]

[0005] Surprisingly, it has been found that compositions of cellulose esters, such as cellulose acetate propionate and cellulose acetate butyrate, having a glass transition temperature (Tg) above 120°C and possessing good transparency and toughness can be produced. In some embodiments of the present invention, this can be achieved by reducing the amount of plasticizer, and in some embodiments by completely eliminating the use of plasticizer in the composition. Eliminating plasticizers can eliminate common problems associated with plasticizer leaching during use. However, reducing or eliminating plasticizers may reduce the toughness of these high-Tg cellulose compositions. Surprisingly, it has been found that certain EVA copolymers can restore the toughness of high-Tg cellulose compositions, providing cellulose ester compositions that are suitable for higher temperature applications, maintain dimensional stability over long periods, have good flow properties and good transparency.

[0006]

[0006] In some embodiments, the present invention relates to dispersing an amount of EVA copolymer in a cellulose ester composition sufficient to improve the mechanical and physical properties of the cellulose ester composition. Cellulose esters modified with EVA copolymer according to some embodiments of the present invention are melt-processable and commercially available plasticized cellulose esters. It possesses the unique characteristic of having a considerably higher Tg compared to plastic resins, and exhibits a high modulus of elasticity, good impact properties, and good resistance to load deformation.

[0007]

[0007] In one embodiment of the present invention, a cellulose ester composition is provided comprising at least one cellulose ester, at least one ethylene vinyl acetate (EVA) copolymer, and optionally at least one plasticizer. In one embodiment, the relative viscosity of the cellulose ester is greater than 6.0 as measured at 25°C with respect to an acetone solution containing 2% by weight of the cellulose ester, and the cellulose ester composition has a Tg of at least 120°C.

[0008]

[0008] In another aspect of the present invention, a cellulose ester composition is provided comprising at least one cellulose ester, at least one EVA copolymer, and at least one plasticizer.

[0009]

[0009] In other embodiments of the present invention, a method is provided for producing a cellulose ester composition comprising contacting at least one cellulose ester, at least one EVA copolymer, and optionally at least one plasticizer, and mixing the combination. In one embodiment, the plasticizer is present in an amount that does not substantially reduce the Tg of the cellulose ester composition compared to a similar composition without the plasticizer. In some embodiments, the Tg does not change (e.g., decrease) by more than 10%, more than 5%, or more than 2% as a result of the presence of the plasticizer.

[0010]

[0010] In some aspects of the present invention, a cellulose ester composition is described that does not contain a plasticizer but contains 1% to 35% by weight, or 2.5% to 30% by weight, or 10 to 30% by weight of an EVA copolymer based on the total weight of the cellulose ester composition, has a Tg value higher than 120°C, and has a notched Izod impact strength value higher than 100 J / m, or higher than 125 J / m, or higher than 150 J / m.

[0011]

[0011] In other embodiments of the present invention, a cellulose ester composition that is free of plasticizers but is melt-workable is provided. In some embodiments, the melt-workable cellulose ester composition comprises 1% to 35% by weight, or 2.5% to 30% by weight, or 10 to 30% by weight of EVA copolymer based on the total weight of the cellulose ester composition, and has a Tg value higher than 120°C, a notched Izod impact strength value higher than 100 J / m, or higher than 125 J / m, or higher than 150 J / m, and a spiral flow value of at least 38 centimeters (15 inches) measured at a barrel temperature of 240°C using the procedure described herein.

[0012]

[0012] In another embodiment of the present invention, the melt-processable cellulose ester composition comprises 2% to 20% by weight, or 5% to 15% by weight, of the total weight of the cellulose ester composition, an Izod impact strength of 10,000 P at 230°C and 100 rad / sec, and a Tg value higher than 120°C, or higher than 100 J / m, or higher than 125 J / m, or higher than 150 J / m. (1,000 Pa·s) It has a viscosity of less than [amount missing].

[0013]

[0013] In other embodiments, the melt-processable cellulose ester composition described above may contain a small amount of plasticizer. In some embodiments, the plasticizer is present in an amount that does not substantially reduce the Tg of the cellulose ester composition compared to a similar composition without a plasticizer. In some embodiments, the Tg does not change (e.g. decrease) by more than 10%, more than 5%, or more than 2% as a result of the inclusion of the plasticizer.

[0014]

[0014] In one embodiment of the present invention, a melt-workable cellulose ester composition is described, comprising 15% by weight or less of a plasticizer, or 10% by weight or less of a plasticizer; comprising 1% to 35% by weight, or 2.5% to 30% by weight, or 10 to 30% by weight of an EVA copolymer; having a Tg value higher than 120°C; and having a notched Izod impact strength value higher than 100 J / m, or higher than 125 J / m, or higher than 150 J / m.

[0015]

[0015] In another aspect of the present invention, a melt-processable cellulose ester composition is described, comprising 15% by weight or less of a plasticizer, or 10% by weight or less of a plasticizer, based on the total weight of the cellulose ester composition; comprising 1% to 35% by weight, or 2.5% to 30% by weight, or 10 to 30% by weight of an EVA copolymer, based on the total weight of the cellulose ester composition; having a Tg value higher than 120°C; having a notched Izod impact strength value higher than 100 J / m; and having a spiral flow value of at least 38 centimeters (15 inches) as measured at a barrel temperature of 240°C using the procedure described herein.

[0016]

[0016] In another aspect of the present invention, the cellulose ester composition comprises 15% by weight or less of a plasticizer, or 10% by weight or less of a plasticizer, based on the total weight; contains 1% to 35% by weight, or 2.5% to 30% by weight, or 10% to 30% by weight of an EVA copolymer, based on the total weight of the cellulose ester composition; has a Tg value higher than 120°C; has a notched Izod impact strength value higher than 100 J / m; and has 10,000 P at 230°C and 100 rad / sec. (1,000 Pa·s) A melt-processable cellulose ester composition having a viscosity of less than is described.

[0017]

[0017] In one aspect of the present invention, there is provided a polymer-based resin comprising at least one type of cellulose ester, at least one type of EVA copolymer, and optionally at least one type of plasticizer, wherein the cellulose ester is CAP, and the resin contains 0 to 5 wt%, 0 to 2 wt%, or 0 to 1 wt% of the plasticizer. In one aspect, the cellulose ester is CAP and the resin does not contain a plasticizer. In one aspect, the cellulose ester is CAP, the EVA is unmodified, the resin does not contain a plasticizer, and contains less than 5 wt% or less than 2 wt% of any other additive.

[0018]

[0018] In another aspect of the present invention, there is provided a cellulose ester composition comprising at least one type of cellulose ester, at least one type of EVA copolymer, and optionally at least one type of plasticizer, wherein the cellulose ester is CAB, and contains 0 to 5 wt%, 0 to 2 wt%, or 0 to 1 wt% of the plasticizer. In one aspect, the cellulose ester is CAB and the resin does not contain a plasticizer. In one aspect, the cellulose ester is CAB, the EVA is unmodified, the resin does not contain a plasticizer, and contains less than 5 wt% or less than 2 wt% of any other additive.

[0019]

[0019] In some embodiments, the cellulose ester resin is selected from at least one cellulose propionate (CP), cellulose butyrate (CB), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose acetate isobutyrate (CAIB), cellulose propionate butyrate (CPB), cellulose trippropionate (CTP), or cellulose tripyrate (CTB). In some embodiments, the resin contains or does not contain any other polymers contributing to the continuous binder phase between the resin and the cellulose ester in amounts of 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. For example, EVA is present as a dispersed phase within the cellulose ester resin and does not contribute to the continuous binder phase between the resin and the cellulose ester.

[0020]

[0020] In some embodiments, the cellulose ester resin is selected from at least one cellulose propionate (CP), cellulose butyrate (CB), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose acetate isobutyrate (CAIB), cellulose propionate butyrate (CPB), cellulose trippropionate (CTP), or cellulose tripyrate (CTB), and has a relative viscosity greater than 6.0. In some embodiments, the cellulose ester resin may be individual grades having a relative viscosity greater than 6.0, or a blend of cellulose esters having one or more grades having a lower relative viscosity (i.e., <6.0) and at least one grade having a higher relative viscosity (i.e., >6.0). In one embodiment, the cellulose ester resin may be a blend of cellulose esters having one or more grades with lower relative viscosity (i.e., <6.0) and at least one grade with higher relative viscosity (i.e., >6.0), the blend resulting in an average relative viscosity greater than 6.0. The relative viscosity is determined for a 2% cellulose ester solution in acetone and measured at a temperature of 25°C.

[0021]

[0021] In some embodiments, the cellulose ester having a relative viscosity higher than 6.0 can be selected from cellulose acetate butyrate containing about 15 to about 57% by weight of butyryl based on the total weight of the polymer. In some embodiments, the cellulose ester having a relative viscosity higher than 6.0 can be selected from cellulose acetate propionate containing about 15 to about 52% by weight of propionyl based on the total weight of the polymer.

[0022]

[0022] In some embodiments, the cellulose ester resin is selected from at least one 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) having a relative viscosity less than 2.5. In some embodiments, the cellulose ester resin may be an individual grade having a relative viscosity lower than 2.5, or may be a blend of cellulose esters having one or more grades with a higher relative viscosity (i.e., higher than 2.5) and at least one grade with a relative viscosity less than 2.5. In one embodiment, the cellulose ester resin may be a blend of cellulose esters having one or more grades with a higher relative viscosity (i.e., higher than 2.5) and at least one grade with a lower relative viscosity (i.e., less than 2.5), which results in an average relative viscosity lower than 2.5. The relative viscosity is determined for a 2% cellulose ester solution in acetone and measured at a temperature of 25°C. In some embodiments, when the cellulose ester has a relative viscosity less than 2.5, the cellulose ester composition / resin may have a reduced melt viscosity (or increased melt fluidity) at an equivalent Tg compared to a cellulose ester composition having a higher relative viscosity.

[0023]

[0023] In some embodiments, the cellulose ester is a cellulose acetate propionate (CAP) having a propionyl content of more than 15% by weight based on the total weight of the polymer. In some embodiments, the cellulose ester is a cellulose acetate propionate (CAP) having a propionyl content of more than 49% (propionic acid content of more than 66%) based on the total weight of the CAP polymer. In some embodiments, the cellulose ester is a cellulose acetate propionate (CAP) having a propionyl content of less than 38% (propionic acid content of less than 50%) based on the total weight of the CAP polymer.

[0024]

[0024] In some embodiments, the cellulose ester is based on the total weight of the polymer. The cellulose ester is a cellulose acetate butyrate (CAB) having a butyryl content of more than 15% by weight. In some embodiments, the cellulose ester is a cellulose acetate butyrate (CAB) having a butyryl content of more than 40% (butyric acid content of more than 50%) based on the total weight of the CAB polymer. In some embodiments, the cellulose ester is a cellulose acetate butyrate (CAB) having a butyryl content of less than 32% (butyric acid content of less than 40%) or in the range of 15-32% by weight based on the total weight of the CAB polymer. [Modes for carrying out the invention]

[0025]

[0025] In one embodiment of the present invention, a cellulose ester composition is provided which comprises at least one cellulose ester, at least one EVA copolymer, and optionally at least one plasticizer.

[0026]

[0026] In some embodiments, the cellulose ester used in the present invention is a C3-C ester with a sufficient content. 10 It may be an acid salt or any cellulose ester having an ester group. Cellulose esters that can be used for the present invention generally have the following structure:

[0027] [ka]

[0028] (In the formula, R 1 , R 2 , and R 3 (These are independently selected from the group consisting of hydrogen or linear alkanoyl chains having 2 to 10 carbon atoms.) It contains repeating units. For cellulose esters, the level of substitution is usually expressed as the degree of substitution (DS), which is the average number of non-OH substituents per anhydrous glucose unit (AGU). Generally, conventional cellulose contains three hydroxyl groups in each AGU unit that can be substituted; therefore, 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 due to the contribution of terminal groups. Natural cellulose is a large polysaccharide with a degree of polymerization of 250 to 5,000 even after pulping and purification, and the assumption that the maximum DS is 3.0 is largely correct. However, as the degree of polymerization decreases, as in low molecular weight cellulose mixed esters, the terminal groups of the polysaccharide backbone become relatively more significant, resulting in a DS that can range above 3.0. Low molecular weight cellulose mixed esters are discussed in more detail below in this specification. Since DS is a statistical mean, a value of 1 does not indicate that all AGUs have a single substituent. In some cases, unsubstituted anhydrous glucose units exist, some having two substituents, some three, and this value is usually a non-integer. Total DS is defined as the average number of all substituents per anhydrous glucose unit. The degree of substitution per AGU may also refer to specific substituents, such as hydroxyl, acetyl, butyryl, or propionyl.

[0029]

[0027] In some embodiments, the cellulose ester used may be a cellulose triester or a secondary cellulose ester. Examples of cellulose triesters include: Examples of secondary cellulose esters include, but are not limited to, cellulose tripionates or cellulose tripylates. Examples of secondary cellulose esters include cellulose acetate propionate and cellulose acetate butylate.

[0030]

[0028] 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 trippropionate (CTP), or cellulose tripylate (CTB), or combinations thereof. Some examples of cellulose esters are described in U.S. Patents 1,698,049; 1,683,347; 1,880,808; 1,880,560; 1,984,147; 2,129,052; and 3,617,201 (all of which are incorporated herein by reference to the extent that they do not contradict the description herein). In one embodiment, the cellulose ester is CAP.

[0031]

[0029] 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 trippropionate (CTP), or cellulose tripyrate (CTB), but not from cellulose acetate (CA).

[0032]

[0030] In some embodiments, the cellulose ester has a relative viscosity (η) of more than 6.0 to about 9.0, or about 6.1 to about 8.5, measured at a temperature of 25°C with respect to a 2 wt% solution of cellulose ester in acetone. rel) may have. Relative viscosity is the ratio of the elution time of the polymer solution to the solvent in which the polymer is dissolved. The relative viscosity according to the present invention can be determined as follows: A capillary-type viscometer (CANNON mini PV-HX) is used to measure the relative viscosity of the sample according to ASTM-D4603. Examples of cellulose esters include, but are not limited to, cellulose propionate (CP), cellulose butyrate (CB), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose acetate isobutyrate (CAIB), cellulose propionate butyrate (CPB), cellulose trippropionate (CTP), or cellulose tripylate (CTB).

[0033]

[0031] In some embodiments of the present invention, the cellulose ester is 15-52%, or 20-52%, or 25-52%, or 30-52%, or 35-52%, or 40-52%, or 45-52%, or 49-52%, or 15-50%, or 20-50%, or 25-50%, or 30-50%, or 35-50%, or 40-50%, or 45-50%, or 15-50%, or less than 50%, or less than 50%, or 25% based on the total weight of the cellulose ester polymer. Having a total percentage of propionyl in the range of less than 50%, or 30 to less than 50%, or 35 to less than 50%, or 40 to less than 50%, or 45 to less than 50%, or 35 to less than 50%, or 40 to less than 50%, or 45 to less than 50%, or 15 to 38%, or 20 to 38%, or 25 to 38%, or 30 to 38%, or 35 to 38%, or 15 to 35%, or 20 to 35%, or 25 to 35%, or 30 to 35%, or 15 to 30%, or 20 to 30%, or 25 to 30%.

[0034]

[0032] In some embodiments of the present invention, the cellulose ester is present in an amount of 15-57%, 20-57%, 25-57%, 30-57%, 35-57%, 40-57%, or more than 40% by weight, based on the total weight of the cellulose ester polymer. Up to 57%, or 41-57%, or 45-57%, or 50-57%, or 15-55%, or 20-55%, or 25-55%, or 30-55%, or 35-55%, or 40-55%, or more than 40% up to 55%, or 41-55%, or 45-55%, or 50-55%, or 15-50%, or 20-50%, or 25-50%, or 30-50%, or 35-50%, or 40-50%, or more than 40% up to 50%, or 41-50%, or It contains a total percentage of butyryl in the range of 45-50%, or 15-45%, or 20-45%, or 25-45%, or 30-45%, or 35-45%, or 40-45%, or more than 40% up to 45%, or 41-45%, or 15-35%, or 20-35%, or 25-35%, or 30-35%, or 15% to less than 32%, or 20% to less than 32%, or 25% to less than 32%, or 15-30%, or 20-30%, or 25-30%.

[0035]

[0033] In some embodiments, the cellulose ester is present in an amount 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 It is a cellulose propionate butyrate or cellulose acetate propionate butyrate having a total propionate and butyryl content in the range of 30%~55%, or 30%~50%, or 30%~45%, or 30%~40%, or 30%~35%, or 35%~55%, or 35%~50%, or 35%~45%, or 40%~50%, or 40%~45%, or 40%~55%, or 40%~55%, or 40%~45%, or 45%~55%, or 45%~50%, or 50%~55%.

[0036]

[0034] Cellulose esters can be produced by any method known in the art. An example of a method for producing cellulose esters is found in Kirk-Othmer, Encyclopedia of This is taught in Chemical Technology, 5th edition, vol. 5, Wiley-Interscience, New York (2004), pp. 394-444. Cellulose is a starting material for producing cellulose esters. Cellulose can be obtained in different grades and from different sources, including cotton linters, softwood pulp, hardwood pulp, corn fiber, and other agricultural raw materials, as well as bacterial cellulose.

[0037]

[0035] One method for producing cellulose ester is the esterification of cellulose by mixing cellulose with a suitable organic acid, acid anhydride, and catalyst. The cellulose is then converted to cellulose triester. Next, the ester is hydrolyzed by adding a water-acid mixture to the cellulose triester, and this can then 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 then dehydrated and dried.

[0038]

[0036] The cellulose triesters to be hydrolyzed may have three substituents independently selected from alkanoyl compounds having 2 to 10 carbon atoms. Examples of cellulose triesters include cellulose triacetate, cellulose trippropionate, and cellulose triptylate, or mixed triesters of cellulose such as cellulose acetate propionate and cellulose acetate butylate. 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 heterogeneously acylating cellulose in a mixture of carboxylic acid and an anhydride in the presence of a catalyst such as H2SO4. -Striesters can also be produced by homogeneous acylation of cellulose dissolved in a suitable solvent such as LiCl / DMAc or LiCl / NMP.

[0039]

[0037] After esterifying cellulose to triesters, some of the acyl substituents can be removed by hydrolysis or alcoholis to give secondary cellulose esters. As described above, the distribution of acyl substituents can be random or non-random depending on the specific method used. Secondary cellulose esters can also be produced directly without hydrolysis by using a limited amount of acylation reagent. This process is particularly useful when the reaction is carried out in a solvent that dissolves cellulose. Using all of these methods, cellulose esters useful in the present invention can be produced.

[0040]

[0038] The most common commercial secondary cellulose esters are produced by first acid-contact heterogeneous acylation of cellulose to form cellulose triesters. 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, random secondary cellulose esters are obtained, that is, the relative degree of substitution (RDS) at each hydroxyl is approximately equivalent.

[0041]

[0039] Some examples of cellulose esters useful in the present invention can be produced using techniques known in the art and can be obtained from Eastman Chemical Company, Kingsport, TN, USA, for example, Eastman® Cellulose Acetate Propionate CAP482-20, Eastman® Cellulose Acetate Propionate CAP141-20 Eastman® Cellulose Acetate Butyrate CAB381-20, and Cellulose The substance is acetate butyrate CAB171-15. Examples of several common cellulose esters are shown in Table 1 below, along with their relative viscosity values. In some embodiments, common cellulose esters having a relative viscosity higher than 6.0 (as shown in Table 1) can be used in the present invention. In some other embodiments, combinations of different common cellulose esters having relative viscosities higher or lower than 6.0 (as shown in Table 1) can be used.

[0042]

[0040]

[0043] [Table 1]

[0044]

[0041] In some embodiments, cellulose esters having a relative viscosity of less than 6.0 (as shown in Table 1, for example) can be used. In some other embodiments, combinations of different general cellulose ester grades having a relative viscosity higher than 6.0 and a relative viscosity of less than 6.0 (as shown in Table 1, for example) can be used. In some embodiments comprising cellulose esters having a relative viscosity of less than 6.0 and EVA copolymers, the cellulose ester composition can be provided for applications requiring a Tg higher than 120°C, or higher than 130°C, or higher than 140°C; and an Izod impact value of less than 150 J / m, or less than 125 J / m, or less than 100 J / m. In some other embodiments, including cellulose ester and EVA copolymers having a relative viscosity of less than 6.0, the cellulose ester composition can be provided for applications requiring higher melt fluidity (or lower melt viscosity) compared to using cellulose esters with a Tg higher than 100°C, or higher than 110°C, or higher than 120°C; and higher relative viscosity, in which case the cellulose ester composition further comprises plasticizers of the type and amount discussed herein. In one embodiment, the plasticizer is of a type that is mainly, substantially, or entirely contained in the discontinuous phase of the EVA copolymer of the cellulose ester composition and not contained (except in trace amounts as may be) in the continuous phase of the continuous cellulose ester polymer.

[0045]

[0042] In some embodiments, cellulose esters having a relative viscosity of less than 2.5 can be used. In some other embodiments, combinations of different grades of cellulose ester, including a grade having a relative viscosity of less than 2.5 and a grade having a relative viscosity of greater than 2.5, can be used. In some embodiments comprising a cellulose ester having a relative viscosity of less than 2.5 and an EVA copolymer, the cellulose ester composition can be provided for applications requiring a Tg higher than 120°C, or higher than 130°C, or higher than 140°C; and a lower melt viscosity (or higher melt fluidity) compared to cellulose esters having a higher relative viscosity.

[0046]

[0043] In some embodiments, the cellulose esters used in the present invention may also contain chemical functional groups, which are described herein as derivatized, modified, or functionalized cellulose esters. Functionalized cellulose esters are cellulose esters Free hydroxyl groups can be produced by reacting a bifunctional reactant having one linking group for grafting onto a 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 by an ester bond and imparts an acid functional group; mercaptosilane, which is linked by an alkoxysilane bond and imparts a mercapto functional group; and isocyanatoethyl methacrylate, which is linked by a urethane bond and imparts a methacrylate functional group.

[0047]

[0044] In one embodiment of the present invention, a functionalized cellulose ester is produced by reacting the free hydroxyl group of a cellulose ester with a bifunctional reactant that produces a cellulose ester having at least one functional group selected from the group consisting of unsaturated (double bond), carboxylic acid, acetacetate, acetacetimide, mercapto, melamine, and long-chain alkyl chain.

[0048]

[0045] Difunctional reactants for producing cellulose esters containing unsaturated (double bond) functional groups are described in U.S. Patents 4,839,230; 5,741,901; 5,871,573; 5,981,738; 4,147,603; 4,758,645; and 4,861,629 (all of which are incorporated herein by reference to the extent that they do not contradict the foregoing). In one embodiment, cellulose esters containing unsaturated groups are produced by reacting cellulose esters containing residual hydroxyl groups with acrylic compounds and m-isopropienyl-α,α'-dimethylbenzyl isocyanate. Grafted cellulose esters are urethane-containing products having suspended (meth)acrylate and α-methylstyrene groups. In other embodiments, cellulose esters including unsaturated compounds are produced by reacting maleic anhydride with a cellulose ester in the presence of an alkaline earth metal or ammonium salt of a lower alkyl monocarboxylic acid catalyst and at least one saturated monocarboxylic acid having 2 to 4 carbon atoms. In other embodiments, cellulose esters including unsaturated compounds are produced from the reaction product of (a) at least one cellulose polymer having an isocyanate-reactive hydroxyl functional group and (b) at least one hydroxyl-reactive poly(α,β-ethylenically unsaturated) isocyanate.

[0049]

[0046] Difunctional reactants for producing cellulose esters containing carboxylic acid functional groups are described in U.S. Patents 5,384,163; 5,723,151; and 4,758,645 (all of which are incorporated herein by reference to the extent that they do not contradict the foregoing). In one embodiment, a cellulose ester containing a carboxylic acid functional group is produced by reacting a cellulose ester with a mono or diester of maleic acid or fumaric acid to obtain a cellulose derivative having a double bond functional group. In another embodiment, a cellulose ester containing a carboxylic acid functional group has first and second residues, the first residue being a residue of a cyclic dicarboxylic acid anhydride, and the second residue being a residue of a lipophilic monocarboxylic acid and / or a hydrophilic monocarboxylic acid. In yet another embodiment, a cellulose ester containing a carboxylic acid functional group is a cellulose acetate phthalate, which can be produced by reacting cellulose acetate with phthalic anhydride.

[0050]

[0047] A bifunctional reactant for producing a cellulose ester containing an acetacetate functional group is described in U.S. Patent 5,292,877 (which is incorporated herein by reference to the extent that it does not contradict the foregoing). In one embodiment, the cellulose ester containing an acetacetate functional group comprises (i) cellulose; (ii) diketene, alkyl acetate, 2,2,6-trimethyl-4H-1,3-dioxin-4-one, or a mixture thereof; and (iii) lithium chloride and a carboxamide selected from the group consisting of 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, or a mixture thereof. It is produced by contacting a solvent system containing a certain amount of solubilization.

[0051]

[0048] A bifunctional reactant for producing a cellulose ester containing an acetacetaimide functional group is described in U.S. Patent 6,369,214 (which is incorporated herein by reference to the extent that it does not contradict the foregoing). The cellulose ester containing an acetacetaimide functional group is a reaction product of a cellulose ester and an amine-functional compound comprising at least one acetoacetyl group and at least one primary amine.

[0052]

[0049] A bifunctional reactant for producing a cellulose ester containing a mercapto functional group is described in U.S. Patent 5,082,914 (which is incorporated herein by reference to the extent that it does not contradict the foregoing). In one embodiment of the present invention, a silicon-containing thiol component is grafted onto a cellulose ester, which is commercially available or can be produced by a procedure known in the art. Examples of silicon-containing thiol compounds include, but are not limited to, (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)dimethyl-methoxysilane, (3-mercaptopropyl)dimethoxymethylsilane, (3-mercaptopropyl)dimethylchlorosilane, (3-mercaptopropyl)dimethylethoxysilane, (3-mercaptopropyl)diethoxymethylsilane, and (3-mercaptopropyl)triethoxysilane.

[0053]

[0050] A bifunctional reactant for producing a cellulose ester containing a melamine functional group is described in U.S. Patent 5,182,379 (which is incorporated herein by reference to the extent that it is not inconsistent with the foregoing). In one embodiment, a cellulose ester containing a melamine functional group is produced by reacting a cellulose ester with a melamine compound to form a grafted cellulose ester in which a melamine group is grafted onto the glucose anhydride ring backbone of the cellulose ester. In one embodiment, the melamine compound is selected from the group consisting of methylol ethers and aminoplast resins of melamine.

[0054]

[0051] A bifunctional reactant for producing cellulose esters containing long-chain alkyl functional groups is described in U.S. Patent 5,750,677 (which is incorporated herein by reference to the extent that it does not contradict the foregoing). In one embodiment, cellulose esters containing long-chain alkyl functional groups are produced by reacting cellulose in a carboxamide diluent or a urea-based diluent with an acylating agent using a titanium-containing species. Cellulose esters containing long-chain alkyl functional groups 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.

[0055]

[0052] In some embodiments, the cellulose ester is a cellulose acetate propionate (CAP) having a propionyl content of more than 49% (propionic acid content of more than 66%) based on the total weight of the CAP polymer. In some embodiments, the cellulose ester is a cellulose acetate propionate (CAP) having a propionyl content of less than 38% (propionic acid content of less than 50%) based on the total weight of the CAP polymer.

[0056]

[0053] In some embodiments, the cellulose ester is 15% to 52%, or 15% to 45%, or 15% to 38%, or 15% to 35%, or 15% to 30%, or 15% to 25%, or 20% to 52%, or 20% to 45%, or 20% to 38%, or 20% to 35%, or 20% to 30%, or 25% to 52%, or 25% to 45%, or 25% This is a cellulose acetate propionate (CAP) having a propionyl content in the range of ~38%, or 25%~35%, or 30%~52%, or 30%~45%, or 30%~38%, or 35%~52%, or 35%~45%, or 35%~38%, or 38%~49%, or 49%~52%.

[0057]

[0054] In some embodiments, the cellulose ester is a cellulose acetate butyrate (CAB) having a butyryl content of more than 40% (butyric acid content of more than 50%) based on the total weight of the CAB polymer. In some embodiments, the cellulose ester is a cellulose acetate butyrate (CAB) having a butyryl content of less than 32% (butyric acid content of less than 40%) based on the total weight of the CAB polymer.

[0058]

[0055] In some embodiments, the cellulose ester is present in a percentage of the total weight of the polymer of 10% to 57%, or 10% to 50%, or 10% to 45%, or 10% to 40%, or 10% to 32%, or 10% to 25%, or 10% to 18%, or 15% to 57%, or 15% to 50%, or 15% to 45%, or 15% to 40%, or 15% to 32%, or 15% to 25%, or 15% to 18%, or 20% to 57%, or 20% to 50%, or 20% to 45%, or 20% to 4%. It is a cellulose acetate butyrate (CAB) having a butyryl content in the range of 0%, or 20%-32%, or 20%-25%, or 25%-57%, or 25%-50%, or 25%-45%, or 25%-40%, or 25%-32%, or 30%-57%, or 30%-50%, or 30%-45%, or 35%-57%, or 35%-50%, or 35%-40%, or 40%-57%, or 40%-50%, or 40%-45%, or 45%-57%, or 45%-50%.

[0059]

[0056] In some embodiments, the cellulose ester 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% It is a cellulose propionate butyrate or cellulose acetate propionate butyrate having a total propionyl and butyryl content of 30%~55%, or 30%~50%, or 30%~45%, or 30%~40%, or 30%~35%, or 35%~55%, or 35%~50%, or 35%~45%, or 40%~55%, or 40%~55%, or 40%~55%, or 40%~45%, or 45%~55%, or 45%~50%, or 50%~55%.

[0060]

[0057] In some embodiments of the present invention, the EVA polymer may be any ethylene vinyl acetate rubber material compatible with the cellulose ester composition. "Compatible" means that the EVA polymer is of a type that has good transparency, maintains a Tg compared to the base cellulose ester (without EVA), has considerably increased toughness, preferably has an Izod impact strength of at least 100 J / m at 23°C, and gives a transparent, cloud-free cellulose ester composition. In some embodiments, the EVA polymer may be a single compatible polymer grade, a blend of different EVA compatible polymer grades, a combination of compatible and incompatible EVA polymers (e.g., using an "incompatible" EVA polymer as is in a similar formulation), or a combination of a compatible EVA polymer and other impact modifiers, provided that the resulting cellulose ester composition has sufficient transparency and toughness. In some embodiments, the EVA is not modified with maleic anhydride. In one embodiment, the EVA is not modified (e.g., functionalized or reacted) with any other chemical substituents. EVA contains vinyl acetate. By adjusting the quantity, it is not considered to be denatured (by other chemical substituents).

[0061]

[0058] In some embodiments, ethylene / vinyl acetate (EVA) copolymers can be produced by known high-pressure and medium-pressure processes, possibly in a solvent such as t-butanol. In some embodiments, the EVA copolymer has a vinyl acetate content of 30 to 98% by weight. In some embodiments of the present invention, the compatible EVA copolymer has a vinyl acetate content of 40% to less than 80% by weight, or in the range of 40 to 70% by weight, preferably in the range of 50 to 65% by weight, or more than 50% by weight up to 65% by weight. In one embodiment, the cellulose ester composition comprises at least one compatible EVA copolymer having a vinyl acetate (VA) composition in the range of 40 to 70% by weight, preferably in the range of 50 to 65% by weight, or more than 50% by weight up to 65% by weight. In some embodiments, the amount of such compatible EVA copolymer (having a VA content of 40-70% by weight, preferably 50-65% by weight, or more than 50% by weight up to 65% by weight) in the cellulose ester composition is 0.5-40% by weight, or 1-35% by weight, or 2.5-30% by weight, or 5-30% by weight, or 10-30% by weight, or more than 10% by weight up to 30% by weight, or 12-25% by weight, or 15-30% by weight, or 15-25% by weight, or 15-20% by weight, based on the total cellulose ester composition.

[0062]

[0059] In one embodiment of the present invention, a plurality of EVA copolymers having different vinyl acetate content can be used, as long as the weight-average vinyl acetate content of the EVA mixture is in the range of 40% to less than 80% by weight, or 40 to 70% by weight, preferably 50 to 65% by weight, or more than 50% by weight and up to 65% by weight. In some embodiments, the total amount of this mixture of compatible EVA copolymers in the cellulose ester composition (having a weight-average VA content in the range of 40-70% by weight, preferably 50-65% by weight, or more than 50% by weight up to 65% by weight) is 0.5-40% by weight, or 1-35% by weight, or 2.5-30% by weight, or 5-30% by weight, or 10-30% by weight, or more than 10% by weight up to 30% by weight, or 12-25% by weight, or 15-30% by weight, or 15-25% by weight, or 15-20% by weight, based on the total cellulose ester composition. In some embodiments, the EVA (or EVA blend) has a VA content (or weight-average VA content) in the range of 50–65% by weight, or more than 50% up to 65% by weight, or 51–65% by weight, or 52–65% by weight, or 53–65% by weight, or 51–64% by weight, or 51–62% by weight, or 51–60% by weight, or 52–64% by weight, or 52–62% by weight, or 52–60% by weight, or 53–64% by weight, or 53–62% by weight, or 53–60% by weight.

[0063]

[0060] In some embodiments, the ethylene / vinyl acetate copolymer produced by the high-pressure process has a melt index value of 0.1 to 100 g, preferably 1.0 to 10 g, more preferably 4.5 to 6 g (measured at 190°C under a load of 2.16 kp according to DIN 53,735). The intrinsic viscosity measured at 120°C in tetralin is generally 0.6 to 1.5 dL / g. The absolute molecular weight determined by light scattering is preferably 50,000 to about 1,000,000. Relational formula M w / M nThe inconsistency factor (U) (G. Shulz, Z., phys. Chem. (B) 43 (1939), pp. 25-34), defined according to -1, is between 1.6 and 30. These copolymers are preferably soluble in hydrocarbons at high temperatures.

[0064]

[0061] For example, an ethylene / vinyl acetate copolymer produced by solution polymerization or emulsion polymerization and containing 30-98% by weight, preferably 0-70% by weight, of vinyl acetate has a melt index value (190°C / 2.16kp) which may exceed 100g, but the melt index range is preferably less than 15g, and more particularly 0.5-5g. The absolute molecular weight measured by light scattering is preferably 40,000-1,000,000. The mismatch coefficient (U) is 1 to 6. This copolymer is soluble in hydrocarbons and alcohols and preferably has an intrinsic viscosity in toluene of 0.5 to 2.5 dL / g.

[0065]

[0062] In one embodiment, one or more impact modifiers may be included with the compatible EVA copolymer, and in some embodiments, the impact modifier may be any polymer material classified as an elastomer having a glass transition temperature (Tg) lower than room temperature. Tg can be measured, for example, using a TA2100 thermal analyzer with a scanning speed of 20°C / min, according to ASTM-D3418. Several classes of impact modifiers fit this description.

[0066]

[0063] In one embodiment, the impact modifier can be selected from a class of materials known as modified polyolefins (or olefin copolymers) other than the EVA component (discussed herein). In this class, the olefin is copolymerized with further monomers that limit the crystallization of the polymer to increase the amount of chains having a Tg below room temperature and reduce the modulus of elasticity to below 500 MPa. Examples of modified olefins include EMA (e.g., Elvaloy 4051, Lotader 3410, and Lotader 8900), EBA, EEA, EPDM (e.g., Royaltuf 498), and EPR.

[0067]

[0064] 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 commonly referred to as thermoplastic elastomers (TPEs). Examples of block copolymers in this class include styrene-based materials such as SBS, SEBS, and SIS (examples include Kraton G1657MS, Kraton FG1901G, and Kraton FG1924G); thermoplastic urethanes (TPUs) (examples include Elastolan 1170Z, Estane 2355, Estane ALR-CL87A, and Estane ALR-72A); and polyester-ether copolymers (examples include Ecdel 9966 and Hytrel 3078). Alternatively, polyamide-ether copolymers (Pebax 5533 is an example) may be used.

[0068]

[0065] In one embodiment, the impact modifier can be selected from a class of emulsion-forming 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 another embodiment, 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 polymethyl methacrylate or styrene-methyl methacrylate copolymer.

[0069]

[0066] In some embodiments, the MBS impact modifier may include 10 to 70% by weight of a butadiene polymer or copolymer, and a graft polymer composition comprising, firstly, methyl (meth)acrylate and a crosslinking agent, secondly, styrene, and thirdly, grafts of methyl (meth)acrylate and optionally a crosslinking agent.

[0070]

[0067] Suitable monomers for polymerization with conjugated diolefins, preferably butadiene, include alkenyl aromatic compounds, preferably vinyl aromatic compounds, such as styrene, divinylbenzene, α-methylstyrene, vinyltoluene, and styrene hydrogenate; and lower (CZ-Cu) alkyl acrylates, such as ethyl acrylate, n-propyl acrylate, n-butyl acrylate, Z-methylbutyl acrylate, and 3-methylbutyl acrylate. , amyl acrylate, n-hexyl acrylate, Z-ethylhexyl acrylate; lower (C2~C 12 Examples include alkyl (meth)acrylates; acrylonitriles; olefins; or any combination of the above.

[0071]

[0068] Suitable crosslinking agents include divinylbenzene; di(meth)acrylate; diacrylate, e.g., mono, di, or polyethylene glycol diacrylate; their (meth)acrylates; divinyl sulfide; divinyl ether; vinyl acrylate; vinyl(meth)acrylate; trivinylbenzene; trimethylolpropane; tri(meth)acrylate; triallyl cyanurate and triallyl isocyanurate.

[0072]

[0069] In one embodiment, the MBS core-shell type impact modifier may contain a copolymer of butadiene and styrene, most preferably a terpolymer of butadiene, styrene, and divinylbenzene. The relative amounts of monomers constituting the copolymer base material may vary, but based on 100 parts by weight of the 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 base material 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 on the same basis, 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.

[0073]

[0070] Examples of methacrylate-butadiene-styrene core-shell polymers are described in, but are not limited to, patents US-4,446,585, US-5,534,594, and US-6,331,580. MBS core-shell 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.

[0074]

[0071] In one embodiment of the present invention, the core-shell type impact modifier is an acrylic impact modifier comprising about 25 to 95% by weight of a first elastomer phase polymerized from a monomer system comprising about 75 to 99.8% by weight of (C1 to C6) alkyl acrylate, 0.1 to 5% by weight of a crosslinkable monomer, and 0.1 to 5% by weight of a graft-linkable monomer, and about 75 to 5% by weight of a final rigid thermoplastic phase that does not contain epoxy groups and is polymerized in the presence of such elastomer phase.

[0075]

[0072] Examples of useful acrylates include methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. In some embodiments, the acrylates are n-butyl acrylate and ethyl acrylate.

[0076]

[0073] Graft-linkable monomers are defined as polyethylene unsaturated monomers having both highly reactive and less reactive double bonds, wherein the highly reactive double bonds polymerize during the polymerization of the first-step monomer, leaving residual double bonds for polymerization in the next step, thereby grafting the second-step polymer onto the first-step polymer. In some embodiments, graft-linkable monomers are allyl methacrylate, allyl acrylate, and diallyl maleate. In one embodiment, 0.05 to 3% of graft-linkable monomers are present relative to the first-step monomer system. Preferably, crosslinkable monomers are also present, generally in an amount of about 0.05 to 3% by weight relative to the first-step monomer system, which are defined as polyethylene unsaturated monomers having at least two double bonds of substantially equal reactivity to cause crosslinking in the first-step polymerization. Typical examples of crosslinkable monomers include 1,3-butylenediacrylate, 1,3-butylenedimethacrylate, and divinylbenzene.

[0077]

[0074] "Epoxy functional group" means an epoxy unit suspended from the final polymer. In some embodiments, the epoxy functional group is introduced into the final polymer by using an epoxy-containing monomer such as glycidyl acrylate or glycidyl methacrylate in the final monomer mixture.

[0078]

[0075] Examples of acrylic core-shell polymers are described in, but are not limited to, patents US-3,448,173, US-3,655,825, and US-3,853,968. Examples of suitable acrylic impact modifiers include Kane Ace ECO100 from Kaneka, Durastrength from Arkema, Elvaloy and Elvaloy HP from DuPont, Metalben W from Mitsubishi Chemical, and Paraloid from Dow.

[0079]

[0076] 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 ABS core-shell type impact modifiers include Blendex from Galata Chemicals and Elix from Elix Polymers.

[0080]

[0077] In one class of this embodiment, the impact modifier is a silicone-acrylic core-shell type impact modifier having a core formed from silicone-acrylic rubber and a shell formed from PMMA copolymer or methyl methacrylate-styrene copolymer. An example of a silicone-acrylic core-shell type impact modifier is Metalben S from Mitsubishi Chemical Company.

[0081]

[0078] In one embodiment, the impact resistance modifier has a neutral acidity. This is thought to help prevent the cellulose ester from decomposing during the melting process of the composition.

[0079] 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 may also improve the mechanical and physical properties of the cellulose ester composition.

[0082]

[0080] In one embodiment, when a non-reactive impact modifier is used, the impact modifier includes a first polymer chain segment that is more chemically or physically compatible with the cellulose ester than other polymer chain segments. In one embodiment, the first segment includes polar functional groups that provide compatibility with the cellulose ester, such as (but not limited to) polar functional groups such as ethers, esters, amides, alcohols, amines, ketones, and acetals. Compatibility is defined by the interaction between the preferred first polymer chain segment and the cellulose ester polymer, which may mean interactions at the molecular or microscale. The first segment may consist of oligomers or polymers of the following: cellulose esters; cellulose ethers; polyoxyalkylenes, e.g., polyoxyethylene, polyoxypropylene, polyoxybutylene; polyglycols, e.g., polyethylene glycol, polypropylene glycol, polybutylene glycol; polyesters, e.g., 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.

[0083]

[0081] In some embodiments, the second segment may be a hydrocarbon group that is either saturated or unsaturated, or may contain both saturated and unsaturated hydrocarbon groups. The second segment may 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, polybutadienes, aromatic polymers, and copolymers. An example of the second segment of an aromatic polymer is polystyrene. An example of the second segment of a copolymer is styrene / butadiene copolymer.

[0084]

[0082] 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% of the polar first segment / about 15 to about 85% of the non-polar second segment.

[0085]

[0083] 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. The C 11 ~C 15 secondary alcohol ethoxylate can be obtained from the Dow Chemical Company as Dow Tergitol® 15S. Polyoxyethylene cetyl ether and polyoxyethylene stearyl ether are available from ICI Surfactants in the Brij® series of products. C is ethoxylated with an oxide. 12 ~C 14 Natural linear alcohols are available from Hoechst Celanese in the Genapol® series of products. Ethoxylated alcohols Examples of lucylphenols include octylphenoxypoly(ethyleneoxy)ethanol and nonylphenoxypoly(ethyleneoxy)ethanol. Octylphenoxypoly(ethyleneoxy)ethanol can be obtained from Rhodia as part of the Igepal® CA series, while nonylphenoxypoly(ethyleneoxy)ethanol can be obtained from Rhodia as part of the Igepal CO series, or from Dow Chemical Company as Tergitol® NP. Examples of ethoxylated fatty acids include Henkel. Examples include polyethylene glycol monostearate or monolaurate, available from Nopalcol® series products. Block polymers of propylene oxide and ethylene oxide are available from BASF in the Pluronic® series products. Polyglycerol esters are available from Stepan in the Drewpol® series. These products are available in the series. Polysaccharide esters are available from Henkel in the Glucopon® series (which are alkyl polyglucosides). Sorbitan esters are available from ICI in the Tween® series.

[0086]

[0084] In another embodiment of the present invention, a non-reactive impact modifier is synthesized in situ in a cellulose ester composition by reacting a cellulose ester-compatible compound. These compounds may be 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 They may have a higher weight-average molecular weight (Mw) of approximately 10,000 to approximately 1,000,000.

[0087]

[0085] In other embodiments of the present invention, the impact modifier may be reactive. A reactive impact modifier may contain a polymer or oligomer compatible with one component of the composition, and a functional group that can react 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 that can react with the cellulose ester. Such functional groups include, but are not limited to, carboxylic acids, anhydrides, acid chlorides, epoxides, and isocyanates. Specific examples of this type of reactive impact modifier include, but are not limited to, 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 acid anhydride (octadecanoic acid 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 ethylene, acrylic acid esters, and maleic anhydride terpolymers; and copolymers of glycidyl methacrylate and olefins and / or acrylic acid esters, such as ethylene, acrylic acid esters, and glycidyl methacrylate terpolymers.

[0088]

[0086] The reactive impact modifiers include SMA® 3000 styrene-maleic anhydride copolymer from Sartomer / Cray Valley, Eastman G-3015® maleic anhydride grafted polypropylene from Eastman Chemical Company, Epolene® E-43 maleic anhydride grafted polypropylene from Westlake Chemical, ethylene, acrylic acid esters, and Lotader® MAH 8200 random maleic anhydride from Arkema. Lotader® GMA AX8900 random terpolymer, ethylene, acrylic acid ester, and glycidyl methacrylate, It can also be obtained as Lotarder® GMA AX8840 random terpolymer, which contains glycidyl methacrylate.

[0089]

[0087] Reactive polyolefin impact modifiers can be obtained as Lotader, Fusabond, Elvloy PTW, Lotryl, Elvaloy AC, and InterLoy.

[0088] The second type of reactive impact modifier has a polar chain compatible with cellulose esters and also has functional groups that can react with cellulose esters. Examples of these types of reactive impact modifiers include cellulose esters or polyethylene glycols having olefin functional groups or thiol functional groups. Examples of reactive polyethylene glycol impact modifiers having olefin functional groups include, but are not limited to, polyethylene glycol allyl ether and polyethylene glycol acrylate. An example of a reactive polyethylene glycol impact modifier having thiol functional groups is polyethylene glycol thiol. An example of a reactive cellulose ester impact modifier is mercaptoacetate cellulose ester.

[0090]

[0089] In some embodiments of the present invention, the amount of impact modifier in the cellulose ester composition may be in the range of about 1% to about 15% by weight, or about 5% to about 10% by weight, based on the weight of the cellulose ester composition. In some embodiments, the cellulose ester composition comprises 55 to 98% by weight of at least one type of cellulose ester, preferably CAP; 1 to 30% by weight of at least one type of EVA copolymer, preferably 40 to 70% by weight, preferably 50 to 65% by weight, or EVA having a VA content of more than 50% by weight and up to 65% by weight, or a blend of EVA (having different VA contents) (the blend having an average VA content of 45 to 65% by weight, or 50 to 65% by weight, or more than 50% by weight and up to 65% by weight); and 1 to 15% by weight of at least one type of impact modifier, preferably a core-shell type impact modifier.

[0091]

[0090] In one embodiment, the cellulose ester and EVA copolymer 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 according to ASTM-D1003. In some embodiments, the polymer-based resin has a transmittance in the range of 70% to 95%, or 75% to 95%, or 80% to 95%, or 85% to 95%, or 85% 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 according to ASTM-D1003. In one class of this embodiment, the cellulose ester composition containing the EVA copolymer has a haze percentage of less than 10%. In some embodiments, the cellulose ester composition containing the EVA polymer has a haze percentage of less than 8%, or less than 6%, or less than 5%.

[0092]

[0091] In other embodiments, the refractive index (RI) of the EVA copolymer is close enough to that of the cellulose ester to give a composition having high transmittance and low haze. In one embodiment, the EVA copolymer has an RI close to that of the cellulose ester, about 1.46 to 1.48, giving a transparent composition. In some embodiments, the EVA copolymer 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 EVA), and the blend has a transmittance of at least 75% and a haze of 10% or less, more preferably 5% or less.

[0093]

[0092] In some aspects of the present invention, the amount of EVA copolymer in the cellulose ester composition may be in the range of about 0.5% to about 40% by weight, or about 1% to about 35% by weight, or about 2.5% to about 30% by weight, or about 5% to about 25% by weight, or about 5% to about 20% by weight, or about 5% to about 15% by weight, or about 5% to about 10% by weight, or about 10% to about 30% by weight, or about 10% to about 25% by weight, or about 10% to about 20% by weight, or about 10% to about 30% by weight, or more than 10% to about 25% by weight, or more than 10% to about 20% by weight, or more than 10% to about 15% by weight, based on the weight of the cellulose ester composition.

[0094]

[0093] 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 the additional polymer component include, but are not limited to, 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) aromatic dihydroxy compounds; or mixtures of any of the above polymers. The blend can be formed by conventional processing techniques known in the art, such as melt blending or solution blending. In some embodiments, the total amount of additional polymer components (excluding EVA) 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 zero, based on the total weight of the cellulose ester composition.

[0095]

[0094] In one embodiment of the present invention, in addition to the EVA copolymer, a plasticizer may be included in the composition. In some embodiments, the plasticizer used in the present invention may be any known in the art that can lower the glass transition temperature and / or melt viscosity of the cellulose ester and improve melt workability. The plasticizer may be any plasticizer suitable for use with the cellulose ester. The level of the plasticizer should be lower than the standard (or usual) level of plasticizer used in ordinary / commercial cellulose esters; the composition should have a higher Tg, good toughness, and good fluidity than a fully plasticized cellulose ester composition. In some embodiments, the plasticizer is present in an amount that does not substantially reduce the Tg of the cellulose ester composition compared to a similar composition without a 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 plasticizer.

[0096]

[0095] The plasticizer may be in the form of a monomer or a polymer. In one embodiment, the 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, polymer 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, glycoside ester plasticizers, citrate ester plasticizers, hydroxyl-functionalized plasticizers, or solid amorphous resin plasticizers.

[0097]

[0096] In one embodiment of the present invention, the plasticizer can be selected from at least one of the following: triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, dibenzyl phthalate, butyl phthalyl butyl glycolate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri-n-butyl citrate, and acetyl tri-n-(2-ethylhexyl) citrate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, or triethylene glycol dibenzoate.

[0098]

[0097] In another embodiment of the present invention, the plasticizer can be selected from at least one ester comprising: (i) an acid residue comprising one or more residues of phthalic acid, adipic acid, trimellitic acid, succinic acid, benzoic acid, azelaic acid, terephthalic acid, isophthalic acid, butyric acid, glutaric acid, citric acid, or phosphoric acid; and (ii) an alcohol residue comprising one or more residues of an aliphatic, alicyclic, or aromatic alcohol containing about 20 or fewer carbon atoms.

[0099]

[0098] In other embodiments of the present invention, the plasticizer can be selected from at least one ester comprising: (i) at least one acid residue selected from the group consisting of phthalic acid, adipic acid, trimellitic acid, succinic acid, benzoic acid, azelaic acid, terephthalic acid, isophthalic acid, butyric acid, glutaric acid, citric acid, 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.

[0100]

[0099] In other embodiments of the present invention, the plasticizer may contain an alcohol residue, the alcohol residue being: stearyl alcohol, lauryl alcohol, phenol, be It is at least one selected from dipropyl alcohol, hydroquinone, catechol, resorcinol, ethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, and diethylene glycol.

[0101]

[0100] In another embodiment of the present invention, the plasticizer is: benzoate, phthalate The plasticizer can be selected from at least one of phosphate, arylene-bis(diarylphosphate), and isophthalate. In other embodiments, the plasticizer includes diethylene glycol dibenzoate (hereinafter abbreviated as "DEGDB").

[0102]

[0101] In another embodiment of the present invention, the plasticizer is: C2~C 10 Diacid residue, For example, residues of malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid; and C2-C 10 It can be selected from at least one aliphatic polyester containing a diol residue.

[0103]

[0102] In other embodiments, the plasticizer is the following C2~C 10 Diol: Ethylene Glycol It may contain a diol residue which may be at least one residue of 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.

[0104]

[0103] In another aspect of the present invention, the plasticizer may be, for example, polyethylene glyco Examples of polyglycols include polypropylene glycol and polybutylene glycol. 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 be in the range of about 200 to about 2000.

[0105]

[0104] In other embodiments of the present invention, the plasticizer includes at least one of the following: Resoflex® R296 plasticizer, Resoflex® 804 plasticizer, SHP (sorbitol hexapropionate), XPP (xylitol pentapropionate), XPA (xylitol pentaacetate), GPP (glucose pentaacetate), GPA (glucose pentapropionate), and APP (arabitol pentapropionate).

[0106]

[0105] In another embodiment of the present invention, the plasticizer is (A) about 5 to about 95% by weight of C2 C 12 Carbohydrate organic esters (carbohydrates contain approximately 1 to 3 monosaccharide units); and (B) approximately 5 to 95% by weight of C2-C 12 It contains one or more polyol esters (polyols are derived from C5 or C6 carbohydrates). In one embodiment, the polyol ester does not contain or does not contain one or more polyol acetates.

[0107]

[0106] In another embodiment, the plasticizer comprises at least one carbohydrate ester, 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.

[0108]

[0107] In another aspect of the present invention, the plasticizer is at least one carbohydrate ester The carbohydrate portion of the carbohydrate ester contains one or more of the following: α-glucose pentaacetate, β-glucose pentaacetate, α-glucose pentapropionate, β-glucose pentapropionate, α-glucose pentatabylate, and β-glucose pentatabylate.

[0109]

[0108] In another embodiment, the plasticizer comprises at least one carbohydrate ester, The carbohydrate portion of the carbohydrate ester includes α-anomeric, β-anomeric, or a mixture thereof.

[0110]

[0109] In other embodiments, the plasticizer is: propylene glycol dibenzoate At least one of the following can be selected: glyceryl tribenzoate, diethylene glycol dibenzoate, triethylene glycol dibenzoate, dipropylene glycol dibenzoate, and polyethylene glycol dibenzoate.

[0111]

[0110] In another embodiment of the present invention, the plasticizer may be a solid amorphous resin. These resins may contain small amounts of aromatic or polar functional groups, which can reduce the melt viscosity of the cellulose ester. In one embodiment of the present invention, the plasticizer may be a solid amorphous compound (resin) such as rosin; hydrogenated rosin; stabilized rosin and their monofunctional alcohol esters or polyol esters; modified rosin such as (but not limited to) maleic acid and phenol-modified rosin and their esters; terpene resins; phenol-modified terpene resins; coumarin-indene resins; phenol resins; alkylphenol-acetylene resins; and phenol-formaldehyde resins.

[0112]

[0111] In another embodiment of the present invention, the plasticizer is triacetin, trimethylphosphate Triethyl phosphate, tributyl phosphate, triphenyl phosphate, triethyl citrate, acetyl trimethyl citrate, acetyl triethyl citrate, acetyl tributyl 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-benzoyl benzoate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, n-ethyltoluenesulfonamide, o-cresyl p- Luene sulfonate, aromatic diol, substituted aromatic diol, aromatic ether, trippropionine, 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-C 20Dicarboxylic 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 bifunctional glycidyl ethers, γ-valerolactone, alkyl phosphate esters, aryl phosphate esters, phospholipids, eugenol, cinnamyl alcohol, camphor, methoxyhydroxyacetophenone, vanillin, ethyl vanillin, 2-phenoxyethanol, glycol ethers, glycol esters, glycol ester ethers, polyglycols Polyglycol ether, polyglycol ester, ethylene glycol ether, propylene glycol ether, ethylene glycol ester, propylene glycol ester, polypropylene glycol ester, acetylsalicylic acid, acetaminophen, naproxen, imidazole, triethanolamine, benzoic acid, benzyl benzoate, salicylic acid, 4-hydroxybenzoic acid, propyl-4-hydroxybenzoate, methyl-4-hydroxybenzoate, ethyl-4-hydroxybenzoate, benzyl-4-hydroxybenzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate The plasticizer is selected from the group consisting of nzhoate, butylated hydroxytoluene, butylated hydroxyanisole, sorbitol, xylitol, ethylenediamine, piperidine, piperazine, hexamethylenediamine, triazine, triazole, pyrrole, and any combination thereof.

[0113]

[0112] The amount of plasticizer in the cellulose ester composition is the amount of plasticizer in the cellulose ester composition The amount may be in the range of 0 to about 15% by weight based on the weight of the material. In one embodiment, this amount may be in the range of about 15% by weight or less based on the weight of the cellulose ester composition. In another embodiment, this amount may be in the range of about 10% by weight or less based on the weight of the cellulose ester composition. In yet another embodiment, this amount may be in the range of about 5% by weight or less based on the weight of the cellulose ester composition, or about 3% by weight or less based on the weight of the cellulose ester composition.

[0114]

[0113] In other embodiments of the present invention, the composition does not contain a plasticizer. In some embodiments, the composition does not contain polyether ester compounds. In some embodiments, the composition does not contain adipic acid compounds. In some embodiments, the cellulose ester composition comprises, based on the total weight of the cellulose ester composition, 65 to 99% by weight of one or more cellulose esters, 1 to 35% by weight of one or more EVA copolymers, and other components totaling less than 5% by weight. In some embodiments, such other components do not contain plasticizers, polyether ester compounds, or adipic acid compounds.

[0115]

[0114] In another embodiment of the present invention, the composition is melt-workable. Melt-workability generally refers to the ability to heat-work a material at a temperature lower than its decomposition temperature to obtain uniform pellets or plastic articles. For example, the composition described is produced in a Werner & Pflerderer 30mm twin-screw extruder at a screw speed of 250 rpm and a barrel temperature of 240°C for 35 pounds. (15.9kg) It can be melt-extruded at a processing rate of / hour, and / or in a Toyo 110 injection molding machine at a barrel temperature of 240°C and 160°F (71.1℃) Using the mold temperature, injection molding can be performed with minimal molecular weight reduction (e.g., a reduction of less than 5% of Mw from the initial Mw) or discoloration (e.g., an increase in cloudiness of less than 5% or a decrease in transmittance of less than 5% relative to a scale of 0-100%).

[0116]

[0115] In one embodiment of the present invention, 1 to 35% by weight, or 2.5 to 30% by weight of EV A melt-workable cellulose ester composition is provided, comprising copolymer A and free of plasticizers, having a glass transition temperature (Tg) of at least 120°C (measured at 20°C / min as further described herein according to ASTM-D3418), a notched Izod impact strength value greater than 100 J / m (measured at 23°C on a 3.2 mm thick rod according to ASTM-D256), and a spiral flow value of at least 38 centimeters (15 inches) measured at a barrel temperature of 240°C using the procedure described herein. Unless otherwise specified, the notched Izod impact strength test was performed at 23°C on a molded rod that had been notched after being conditioned at 23°C and 50% RH for 48 hours, according to ASTM method D256.

[0117]

[0116] The spiral flow was determined as follows: A reciprocating screw injection molding machine with a clamping force of 110 tons and a screw diameter of 32 mm was used to form a 0.50 inch wide mold. (1.3cm) × Depth 0.030 inches (0.08cm) × Length 60.00 inches (152cm) A water-cooled cold runner mold was installed, having a helical cavity with dimensions of 0.400 inches. (1.0cm) A 3.5-inch long cold sprue with a nominal diameter and a 3° taper, followed by a 0.30-inch (0.76cm) A nominal diameter of 1.0 inch in length. (2.5cm) The cold runner, next to 0.25 inches wide. (0.64cm) × Thickness 0.030 inches (0.08cm) × Length 0.10 inches (0.25cm)The resin was supplied through a rectangular gate. Controlled variables within 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 related to screw recovery, injection time, and cycle time. For each combination of variables, the response included the actual melting temperature and the distance the molten material traveled in the helical cavity (excluding the runner and gate). The injection process could be stabilized in each set of conditions (typically 10-15 shots), and 10 molded specimens were then recovered with respect to the reported average flow length. All materials were subjected to pressure control at 120°F. (48.9℃) Mold temperature, 1 inch (2.5cm) Initial injection velocity of 2000 psi / second. (13.8 MPa) Injection unit pressure limit, 5-second injection time, 32-second cycle time, 0.2 inches (0.51cm) Maximum cushioning, screw recovery rotation speed of 150 rpm, and 100 psi. (689kPa) The molding was performed using screw recovery back pressure.

[0118]

[0117] In another embodiment of the present invention, the composition is measured using a frequency scan between 1 rad / sec and 100 rad / sec in accordance with ASTM-D4440, and measured using a plate-plate melt rheometer such as a Rheometrics Dynamic Analyzer (RDA II) with a parallel plate of 25 mm in diameter, a gap of 1 mm, and a strain of 10% to 10,000 P (1,000 Pa·s) It has the following melt viscosity at 230°C and 100 rad / second.

[0119]

[0118] In one embodiment, an EVA copolymer or a mixture of a plurality of EVA copolymers In addition, the melt-workable cellulose ester composition contains 0 to 15% by weight of an impact-resistant agent and 0 to 15% by weight of a plasticizer, and has a Tg higher than 120°C. In another embodiment, the melt-workable cellulose ester composition contains 0 to 15% by weight of an impact-resistant agent and 0 to 10% by weight of a plasticizer, and has a Tg higher than 130°C. In yet another embodiment, the melt-workable cellulose ester composition contains 0 to 10% by weight of an impact-resistant agent and 0 to 10% by weight of a plasticizer, and has a Tg higher than 140°C. In yet another embodiment, the melt-workable cellulose ester composition contains 0 to 10% by weight of an impact-resistant agent and 0 to 5% by weight of a plasticizer, and has a Tg higher than 140°C.

[0120]

[0119] In another embodiment of the present invention, the cellulose ester composition is an EVA copolymer Alternatively, by introducing a mixture of multiple EVA copolymers and not introducing plasticizers, the Tg is equivalent to that of the base cellulose ester polymer, with only a few degrees Celsius (e.g., less than 5°C or less than 2°C) of reduction. In some embodiments, the impact properties of these compositions also exceed 100 J / m (notched Izod impact strength at 23°C).

[0121]

[0120] In some embodiments of the present invention, the polymer-based resin is heated to temperatures higher than 100°C. The Tg is either 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. In some embodiments, the polymer-based resin has a Tg in the range of 100°C to 150°C, 100°C to 145°C, 100°C to 140°C, 100°C to 135°C, 100°C to 130°C, 100°C to 125°C, 110°C to 150°C, 110°C to 145°C, 115°C to 150°C, 115°C to 145°C, 120°C to 150°C, 125°C to 150°C, 125°C to 150°C, 125°C to 145°C, 130°C to 150°C, 130°C to 145°C, 135°C to 150°C, 135°C to 145°C, 140°C to 150°C, 140°C to 145°C, or 145°C to 150°C.

[0122]

[0121] In some embodiments of the present invention, the polymer-based resin is ASTM-D2 In accordance with 56, measurements were taken using a 3.2 mm thick rod that had been exposed to 50% relative humidity at 23°C for 48 hours, and the measured values ​​were 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 It has a notched Izod impact strength of 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 of approximately 80 J / m to approximately 500 J / m, approximately 80 J / m to approximately 400 J / m, approximately 80 J / m to approximately 300 J / m, approximately 80 J / m to approximately 200 J / m, and approximately 100 J / m, measured according to ASTM-D256 using a 3.2 mm thick rod subjected to 50% relative humidity at 23°C for 48 hours. m ~ about 500J / m, about 100J / m - about 400J / m, about 100J / m - about 300J / m, about 100J / m - about 200J / m, about 120J / m - about 500J / m, Approx. 120J / m~Approx. 400J / m, Approx. 120J / m~Approx. 300J / m, Approx. 120J / m~Approx. 200J / m, Approx. 150J / m~Approx. 500J / m, Approx. 150J / m~Approx. 40 0J / m, about 150J / m to about 300J / m, about 150J / m to about 200J / m, about 170J / m to about 500J / m, about 170J / m to about 400J / m, about 170J / m~Approx. 300J / m, Approx. 170J / m~Approx. 200J / m, 180J / m~Approx. 500J / m, Approx. 180J / m~Approx. 400J / m, Approx. 180J / m~Approx. 300J / m, Approx. It has notched Izod impact strengths in the range of 180 J / m to approximately 200 J / m, 190 J / m to approximately 500 J / m, approximately 190 J / m to approximately 400 J / m, approximately 190 J / m to approximately 300 J / m, approximately 190 J / m to approximately 200 J / m, 200 J / m to approximately 500 J / m, approximately 200 J / m to approximately 400 J / m, or approximately 200 J / m to approximately 300 J / m.

[0123]

[0122] In some embodiments, the polymer-based resin is ASTM-D256 Therefore, when measured using a 3.2 mm thick rod that has been subjected to 50% relative humidity at 23°C for 48 hours, it has a notched Izod impact strength of at least 300 J / m, or at least 325 J / m, or at least 350 J / m, or at least 400 J / m, or at least 450 J / m, or at least 500 J / m. In some embodiments, if the notched Izod impact strength is at least 300 J / m, or at least 325 J / m, or at least 350 J / m, or at least 400 J / m, or at least 450 J / m, or at least 500 J / m, then Tg may be in the range of 80°C to 130°C, 80°C to 125°C, 80°C to 120°C, 85°C to 130°C, 85°C to 125°C, 90°C to 130°C, 90°C to 125°C, 95°C to 130°C, 95°C to 125°C, 100°C to 130°C, 100°C to 125°C, 105°C to 130°C, 105°C to 125°C, 110°C to 130°C, 110°C to 125°C, or 110°C to 120°C.

[0124]

[0123] In some embodiments of the present invention, a polymer-based resin with a thickness of 3.2 mm The plaque exhibits ductile fracture as defined in section 1.8 of ASTM-D3763 when tested by instrumented impact according to ASTM-D3763.

[0125]

[0124] In some embodiments of the present invention, the polymer-based resin is ASTM-D7 According to ASTM-D790, the flexural modulus is higher than 1800 MPa when measured using a 3.2 mm thick rod that has been exposed to 50% relative humidity at 23°C for 48 hours. In some embodiments, the polymer-based resin has a flexural modulus of at least 1900 MPa, at least 2000 MPa, at least 2100 MPa, at least 2200 MPa, at least 2300 MPa, or at least 2400 MPa when measured using a 3.2 mm thick rod that has been exposed to 50% relative humidity at 23°C for 48 hours, according to ASTM-D790. In some embodiments, the polymer-based resin has a flexural modulus of approximately 1800 to approximately 3000 MPa, approximately 1900 to approximately 3000 MPa, approximately 2000 to approximately 3000 MPa, approximately 2100 to approximately 3000 MPa, approximately 2200 to approximately 3000 MPa, approximately 2300 to approximately 3000 MPa, approximately 2400 to approximately 3000 MPa, or approximately 2500 to approximately 3000 MPa, measured using a 3.2 mm thick rod after being subjected to 50% relative humidity at 23°C for 48 hours, according to ASTM-D790. When measured using a 3.2 mm thick rod, it exhibits a flexural modulus of approximately 1900 to 2500 MPa, approximately 1900 to 2800 MPa, or approximately 1900 to 3000 MPa.

[0126]

[0125] In some embodiments of the present invention, the cellulose ester composition comprises 2.5% to 30% by weight of EVA copolymer or a mixture of multiple EVA copolymers based on the total weight of the cellulose ester composition, a Tg value higher than 120°C, a notched Izod impact strength value higher than 100 J / m, or higher than 125 J / m, or higher than 150 J / m, and 10,000 P at 230°C and 100 rad / sec. (1,000 Pa·s) It has a viscosity of less than [amount missing].

[0127]

[0126] In some embodiments of the present invention, the cellulose ester composition is cellulose The ester composition comprises 2.5% to 30% by weight of EVA copolymer or a mixture of multiple EVA copolymers based on the total weight, has a Tg value higher than 120°C, a notched Izod impact strength value higher than 100 J / m, higher than 125 J / m, or higher than 150 J / m, and has 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 setting point of 249°C and a residence time of 5 minutes according to ASTM-D1003.

[0128]

[0127] Cellulose esters that do not contain plasticizers or contain low levels of plasticizers are screened. One problem that can occur during melting in a new plasticizing injection molding machine is that the screw may have difficulty recovering smoothly, which can result in poor material feeding and a "squeaking" noise. Surprisingly, it has been found that these problems during injection molding can be eliminated by adding an EVA copolymer according to several aspects of the present invention.

[0129]

[0128] In some embodiments of the present invention, the cellulose ester composition is cellulose The ester composition contains 2.5% to 30% by weight of EVA copolymer or a mixture of multiple EVA copolymers based on the total weight, has a Tg value higher than 120°C, a notched Izod impact strength higher than 100 J / m, or higher than 125 J / m, or higher than 150 J / m, does not produce squeaking noises or have screw recovery problems during injection molding at a barrel setting point of 249°C.

[0130]

[0129] In some embodiments of the present invention, the cellulose ester composition is cellulose The ester composition contains 2.5% to 30% by weight of EVA copolymer or a mixture of multiple EVA copolymers (having a VA content of 40 to 70% by weight, preferably 50 to 65% by weight, or a weight-average VA content of more than 50% by weight up to 65% by weight), has a Tg value higher than 120°C, a notched Izod impact strength value higher than 150 J / m, does not produce squeaking noises or have screw recovery problems during injection molding at a barrel setting point of 249°C.

[0131]

[0130] In some embodiments of the present invention, the cellulose ester composition comprises 2.5% to 30% by weight of EVA copolymer or a mixture of multiple EVA copolymers based on the total weight of the cellulose ester composition, with a Tg value higher than 100°C, a notched Izod impact strength value higher than 200 J / m, and 10,000 P at 230°C and 100 rad / sec. (1,000 Pa·s) It has a viscosity of less than [amount missing].

[0132]

[0131] In some embodiments of the present invention, the cellulose ester composition is cellulose The ester composition contains 2.5% to 30% by weight of EVA copolymer or a mixture of multiple EVA copolymers based on the total weight, a Tg value higher than 120°C, a notched Izod impact strength value higher than 200 J / m, and 249°C according to ASTM-D1003. The light transmittance values ​​measured using a 3.2 mm plaque after injection molding at the barrel setting point and a residence time of 5 minutes are higher than 80%, or at least 85%, or at least 90%.

[0133]

[0132] In some embodiments, the cellulose ester composition comprises a CAP resin, 5 to 20% by weight of an EVA copolymer or a mixture of multiple EVA copolymers based on the total weight of the cellulose ester composition, and 5 to 15% by weight of a plasticizer, and has a Tg value higher than 80°C, a notched Izod impact strength higher than 500 J / m or higher than 600 J / m, and 10,000 P at 230°C and 100 rad / sec. (1,000 Pa·s)It has a viscosity of less than 80%, and a light transmittance value of more than 80%, or at least 85%, or at least 90%, as measured using a 3.2 mm plaque after injection molding at a barrel setpoint of 249°C and a residence time of 5 minutes according to ASTM-D1003.

[0134]

[0133] In some embodiments, the cellulose ester composition comprises a CAP resin, 5 to 20% by weight of an EVA copolymer or a mixture of multiple EVA copolymers based on the total weight of the cellulose ester composition, and 5 to 15% by weight of a plasticizer, and has a Tg value higher than 120°C, a notched Izod impact strength higher than 350 J / m or higher than 400 J / m, and 10,000 P at 230°C and 100 rad / sec. (1,000 Pa·s) It has a viscosity of less than 80%, and a light transmittance value of more than 80%, or at least 85%, or at least 90%, as measured using a 3.2 mm plaque after injection molding at a barrel setpoint of 249°C and a residence time of 5 minutes according to ASTM-D1003.

[0135]

[0134] In some embodiments, the cellulose ester composition comprises a CAP resin, 5 to 10% by weight of an EVA copolymer or a mixture of multiple EVA copolymers (having a VA content of 45 to 65%, or 50 to 65%, or a weight-average VA content) based on the total weight of the cellulose ester composition, a Tg value higher than 140°C, a notched Izod impact strength value higher than 200 J / m, and 10,000 P at 230°C and 100 rad / sec. (1,000 Pa·s) It has a viscosity of less than 80%, and a light transmittance value of more than 80%, or at least 85%, or at least 90%, as measured using a 3.2 mm plaque after injection molding at a barrel setpoint of 249°C and a residence time of 5 minutes according to ASTM-D1003.

[0136]

[0135] In some embodiments, the cellulose ester composition comprises a CAP resin, 10 to 25% by weight of an EVA copolymer or a mixture of multiple EVA copolymers (having a VA content of 50 to 65% or a weight-average VA content) based on the total weight of the cellulose ester composition, a Tg value higher than 140°C, a notched Izod impact strength higher than 250 J / m, or higher than 300 J / m, or higher than 400 J / m, and 10,000 P at 230°C and 100 rad / sec. (1,000 Pa·s) It has a viscosity of less than 80%, and a light transmittance value of more than 80%, or at least 85%, or at least 90%, as measured using a 3.2 mm plaque after injection molding at a barrel setpoint of 249°C and a residence time of 5 minutes according to ASTM-D1003.

[0137]

[0136] In some embodiments, the cellulose ester composition comprises a CAB resin, 5 to 15% by weight of an EVA copolymer or a mixture of multiple EVA copolymers (having a VA content of 45 to 65, or 50 to 65%, or a weight-average VA content) based on the total weight of the cellulose ester composition, a Tg value higher than 130°C, a notched Izod impact strength value higher than 250 J / m, and 10,000 P at 230°C and 100 rad / sec. (1,000 Pa·s) It has a viscosity of less than 80%, and a light transmittance value of more than 80%, or at least 85%, or at least 90%, as measured using a 3.2 mm plaque after injection molding at a barrel setpoint of 249°C and a residence time of 5 minutes according to ASTM-D1003.

[0138]

[0137] In some aspects of the present invention, the cellulose ester composition has a thickness of 3.2 m Plaque m contains 2.5% to 30% by weight of EVA copolymer or a mixture of multiple EVA copolymers (having a VA content of 50 to 65%, or more than 50% and up to 65%, or a weight-average VA content) based on the total weight of the cellulose ester composition, and the polymer-based resin exhibits ductile fracture as specified in section 1.8 of ASTM-D3763 when tested by instrumented impact according to ASTM-D3763, and has a Tg value higher than 120°C.

[0139]

[0138] In some embodiments of the present invention, a 3.2 mm thick plaque of a cellulose ester composition contains 2.5% to 30% by weight of EVA copolymer or a mixture of multiple EVA copolymers (having a VA content of 50 to 65%, or more than 50% and up to 65%, or a weight-average VA content) based on the total weight of the cellulose ester composition, and the polymer-based resin exhibits ductile fracture as defined in section × 1.8 of ASTM-D3763 when tested by instrumented impact according to ASTM-D3763, a Tg value higher than 120°C, a notched Izod impact strength value higher than 100 J / m, or higher than 125 J / m, or higher than 150 J / m, and 10,000 P at 230°C and 100 rad / sec. (1,000 Pa·s) It has a viscosity of less than [amount missing].

[0140]

[0139] In some embodiments of the present invention, a 3.2 mm thick plaque of a cellulose ester composition contains 2.5% to 30% by weight of EVA copolymer or a mixture of multiple EVA copolymers (having a VA content of 50 to 65%, or more than 50% and up to 65%, or a weight-average VA content) based on the total weight of the cellulose ester composition, and the polymer-based resin exhibits ductile fracture as defined in section × 1.8 of ASTM-D3763 when tested by instrumented impact according to ASTM-D3763, with a Tg value higher than 120°C, a notched Izod impact strength value higher than 250 J / m, and 10,000 P at 230°C and 100 rad / sec. (1,000 Pa·s)It has a viscosity of less than 80%, and a light transmittance value of more than 80%, or at least 85%, or at least 90%, as measured using a 3.2 mm plaque after injection molding at a barrel setpoint of 249°C and a residence time of 5 minutes according to ASTM-D1003.

[0141]

[0140] In some aspects of the present invention, a 3.2 mm thick plaque of the CAP composition The composition contains 2.5% to 30% by weight of EVA copolymer or a mixture of multiple EVA copolymers (having a VA content of 50 to 65%, or more than 50% and up to 65%, or a weight-average VA content) based on the total weight of the cellulose ester composition, and the polymer-based resin exhibits ductile fracture as defined in section 1.8 of ASTM-D3763 when tested by instrumented impact according to ASTM-D3763, and has a Tg value higher than 120°C.

[0142]

[0141] In some embodiments of the present invention, a 3.2 mm thick plaque of the CAP composition contains 2.5% to 30% by weight of EVA copolymer or a mixture of multiple EVA copolymers (having a VA content of 50 to 65%, or more than 50% and up to 65%, or a weight-average VA content) based on the total weight of the cellulose ester composition, and the polymer-based resin exhibits ductile fracture as defined in section × 1.8 of ASTM-D3763 when tested by instrumented impact according to ASTM-D3763, a Tg value higher than 120°C, a notched Izod impact strength value higher than 100 J / m, or higher than 125 J / m, or higher than 150 J / m, and 10,000 P at 230°C and 100 rad / sec. (1,000 Pa·s) It has a viscosity of less than [amount missing].

[0143]

[0142] In some embodiments of the present invention, a 3.2 mm thick plaque of the CAP composition contains 2.5% to 30% by weight of EVA copolymer or a mixture of multiple EVA copolymers (having a VA content of 50 to 65%, or more than 50% and up to 65%, or a weight-average VA content) based on the total weight of the cellulose ester composition, and the polymer-based resin exhibits ductile fracture as defined in section × 1.8 of ASTM-D3763 when tested by instrumented impact according to ASTM-D3763, with a Tg value higher than 120°C, a notched Izod impact strength value higher than 250 J / m, and 10,000 P at 230°C and 100 rad / sec. (1,000 Pa·s) It has a viscosity of less than 80%, and a light transmittance value of more than 80%, or at least 85%, or at least 90%, as measured using a 3.2 mm plaque after injection molding at a barrel setpoint of 249°C and a residence time of 5 minutes according to ASTM-D1003.

[0144]

[0143] In some aspects of the present invention, the cellulose ester composition has a thickness of 3.2 m Plaque m contains two or more EVA copolymers (with a weight-average VA content of 50-65%, or more than 50% up to 65%) in total weight of 2.5% to 30% based on the total weight of the cellulose ester composition, and the polymer-based resin exhibits ductile fracture as specified in section 1.8 of ASTM-D3763 when tested by instrumented impact according to ASTM-D3763, and has a Tg value higher than 120°C.

[0145]

[0144] In some embodiments of the present invention, a 3.2 mm thick plaque of a cellulose ester composition contains two or more EVA copolymers (having a weight-average VA content of 50-65%, or more than 50% and up to 65%) in total weight of 2.5% to 30% based on the total weight of the cellulose ester composition, and the polymer-based resin exhibits ductile fracture as defined in section 1.8 of ASTM-D3763 when tested by instrumented impact according to ASTM-D3763, a Tg value higher than 120°C, a notched Izod impact strength value higher than 100 J / m, or higher than 125 J / m, or higher than 150 J / m, and 10,000 P at 230°C and 100 rad / sec. (1,000 Pa·s) It has a viscosity of less than [amount missing].

[0146]

[0145] In some embodiments of the present invention, a 3.2 mm thick plaque of cellulose ester contains two or more EVA copolymers (having a weight-average VA content of 50-65%, or more than 50% up to 65%) in total weight of 2.5% to 30% based on the total weight of the cellulose ester composition, and the polymer-based resin exhibits ductile fracture as defined in section 1.8 of ASTM-D3763 when tested by instrumented impact according to ASTM-D3763, with a Tg value higher than 120°C, a notched Izod impact strength value higher than 250 J / m, and 10,000 P at 230°C and 100 rad / sec. (1,000 Pa·s) It has a viscosity of less than 80%, and a light transmittance value of more than 80%, or at least 85%, or at least 90%, as measured using a 3.2 mm plaque after injection molding at a barrel setpoint of 249°C and a residence time of 5 minutes according to ASTM-D1003.

[0147]

[0146] In some aspects of the present invention, a 3.2 mm thick plaque of the CAP composition The composition contains two or more EVA copolymers (with a weight-average VA content of 50-65%, or more than 50% up to 65%) in total weight of 2.5% to 30% based on the total weight of the cellulose ester composition, and the polymer-based resin exhibits ductile fracture as specified in section 1.8 of ASTM-D3763 when tested by instrumented impact according to ASTM-D3763, and has a Tg value higher than 120°C.

[0148]

[0147] In some embodiments of the present invention, a 3.2 mm thick CAP plaque contains two or more EVA copolymers (having a weight-average VA content of 50-65%, or more than 50% and up to 65%) in total weight of 2.5% to 30% based on the total weight of the cellulose ester composition, and the polymer-based resin exhibits ductile fracture as defined in section ×1.8 of ASTM-D3763 when tested by instrumented impact according to ASTM-D3763, with a Tg value higher than 120°C, a notched Izod impact strength value higher than 100 J / m, or higher than 125 J / m, or higher than 150 J / m, and 10,000 P at 230°C and 100 rad / sec. (1,000 Pa·s) It has a viscosity of less than [amount missing].

[0149]

[0148] In some embodiments of the present invention, a 3.2 mm thick CAP plaque contains two or more EVA copolymers (having a weight-average VA content of 50-65%, or more than 50% up to 65%) in total weight of 2.5% to 30% based on the total weight of the cellulose ester composition, and the polymer-based resin exhibits ductile fracture as defined in section 1.8 of ASTM-D3763 when tested by instrumented impact according to ASTM-D3763, with a Tg value higher than 120°C, a notched Izod impact strength value higher than 250 J / m, and 10,000 P at 230°C and 100 rad / sec. (1,000 Pa·s) It has a viscosity of less than 80%, and a light transmittance value of more than 80%, or at least 85%, or at least 90%, as measured using a 3.2 mm plaque after injection molding at a barrel setpoint of 249°C and a residence time of 5 minutes according to ASTM-D1003.

[0150]

[0149] In another embodiment of the present invention, the cellulose ester composition is an antioxidant, heat The present invention further comprises at least one additive selected from the group consisting of stabilizers, release agents, antistatic agents, whitening agents, colorants, flow aids, processing aids, plasticizers, anti-fogging additives, inorganic substances, 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.

[0151]

[0150] In some embodiments, in addition to EVA (discussed here), cellulose The ester composition contains a stabilizer selected from the group consisting of a secondary antioxidant, an acid scavenger, or a combination thereof. In some embodiments, in addition to EVA (discussed herein), the cellulose ester composition contains a secondary antioxidant in an amount ranging from about 0.1 to about 0.8% by weight, based on the total weight of the composition. In some embodiments, in addition to EVA (discussed herein), the cellulose ester composition contains an acid scavenger in an amount ranging from about 0.2 to about 2.0% by weight, based on the total weight of the composition. In one embodiment, in addition to EVA (discussed herein), the cellulose ester composition contains a secondary antioxidant in an amount ranging from about 0.1 to about 0.8% by weight, and an acid scavenger in an amount ranging from about 0.2 to about 2.0% by weight, 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, for example, a salt stabilizer in the range of about 0.1 to about 0.5% by weight based on the total weight of the composition. In one embodiment, in addition to the cellulose ester (discussed herein), EVA, and stabilizer, the cellulose ester composition comprises any other components in total amounts of less than 5% by weight or less than 2% by weight based on the total weight of the composition.

[0152]

[0151] In some embodiments, the cellulose ester composition is maleic anhydride modified E It does not contain VA. In some embodiments, the cellulose ester composition does not contain polyether ester compounds. In some embodiments, the cellulose ester composition does not contain adipic acid compounds. In some embodiments, the cellulose ester composition contains, based on the total weight of the cellulose ester composition, 65 to 99% by weight of one or more cellulose esters, 1 to 35% by weight of one or more EVA copolymers, and other components totaling less than 5% by weight. In some embodiments, such other components do not contain plasticizers, polyether ester compounds, or adipic acid compounds. In some embodiments, the cellulose ester composition contains dioctyl adipate (DOA) plasticizer and does not contain other adipic acid compounds.

[0153]

[0152] In another aspect of the present invention, a method for producing a cellulose ester composition is provided. The method involves contacting at least one cellulose ester, at least one EVA copolymer, and optionally at least one plasticizer. The cellulose ester, plasticizer, and EVA copolymer are discussed above in this specification. In one embodiment, the cellulose ester, EVA copolymer, and optional plasticizer can be mixed in any order of addition.

[0154]

[0153] In another aspect of the present invention, (a) at least one EVA copolymer, A method for producing a cellulose ester composition is provided, comprising mixing at least one cellulose ester and optionally at least one plasticizer for a time and temperature sufficient to disperse an EVA copolymer and 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 in upper limits by the processing temperature of the EVA copolymer and in lower limits by the maximum usable temperature of the cellulose ester composition.

[0155]

[0154] The mixing efficiency of two or more viscoelastic materials is determined by the ratio of the viscosities of the viscoelastic materials. It is possible. In one embodiment, with respect to a given mixing apparatus and shear rate range, the viscosity ratio of the dispersed phase (EVA copolymer) to the continuous phase (cellulose ester) must be within a specified limit to obtain an appropriate particle size.

[0156]

[0155] In some embodiments, EVA copolymer, cellulose ester, and optional The mixing of the plasticizer and any additives can be carried out by any method known in the art that is suitable for dispersing the EVA copolymer, plasticizer, and additives in the cellulose ester. Examples of mixing apparatus include, but are not limited to, Banbury mixers, Bravender mixers, roll mills, and extruders (single-screw or twin-screw). The shear energy during mixing is determined by a combination of the apparatus, blade design, rotational speed (rpm), and mixing time. The shear energy must be sufficient to disperse the EVA copolymer throughout the cellulose ester.

[0157]

[0156] In some embodiments, cellulose ester, EVA copolymer, plasticizer, The additives can be mixed in any order during the process. In one embodiment, the cellulose ester is pre-mixed with the EVA copolymer and / or plasticizer. Then, the cellulose ester containing the EVA copolymer and / or plasticizer is mixed with the additives. In another embodiment of the present invention, if a reactive impact modifier is used, the reactive impact modifier can be mixed with the cellulose ester first, and then the other components can be added.

[0158]

[0157] The composition of the present invention can be used as a molded plastic part or as a solid plastic part. It is useful as a product. This composition is suitable for use in any application where a hard, transparent plastic is required. Examples of such parts include disposable knives, forks, spoons, plates, cups, straws, as well as eyeglass frames, toothbrush handles, toys, automobile trim, tool handles, camera parts, electronic equipment parts, razor parts, ink pen barrels, disposable syringes, bottles, etc. In one embodiment, the composition of the present invention is useful as a plastic, film, fiber (including melt-spun fibers and solution-spun fibers), and sheet. In one embodiment, this composition is useful for manufacturing bottles, bottle caps, eyeglass frames, cutlery, disposable cutlery, cutlery handles, shelves, shelf dividers, electronic equipment housings, electronic equipment cases, computer monitors, printers, keyboards, pipes, automobile parts, automobile interior parts, automobile trim, signs, thermoformed letters, siding, toys, thermally conductive plastics, ophthalmic lenses, tools, tool handles, and household goods. It is useful as a plastic for eyes. In other embodiments, the compositions of the present invention are suitable for use as films, sheetings, fibers, molded articles, medical devices, packaging materials, bottles, bottle caps, eyeglass frames, cutlery, disposable cutlery, cutlery handles, shelves, shelf dividers, furniture parts, electronic equipment housings, electronic equipment cases, computer monitors, printers, keyboards, pipes, toothbrush handles, automotive parts, automotive interior parts, automotive trim, signs, outdoor signs, skylights, multilayer films, thermoformed letters, siding, toys, toy parts, thermally conductive plastics, ophthalmic lenses and frames, tools, tool handles, and household goods, healthcare products, commercial food service products, boxes, films for graphic art applications, and plastic films for plastic-glass laminates.

[0159]

[0158] This cellulose ester composition is used for fibers, films, molded articles, and sheets. It is useful for forming cellulose ester compositions. Methods for forming cellulose ester compositions into fibers, films, molded articles, and sheetings can follow methods known in the art. Examples of possible molded articles include, without limitation, medical devices, medical packaging materials, healthcare products, commercial food service products such as food pans, tumblers and storage boxes, bottles, food processors, blenders and mixer bowls, household goods, water bottles, crisper trays, washing machine fronts, vacuum cleaner parts, and toys. Other possible molded articles include ophthalmic lenses and frames.

[0160]

[0159] The present invention further comprises one or the cellulose ester compositions described herein. The present invention relates to a manufactured article comprising multiple films and / or sheets. In some embodiments, the films and / or sheets of the present invention may be of any thickness that is obvious to those skilled in the art.

[0161]

[0160] The present invention further includes one or more films and / or sheets as described herein. This invention relates to the following. Methods for forming a cellulose ester composition into one or more films and / or sheets 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 producing films and / or sheets include, but are not limited to, extrusion, calendering, compression molding, wet block processing, dry block processing, and solution casting.

[0162]

[0161] The present invention further relates to molded articles as described herein. Cellulose ester compound Methods for forming a product into a molded article include methods known in the art. Examples of molded 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 extruded-blow-molded articles. Methods for manufacturing molded articles include, but are not limited to, injection molding, extrusion, injection-blow molding, injection-stretch-blow molding, and extruded-blow molding. Methods of the present invention include any blow molding process known in the art, such as (but not limited to) extruded-blow molding, extruded-stretch-blow molding, injection-blow molding, and injection-stretch-blow molding.

[0163]

[0162] The present invention encompasses any injection blow molding manufacturing process known in the art. A typical description of the injection blow molding (IBM) manufacturing process, though not limited to this, is: (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) that is 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; and (4) blowing air into the preform to stretch and inflate it and fill the mold. (5) Cooling the molded article; (6) Removing the article from the mold; are involved.

[0164]

[0163] The present invention relates to any injection stretch blow molding manufacturing process known in the art This includes, but is not limited to, a typical description of an injection stretch blow molding (ISBM) manufacturing process, which involves: (1) melting a 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) that is 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 stretch rod and blowing air into the preform to stretch and expand it and fill the mold; (5) cooling the molded article; and (6) removing the article from the mold.

[0165]

[0164] The present invention encompasses any extrusion blow molding manufacturing process known in the art. A typical description of an extrusion blow molding manufacturing process, though not limited to the above, involves: (1) melting a composition in an extruder; (2) extruding the molten composition through a die to form a tube of molten polymer (i.e., a parison); (3) fitting a mold having the desired final shape around the parison; (4) blowing air into the parison to stretch and expand the extruded material and fill the mold; (5) cooling the molded article; (6) removing the article from the mold; and (7) removing excess plastic (usually called burrs) from the article.

[0166]

[0165] The present invention can be further illustrated by the following embodiments of its preferred aspects, but these embodiments are included for illustrative purposes only and are not intended to limit the scope of the invention unless otherwise specifically indicated. Examples 6A, F, G, H, I, J, and K correspond to examples included in the present invention, while the other examples correspond to reference examples. [Examples]

[0167]

[0166] Cellulose ester compositions were prepared by mixing the selected cellulose ester with an EVA copolymer and / or a plasticizer. Unless otherwise specified, the cellulose ester compositions were mixed in a Leistritz 18 mm (L / D ratio of 50:1) twin-screw extruder at 18 pounds. (8.2kg) The processing was carried out at a rate of 250 rpm per hour using a screw speed of 250 rpm and a barrel temperature of 220°C. For the mixing of CA and CAP141-20 based compositions, the barrel temperature was 230°C. The grades of the cellulose ester compositions used in the following examples are shown in Table 1 above.

[0168]

[0167] The EVA copolymers used in the examples are shown in Table 2 below.

[0168]

[0169] [Table 2]

[0170]

[0169] The examples include tests on injection-molded plaques and rods. Unless otherwise specified, molding was performed using a Toyo injection molding machine with 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 / determined as discussed below.

[0171]

[0170] ASTM standard method D: Heat the sample from -100°C at a heating rate of 20°C / min. The glass transition temperature (Tg) was measured according to 3418. A DSC scan of a blend of multiple materials may show multiple Tg transitions. If more than one Tg transition is detected during the scan, the glass transition of the matrix is ​​defined as the highest Tg measured during the scan.

[0172]

[0171] The degree of cloudiness (%) and light transmittance are calculated according to ASTM-D1003, 102mm × Measurements were taken on injection-molded plaques measuring 102 mm x 3.2 mm. In the examples, where transparency grading is given, the grading is determined by visual inspection, with transparency corresponding to a cloudiness percentage of less than approximately 10%, slight cloudiness corresponding to a cloudiness percentage of more than approximately 10% or more than approximately 15% and less than approximately 25%, and cloudiness or turbidity corresponding to a cloudiness percentage of more than approximately 25%.

[0173]

[0172] Melt viscosity was measured using a Rheometrics Dynamic Analysis Instrument (RDA II) plate-plate melt rheometer with a 25 mm diameter parallel plate, a 1 mm gap, and a 10% strain, and measured using frequency scans between 1 rad / sec and 100 rad / sec according to ASTM-D4440.

[0174]

[0173] Notched Izod impact strength test involves exposing the rod material to 23°C and 50% RH. After conditioning for 48 hours, the notched, 3.2 mm thick molded rod material was subjected to a 23°C procedure according to ASTM method D256.

[0175] Example 1: Capsules with and without plasticizers:

[0174] CAP Grade 1 (without plasticizer (Example 1A) and 10 from Table 1 A material containing % DOA plasticizer (Example 1B) was injection molded into a 3.2 mm thick x 12.8 mm wide rod using a Toyo 110-ton injection molding machine, with a barrel temperature of 240°C and a mold temperature of 70°C.

[0176]

[0175] For each sample, transparency, melt viscosity, Tg, and Izod impact strength were measured. The following was determined. The composition and properties of the materials for Examples 1A and 1B are shown in Table 3 below.

[0176]

[0177] [Table 3]

[0178]

[0177] Table 3 shows CAP482-20 (blended with plasticizer and unblended) The properties of the two types of plastics are shown. Examining the table reveals that the two types of plastics remained transparent. The CAP plastic without plasticizer had a relatively high glass transition temperature but low impact resistance. In contrast, the plasticized CAP compound had a higher impact strength but a lower Tg. It would be desirable to provide a cellulose ester composition that possesses both the advantages of high Tg and good impact resistance.

[0179] Example 2: Blend of CE and EVA:

[0178] Different grades of cellulose esters (from Table 1) The mixture was blended with a certain amount of EVA copolymer and injection molded into a 3.2 mm thick x 12.8 mm wide rod using a Toyo 110-ton injection molding machine with a barrel temperature of 240°C and a mold temperature of 70°C.

[0180]

[0179] For each sample, transparency, melt viscosity, Tg, and Izod impact strength were measured. The following was determined. The composition and properties of the material for Example 2 are shown in Table 4 below.

[0180]

[0181] [Table 4]

[0182]

[0181] Examining Table 4, the CE / EVA compounds are similar to the plasticizing CAP compounds from Table 3. In comparison, it was found to have a considerably higher Tg. Furthermore, for CAP482-20 (Grade 1), it was shown that when the VA content (of the EVA copolymer) was in the range of approximately 40% to 70% by weight, or 50% to 65% by weight, formulations with both good transparency and increased toughness (i.e., impact strength higher than 150 J / m) were obtained. This is thought to be the result of appropriate interfacial adhesion, close refractive index matching, and fine dispersion of EVA rubber particles. Furthermore, when the VA content is excessively high (e.g., 80%), the EVA and cellulose ester are considered to be completely miscible (single composition-dependent glass transition temperature). As a result, although such formulations may be transparent, this blend had a lower Tg and less good toughness.

[0183]

[0182] Furthermore, examining Table 4, it can be seen that the VA content (of the EVA copolymer) is excessively low (immediately It can also be seen that formulations with a concentration of <40% were obtained that were cloudy and generally more brittle. These formulations were cloudy because they lacked proper interphase adhesion between the EVA rubber particles and the cellulose ester.

[0184] Example 3: Blends of high Mw and low Mw CAP and EVA:

[0183] CAP grades with different molecular weight (Mw) ratios (from Table 1) (one grade) One grade has a relative viscosity of 7.4, and another grade has a relative viscosity of 2.5. These were blended with different amounts of Levamelt 600EVA copolymer and injection molded into 3.2mm thick x 12.8mm wide rods using a Toyo 110-ton injection molding machine with a barrel temperature of 240°C and a mold temperature of 70°C.

[0185]

[0184] For each sample, transparency, melt viscosity, Tg, and Izod impact strength were measured. The following was determined. The composition and properties of the material for Example 3 are shown in Table 5 below.

[0185]

[0186] [Table 5]

[0187]

[0186] Examining Table 5, it is found that blending lower molecular weight cellulose esters into the formulation This results in better fluidity (or lower melt viscosity). Blending with lower Mw cellulose esters may also provide improved color stability for lower processing temperatures. Also, CAP482-20 and CAP482-0.5 and E The blend with VA also showed slightly lower toughness than similar CAP482-20 / EVA compositions with equivalent EVA loads. The tensile and bending properties (not shown) were substantially unchanged compared to similar compositions containing only CAP482-20.

[0188] Example 4: A blend of medium-weight CAP and EVA:

[0187] A CAP grade with a relative viscosity of 4.26 and a medium molecular weight (Mw) (Table 1) The material was blended with 10% by weight of different grades of EVA copolymer and injection molded into a 3.2 mm thick x 12.8 mm wide rod using a Toyo 110-ton injection molding machine with a barrel temperature of 240°C and a mold temperature of 70°C.

[0189]

[0188] For each sample, transparency, melt viscosity, Tg, and Izod impact strength were measured. The following was determined. The composition and properties of the material for Example 4 are shown in Table 6 below.

[0189]

[0190] [Table 6]

[0191]

[0190] When examining Table 6, high molecular weight cellulose esters and low molecular weight cellulose esters It is shown that medium molecular weight cellulose esters can be used instead of ester blends. The table shows that medium molecular weight cellulose esters provide good compatibility with EVA, allowing for the use of EVA with a lower VA content (VA = approximately 28-40%), while still providing toughness (shown in 4E) that may be suitable for some applications. However, when higher toughness is required, comparisons of Examples 4B and 2D, and 4C and 2G show that using CAP with a relative viscosity higher than 6.0 provides considerably higher impact strength and equivalent Tg values ​​compared to using CAP with a lower relative viscosity for the same amount of EVA loading. Thus, in some embodiments of the present invention, cellulose ester compositions having a relative viscosity value higher than 6.0 are preferred.

[0192] Example 5: Blend of CAP, EVA, and plasticizer:

[0191] Cellulose ester grade 1 (from Table 1) is used with different grades of EVA. The polymer and different types and amounts of plasticizers were blended and injection molded into 3.2 mm thick x 12.8 mm wide rods using a Toyo 110-ton injection molding machine with a barrel temperature of 240°C and a mold temperature of 70°C. DOA is dioctyl adipate and TEGEH is triethylene glycol bis-2-ethylhexanoate.

[0193]

[0192] For each sample, transparency, melt viscosity, Tg, and Izod impact strength were measured. The following was determined. The composition and properties of the material for Example 5 are shown in Table 7 below.

[0193]

[0194] [Table 7]

[0195]

[0194] Examining Table 7, the addition of plasticizers relates to cellulose ester compositions. It is shown that it can function as a flow aid. Furthermore, it is shown that in order to give compounds with a higher Tg than fully plasticized cellulose ester compounds, as well as good toughness and good flowability, the level of the flow aid must be kept lower than the normal plasticizer level for cellulose esters. In some cases, certain plasticizers were found to function in EVA (dispersed phase or minor phase) rather than in CE (continuous phase or major phase), as in Example 5A. As a result, the addition of the plasticizer (DOA) reduced viscosity without a significant negative impact on the glass transition temperature compared to Example 2D. This is thought to provide better flowability and improved color stability for lower processing temperatures for some applications.

[0196] Example 6: Blend of CAP and EVA copolymer:

[0195] Multiple different grades of cellulose esters (from Table 1) The EVA copolymer was blended with other materials and injection molded into a 3.2 mm thick x 12.8 mm wide rod using a Toyo 110-ton injection molding machine with a barrel temperature of 240°C and a mold temperature of 70°C.

[0197]

[0196] For each sample, transparency, Tg, and Izod impact strength were determined. The composition and properties of the material for Example 6 are shown in Table 8 below.

[0197]

[0198] [Table 8]

[0199]

[0198] Examining Table 8 reveals different multipliers with higher VA content and lower VA content. Blending several EVA copolymers with CAP resulted in higher impact strength (Example 6B) and good transparency compared to only equivalent amounts of EVA copolymers with higher VA content (Example 4A) or lower VA content (Example 4E).

[0200]

[0199] In addition, the materials selected from Tables 4 and 8 are used for instrumentation according to ASTM-D3763. For impact testing, plaques measuring 3.2 mm thick × 102 mm wide × 102 mm in width were injection molded using a Toyo 110-ton injection molding machine with a barrel temperature of 240°C and a mold temperature of 70°C. Table 9 shows the fracture modes for each sample. The ductile fracture mode is given when the specimen plastically deforms without forming cracks that radiate beyond 10 mm from the center of the impact point before fracture. The brittle fracture mode is given when the test area of ​​the specimen decomposes into two or more pieces with sharp edges and little or no plastic flow is observed. Surprisingly, even at similar EVA% and average VA content%, compositions using mixtures of multiple EVA copolymers exhibit ductile fracture, while compositions using a single EVA copolymer exhibit brittle fracture.

[0201]

[0200]

[0202] [Table 9]

[0203] Example 7: Haze degree % and light transmittance for CAP composition:

[0201] CAP composition without impact-resistant modifier (IM) or EVA copolymer, impact-resistant For CAP compositions containing a detonation modifier and CAP compositions containing different levels of EVA copolymer, the degree of cloudiness and light transmittance were determined after injection molding at 240°C with a residence time of 5 minutes. All samples also contained 0.5% by weight of Irganox 1010. The composition and properties of the materials for Example 7 are shown in Table 9 below.

[0204]

[0202]

[0205] [Table 10]

[0206]

[0203] When examining Table 10, (specified amount) acrylic impact modifier or EVA copolymer The addition of mer increased the degree of cloudiness in the CAP composition compared to CAPs without IM or EVA, and the increase in cloudiness was less in CAP compositions with EVA copolymer than in CAP compositions with acrylic impact modifier. Furthermore, the effect of EVA copolymer on transmittance % was smaller than that of impact modifier.

[0207]

[0204] The above detailed descriptions of multiple aspects of the present invention are intended to be useful for those skilled in the art to implement the present invention. It is intended to describe various forms of the present invention in sufficient detail to enable it. Without departing from the scope of the invention, other aspects can be used and modifications can be made. Therefore, 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 applications, together with the full scope of equivalents to which the claims are entitled.

[0208]

[0205] As used herein, the recitation of "one aspect", "an aspect", or "aspects" means that one or more related features are included in at least one aspect of the technology. Separate recitations of "one aspect", "an aspect", or "aspects" herein do not necessarily refer to the same aspect, and are not mutually exclusive unless stated otherwise and / or obvious to those skilled in the art from the recitation. For example, features, steps, etc. described in one aspect may or may not also be included in other aspects. Thus, the present invention can encompass various combinations and / or integrations of the multiple aspects described herein. The present invention includes the following embodiments. (1) A cellulose ester composition comprising at least one cellulose ester, at least one ethylene vinyl acetate (EVA) copolymer, and optionally at least one plasticizer, The at least one cellulose ester is selected from cellulose propionate (CP), cellulose butyrate (CB), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose propionate butyrate (CPB), cellulose trippropionate (CTP), or cellulose tripylate (CTB); The relative viscosity of the aforementioned at least one cellulose ester is greater than 6.0 when measured at 25°C with respect to an acetone solution containing 2% by weight of the cellulose ester; and The cellulose ester composition is the cellulose ester composition having a Tg of at least 120°C. (2) The cellulose ester composition according to (1), wherein the composition comprises 65 to 99% by weight of the cellulose ester, 1 to 35% by weight of the EVA, and 0 to 15% by weight of the plasticizer. (3) The cellulose ester composition according to (1), wherein the composition comprises 65 to 99% by weight of the cellulose ester, 1 to 35% by weight of the EVA, and 0 to 5% by weight of the plasticizer. (4) The cellulose ester composition according to (1), wherein the composition comprises 70 to 97.5% by weight of the cellulose ester and 2.5 to 30% by weight of the EVA, and does not contain a plasticizer. (5) The cellulose ester composition according to any one of (1) to (4), wherein the cellulose ester is selected from cellulose acetate propionate (CAP) or cellulose acetate butyrate (CAB). (6) The cellulose ester composition comprises at least two different cellulose esters selected from cellulose propionate (CP), cellulose butyrate (CB), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose propionate butyrate (CPB), cellulose trippropionate (CTP), or cellulose tripylate (CTB), The cellulose ester composition according to any one of (1) to (5), wherein at least one of the cellulose esters has a relative viscosity greater than 6.0 as measured at 25°C with respect to an acetone solution containing 2% by weight of the cellulose ester; and the cellulose ester composition has a Tg of at least 120°C. (7) The cellulose ester composition according to any one of (1) to (6), wherein the EVA has a vinyl acetate content in the range of 40 to 70% by weight. (8) The cellulose ester composition according to any one of (1) to (7), wherein the EVA has a vinyl acetate content in the range of 50 to 65% by weight. (9) The cellulose ester composition according to any one of (1) to (8), wherein the EVA is a combination of at least two EVA copolymers having different vinyl acetate (VA) content, the average VA content of the combination is in the range of 50 to 65% by weight, and the composition exhibits ductile fracture (when tested according to the examples). (10)(i) at least one cellulose ester selected from cellulose propionate (CP), cellulose butyrate (CB), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose propionate butyrate (CPB), cellulose trippropionate (CTP), or cellulose tripyrate (CTB); (ii) at least one ethylene vinyl acetate (EVA) copolymer; and (iii) at least one type of plasticizer; A cellulose ester composition comprising, The cellulose ester composition has a Tg of at least 120°C, and a notched Izod impact strength of at least 200 J / m measured after conditioning a 3.2 mm rod at 23°C and 50% RH for 48 hours according to ASTM method D256. (11) The cellulose ester composition according to (10), wherein the cellulose ester composition has a continuous cellulose ester phase and a discontinuous EVA copolymer phase, and the plasticizer is contained in the discontinuous EVA phase. (12) The cellulose ester composition according to (10) or (11), wherein the cellulose ester composition has a Tg that is 5% or less different from the Tg of a similar cellulose ester composition that does not contain a plasticizer. (13) The cellulose ester composition according to any one of (10) to (12), wherein the cellulose ester is CAP, the plasticizer is dioctyl adipate (DOA), and the EVA has a vinyl acetate content in the range of 40 to 70% by weight. (14) The cellulose ester composition according to any one of (10) to (13), wherein the cellulose ester is CAP, the plasticizer is dioctyl adipate (DOA), and the EVA has a vinyl acetate content in the range of 50 to 65% by weight. (15) The cellulose ester composition according to any one of (1) to (14), wherein the composition further comprises at least one additive selected from the group consisting of antioxidants, heat stabilizers, mold release agents, antistatic agents, whitening agents, colorants, plasticizers, inorganic substances, UV stabilizers, lubricants, nucleating agents, reinforcing fillers, glass fibers, carbon fibers, flame retardants, dyes, pigments, colorants, further resins, and combinations thereof. (16) A cellulose ester composition according to any one of (1) to (15), further comprising as a blend at least one polymer component, wherein the polymer is selected from the group consisting of nylon; polyester; polyamide; polystyrene; other cellulose esters, cellulose ethers; polystyrene copolymer; styrene acrylonitrile copolymer; polyolefin; polyurethane; acrylonitrile butadiene styrene copolymer; poly(methyl methacrylate); acrylic copolymer; 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) aromatic dihydroxy compounds; and combinations thereof. (17) A method for producing a cellulose ester composition, (a) at least one cellulose ester selected from cellulose propionate (CP), cellulose butyrate (CB), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose propionate butyrate (CPB), cellulose trippropionate (CTP), or cellulose tripyrate (CTB): and (b) at least one type of EVA; This includes mixing the EVA for a sufficient amount of time and at a temperature to disperse it throughout the cellulose ester to produce the composition; The above method wherein the relative viscosity of at least one type of cellulose ester is greater than 6.0 when measured at 25°C with respect to an acetone solution containing 2% by weight of the cellulose ester. (18) A manufactured article comprising the cellulose ester composition described in any of (1) to (16). (19) The manufactured article according to (18), wherein the article is selected from injection-molded articles, extruded articles, injection-blow-molded articles, injection-stretched blow-molded articles, and extruded blow-molded articles, which contain the cellulose ester composition described in (1). (20) A film or sheet containing the cellulose ester composition described in any of (1) to (16).

Claims

[Claim 1] A cellulose ester composition comprising at least one cellulose ester, an ethylene vinyl acetate (EVA) copolymer, and optionally at least one plasticizer, The at least one cellulose ester is selected from cellulose propionate (CP), cellulose butyrate (CB), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose propionate butyrate (CPB), cellulose trippropionate (CTP), or cellulose tripylate (CTB); The relative viscosity of the at least one cellulose ester is greater than 6.0 when measured at 25°C with respect to an acetone solution containing 2% by weight of the cellulose ester; The cellulose ester composition has a Tg of at least 120°C; and The aforementioned EVA copolymer is a combination of at least two EVA copolymers having different vinyl acetate (VA) content, and the average VA content of the combination is in the range of 50 to 65% by weight. The cellulose ester composition wherein the combination comprises a first EVA copolymer and a second EVA copolymer, and the first EVA copolymer and the second EVA copolymer differ by 20 or more in the vinyl acetate (VA) content [weight %].

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