Composition of a cellulose ester and an impact resistance improver, and an article manufactured using these compositions

Abstract

Cellulose ester compositions are provided that include at least one cellulose ester, at least one impact modifier, and optionally at least one plasticizer. Methods for producing the cellulose ester compositions are also provided, as well as articles made using these compositions, such as eyeglass frames, automobile parts, and toys. [Selection diagram] None

Description

Technical Field

[0001]

[0001] The present invention belongs to the field of cellulose ester chemistry, particularly cellulose esters containing impact modifiers and optionally plasticizers. The present invention also belongs to the field of cellulose ester compositions containing at least one impact modifier and optionally at least one plasticizer. Also provided are methods for producing these cellulose ester compositions, and plastic articles produced using these compositions such as spectacle frames, automotive parts, and toys.

Background Art

[0002]

[0002] Cellulose acetate compositions typically have a heat distortion temperature (HDT) of less than 90°C. Commercially available cellulose esters used in the thermoforming of articles typically contain a significant amount of plasticizer to enable processing and impart sufficient toughness to the formed article. However, adding a plasticizer has the drawback that this lowers the HDT compared to the base cellulose ester, limiting the use of the cellulose ester material to applications that can accept an HDT lower than about 90°C. Also, cellulose ester molded articles may exhibit exudation of the plasticizer during use.

Summary of the Invention

Problems to be Solved by the Invention

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

Means for Solving the Problems

[0004]

[0003] Surprisingly, it has been found that a composition of a cellulose ester having an HDT exceeding 95° C. can be produced. In some embodiments of the present invention, this can be achieved by reducing the amount of the plasticizer and, in some embodiments, by completely eliminating the use of the plasticizer in the composition. By eliminating the plasticizer, the common problems associated with the leaching of the plasticizer during use can be eliminated. However, reducing or eliminating the plasticizer may reduce the toughness of these high-HDT cellulose compositions. Surprisingly, it has been found that a specific material called an impact resistance improver can restore the toughness of a high-HDT cellulose composition even when added at a relatively low level, for example, at a level of about 2% by weight based on the total weight of the cellulose ester composition.

[0005]

[0004] In some embodiments, the present invention relates to dispersing an amount of an impact resistance improver sufficient to improve the mechanical and physical properties of a cellulose ester composition in the cellulose ester composition in the form of small discrete particles. The impact resistance-improved cellulose ester according to the present invention has the unique property of being melt-processable and having a considerably higher HDT compared to commercially available plasticized cellulose ester thermoplastic resins, and has a high modulus of elasticity, good impact properties, and good resistance to load deformation.

[0006]

[0005] In one embodiment of the present invention, there is provided a cellulose ester composition comprising at least one cellulose ester, at least one impact resistance improver, and optionally at least one plasticizer.

[0007]

[0006] In another embodiment of the present invention, there is provided a cellulose ester composition comprising at least one cellulose ester, at least one impact resistance improver, and at least one plasticizer.

[0008]

[0007] In another aspect of the present invention, there is provided a method for producing a cellulose ester composition, which includes bringing at least one type of cellulose ester, at least one type of impact resistance improver, and optionally at least one type of plasticizer into contact with each other, and blending such a combination. In one aspect, the plasticizer is present in an amount that does not substantially reduce the HDT of the cellulose ester composition compared to a similar composition without the plasticizer. In some aspects, as a result of including the plasticizer, the HDT does not change (e.g., decrease) by more than 10%, or more than 5%, or more than 2%.

[0009]

[0008] In one aspect of the present invention, there is described a cellulose ester composition that does not contain a plasticizer, but contains 1 to 30% by weight, or 1 to 15% by weight, or 2 to 10% by weight, or 10 to 30% by weight, or 15 to 30% by weight of an impact resistance improver based on the total weight of the cellulose ester composition, has an HDT value higher than 95°C, and has a notched Izod impact strength value higher than 80 J / m.

[0010]

[0009] In another aspect of the present invention, there is provided a melt-processable cellulose ester composition that does not contain a plasticizer. In some aspects, the melt-processable cellulose ester composition contains 1 to 30% by weight, or 1 to 15% by weight, or 2 to 10% by weight, or 10 to 30% by weight, or 15 to 30% by weight of an impact resistance improver based on the total weight of the cellulose ester composition, has an HDT value higher than 95°C, a notched Izod impact strength value higher than 80 J / m, and a spiral flow value of at least 15 inches (38.1 cm) measured at 240°C.

[0011]

[0010] In another aspect of the present invention, the melt-processable cellulose ester composition contains 2% to 15% by weight of an impact resistance improver based on the total weight of the cellulose ester composition, has an HDT value higher than 95°C, a notched Izod impact strength value higher than 80 J / m, and 10,000 P at 240°C and 400 rad / sec (1,000 Pa·s)Has a viscosity below

[0012]

[0011] In another aspect, there is provided a cellulose ester composition having a total DS / AGU in the range of about 2 to about 2.99, wherein the DS / AGU of acetyl is in the range of about 0 to about 2.2, and the remainder of the ester groups comprises propionyl, butyryl, or a combination thereof.

[0013]

[0012] In one aspect of the present invention, a melt-processable cellulose ester composition is described, which contains a plasticizer of 15 wt% or less, or 10 wt% or less; an impact resistance improver of 1 to 30 wt%, or 1 to 15 wt%, or 2 to 10 wt%; has an HDT value higher than 95 °C and a notched Izod impact strength value higher than 80 J / m.

[0014]

[0013] In another aspect of the present invention, a plasticizer of 15 wt% or less, or 10 wt% or less based on the total weight of the cellulose ester composition; an impact resistance improver of 1 to 30 wt%, or 1 to 15 wt%, or 2 to 10 wt% based on the total weight of the cellulose ester composition; is included; and it has an HDT value higher than 95 °C, a notched Izod impact strength value higher than 80 J / m, and a spiral flow value of at least 15 inches measured at 240 °C. (38.1 cm) A melt-processable cellulose ester composition having the above properties is described.

[0015]

[0014] In another aspect of the present invention, a plasticizer of 15 wt% or less, or 10 wt% or less based on the total weight of the cellulose ester composition; an impact resistance improver of 1 to 30 wt%, or 1 to 15 wt%, or 2 to 10 wt% based on the total weight of the cellulose ester composition; is included; and it has an HDT value higher than 95 °C, a notched Izod impact strength value higher than 80 J / m, and a viscosity of less than 10,000 P at 240 °C and 400 rad / sec. (1,000 Pa·s) A melt-processable cellulose ester composition having the above properties is described.

[0016]

[0015] In other embodiments, the melt-processable cellulose ester composition described above may optionally contain some plasticizer. In some embodiments, the plasticizer is present in an amount that does not substantially reduce the HDT of the cellulose ester composition compared to a similar composition without the plasticizer. In some embodiments, the HDT does not change (e.g., decrease) by more than 10%, or more than 5%, or more than 2% as a result of including the plasticizer.

[0017]

[0016] In one embodiment of the present invention, there is provided a cellulose ester composition comprising at least one type of cellulose ester, at least one type of impact resistance improver, and optionally at least one type of plasticizer. In one embodiment, the cellulose ester is CAP, and the composition contains 0 to 5 wt%, 0 to 2 wt%, less than 0 to 2 wt%, or 0 to 1 wt% of the plasticizer. In one embodiment, the cellulose ester is CAP and does not contain a plasticizer.

[0018]

[0017] In another embodiment of the present invention, there is provided a cellulose ester composition comprising at least one type of cellulose ester, at least one type of impact resistance improver, and at least one type of plasticizer. In one embodiment, the cellulose ester is CA and contains 1 to 15 wt% of the plasticizer. In some embodiments, the cellulose ester is CA, and the composition contains 1 to 10 wt%, or less than 1 to 10 wt%, or 1 to 9 wt% of the plasticizer.

Embodiments for Carrying Out the Invention

[0019]

[0018] In one embodiment of the present invention, there is provided a cellulose ester composition comprising at least one type of cellulose ester, at least one type of impact resistance improver, and optionally at least one type of plasticizer.

[0020]

[0019] In some embodiments, the cellulose ester used in the present invention may be any known in the art. The cellulose ester that can be used for the present invention generally has the structure:

[0021] [Chem.]

[0022] (wherein R 1 , R 2 , and R 3 are independently selected from the group consisting of hydrogen or a linear alkanoyl having 2 to 10 carbon atoms) contains repeating units of. For cellulose esters, the substitution level is usually expressed as the degree of substitution (DS), which is the average number of non-OH substituents per anhydroglucose unit (AGU). Generally, conventional cellulose contains three hydroxyl groups in each AGU unit that can be substituted; thus, the DS can have a value between 0 and 3. However, low molecular weight cellulose mixed esters can have a total degree of substitution slightly higher than 3 due to the contribution of end groups. Natural cellulose is a large polysaccharide having a degree of polymerization of 250 to 5,000 even after pulping and purification, and thus the premise that the maximum DS is 3.0 is approximately correct. However, as the degree of polymerization decreases, as in the case of low molecular weight cellulose mixed esters, the end groups of the polysaccharide backbone become relatively more significant, resulting in a DS that can be in the range exceeding 3.0. Low molecular weight cellulose mixed esters are discussed in more detail below. Since the DS is a statistical average value, a value of 1 does not mean that all AGUs have a single substituent. In some cases, unsubstituted anhydroglucose units are present, some may have two, and some may have three substituents, and usually this value is non-integer. The total DS is defined as the average number of all substituents per anhydroglucose unit. The degree of substitution per AGU may also refer to a specific substituent such as hydroxyl, acetyl, butyryl, or propionyl, for example.

[0023]

[0020] In some embodiments, the cellulose ester used may be a cellulose triester or a secondary cellulose ester. Examples of cellulose triesters include, but are not limited to, cellulose triacetate, cellulose tripropionate, or cellulose tributyrate. Examples of secondary cellulose esters include cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate.

[0024]

[0021] In one embodiment of the present invention, the cellulose ester can be selected from cellulose acetate (CA), cellulose propionate (CP), cellulose butyrate (CB), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose propionate butyrate (CPB), cellulose acetate isobutyrate (CAIB), etc., or a combination thereof. Examples of such cellulose esters are described in U.S. Pat. Nos. 1,698,049; 1,683,347; 1,880,808; 1,880,560; 1,984,147; 2,129,052; and 3,617,201 (all of which are incorporated herein by reference to the extent not inconsistent with the description herein). In one embodiment, the cellulose ester is CAP.

[0025]

[0022] 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 tripropionate (CTP), or cellulose tributyrate (CTB), but not from cellulose acetate (CA).

[0026]

[0023] In some embodiments of the present invention, the cellulose ester has at least two anhydroglucose rings and may have between at least 50 and 5,000 or less anhydroglucose rings. The number of anhydroglucose units per molecule is defined as the degree of polymerization (DP) of the cellulose ester. In some embodiments, the cellulose ester has an inherent viscosity (IV) of about 0.2 to about 3.0 deciliters / gram, or about 0.5 to about 1.8 deciliters / gram, or about 1 to about 1.5 deciliters / gram, as measured at a temperature of 25 °C for a 0.25 gram sample in 100 mL of a 60 / 40 solution by weight of phenol / tetrachloroethane. Examples of cellulose esters include, but are not limited to, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose propionate butyrate, and the like. In some embodiments, the cellulose ester useful in the present invention may have a DS / AGU of about 2 to about 2.99, and the substituted esters may include acetyl, propionyl, and butyryl, or any combination thereof. In other embodiments of the present invention, the total DS / AGU ranges from about 2 to about 2.99, the DS / AGU of acetyl ranges from about 0 to 2.2, and the remainder of the ester groups includes propionyl, butyryl, or a combination thereof.

[0027]

[0024] In other embodiments of the present invention, the total DS / AGU ranges from about 2 to about 2.99, the DS / AGU of acetyl ranges from about 0 to about 1.2, and the remainder of the ester groups includes propionyl, butyryl, or a combination thereof. In other embodiments of the present invention, the total DS / AGU ranges from about 2 to about 2.99, the DS / AGU of acetyl ranges from about 0 to 0.5, and the remainder of the ester groups includes propionyl, butyryl, or a combination thereof.

[0028]

[0025] The cellulose ester can be produced by any method known in the art. Examples of methods for producing cellulose esters are taught in Kirk-Othmer, Encyclopedia of Chemical Technology, 5th edition, vol. 5, Wiley-Interscience, New York (2004), pp. 394-444. Cellulose, which is the starting material for producing cellulose esters, can be obtained from different grades and sources, among others, cotton linter, softwood pulp, hardwood pulp, corn fiber, and other agricultural raw materials, and bacterial cellulose.

[0029]

[0026] One method for producing cellulose esters 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, hydrolysis of the ester is carried out by adding a water-acid mixture to the cellulose triester, which can then be filtered to remove gel particles or fibers. Next, water is added to the mixture to precipitate the cellulose ester. The cellulose ester can then be washed with water to remove reaction by-products and then dehydrated and dried.

[0030]

[0027] The cellulose triester to be hydrolyzed may have three substituents independently selected from alkanoyl groups having 2 to 10 carbon atoms. Examples of cellulose triesters include cellulose triacetate, cellulose tripropionate, and cellulose tributyrate, or mixed triesters of cellulose such as cellulose acetate propionate and cellulose acetate butyrate. These cellulose esters can be 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 a carboxylic acid and an anhydride in the presence of a catalyst such as H2SO4. Cellulose triesters can also be produced by the homogeneous acylation of cellulose dissolved in a suitable solvent such as LiCl / DMAc or LiCl / NMP.

[0031]

[0028] Those skilled in the art will understand that the commercial term for cellulose triester also includes cellulose esters that are not completely substituted by acyl groups. For example, cellulose triacetate commercially available from Eastman Chemical Company, Kingsport, TN, USA, typically has a DS of about 2.85 to about 2.99.

[0032]

[0029] After esterifying cellulose to a triester, a part of the acyl substituents can be removed by hydrolysis or alcoholysis to give a secondary cellulose ester. As described above, depending on the specific method used, the distribution of acyl substituents can be random or non-random. Secondary cellulose esters can also be 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. All of these methods produce cellulose esters useful in the present invention.

[0033]

[0030] In one aspect, the secondary cellulose ester useful in the present invention has an absolute weight average molecular weight (Mw) of about 5,000 to about 400,000 as measured by gel permeation chromatography (GPC) in accordance with ASTM-D6474. To calculate the value (Mw) of the absolute weight average molecular weight for CE, the following method is used. The solvent is THF stabilized with a BHT preservative. The apparatus for the THF / cellulose ester procedure consists of the following Agilent 1200 series components: a degasser, an isocratic pump, an autosampler, a column oven, a UV / Vis detector, and a refractive index detector. The test temperature is 30 °C and the flow rate is 1.0 mL / min. Prepare a sample solution of 25 mg of cellulose ester in 10 mL of THF with a BHT preservative and a 10 μL toluene flow rate marker. The injection volume is 50 μL. The column set is 5 μm-PLgel, Guard+Mixed C+Oligopore from Polymer Laboratories. Detection is by refractive index. The calibration standards are monodisperse polystyrene standard samples from Polymer Laboratories, Mw = 580 to 3,220,000. The universal calibration parameters are as follows: PS (K = 0.0001280 and a = 0.7120) and CE (K = 0.00007572 and a = 0.8424). The above universal calibration parameters are determined by light scattering and viscometer to obtain the accurate weight average molecular weight. In a further aspect, Mw is about 15,000 to about 300,000. In a further aspect, Mw is in the range of about 10,000 to about 250,000; about 15,000 to about 200,000; about 20,000 to about 150,000; about 50,000 to about 150,000; or about 70,000 to about 120,000.

[0034]

[0031] In some embodiments of the present invention, the polymer-based resin comprises a cellulose ester having an absolute weight average molecular weight in the range of about 40,000 Da to about 200,000 Da, as measured according to ASTM-D5296 using tetrahydrofuran as a solvent and a flow rate of 1 mL / min. In some embodiments, the cellulose ester has an absolute weight average molecular weight in the range of about 50,000 Da to about 200,000 Da, or 50,000 Da to about 170,000 Da, or 50,000 Da to about 120,000 Da, or 50,000 Da to about 90,000 Da, or 60,000 Da to about 200,000 Da, or 60,000 Da to about 170,000 Da, or 60,000 Da to about 120,000 Da, or 60,000 Da to about 90,000 Da, or 90,000 Da to about 170,000 Da, or 90,000 Da to about 120,000 Da, or 120,000 Da to about 170,000 Da, or 120,000 Da to about 200,000 Da, as measured according to ASTM-D5296 using tetrahydrofuran as a solvent and a flow rate of 1 mL / min.

[0035]

[0032] The most common commercial secondary cellulose esters are produced by first subjecting cellulose to acid-catalyzed heterogeneous acylation to form a cellulose triester. After obtaining a homogeneous solution of the cellulose triester in the corresponding carboxylic acid, the cellulose triester is then hydrolyzed until the desired degree of substitution is obtained. After isolation, a random secondary cellulose ester is obtained. That is, the relative degree of substitution (RDS) at each hydroxyl is approximately equal.

[0036]

[0033] Some examples of cellulose esters that may be useful in the present invention can be manufactured using techniques known in the art and obtained from Eastman Chemical Company, Kingsport, TN, USA, such as Eastman® cellulose acetate propionate CAP482-20, Eastman® cellulose acetate propionate CAP141-20, Eastman® cellulose acetate butyrate CAB381-20, cellulose acetate butyrate CAB171-15, and Eastman® cellulose acetate CA398-30.

[0037]

[0034] In some embodiments, the cellulose esters used in the present invention may also contain chemical functional groups, which are described herein as either derivatized, modified, or functionalized cellulose esters. Functionalized cellulose esters can be produced by reacting the free hydroxyl groups of the cellulose ester with a bifunctional reactant having one linking group for grafting to the cellulose ester and one functional group for imparting a new chemical group to the cellulose ester. Examples of such bifunctional reactants include succinic anhydride, which is linked by an ester bond to provide an acid functional group; mercaptopropyltrimethoxysilane, which is linked by an alkoxysilane bond to provide a mercapto functional group; and isocyanatoethyl methacrylate, which is linked by a urethane bond to provide a methacrylate functional group.

[0038]

[0035] In one embodiment of the present invention, the functionalized cellulose ester is produced by reacting the free hydroxyl groups of the cellulose ester with a bifunctional reactant that produces a cellulose ester having at least one functional group selected from the group consisting of unsaturated (double bond), carboxylic acid, acetoacetate, acetoacetate imide, mercapto, melamine, and long-chain alkyl chains.

[0039]

[0036] Bifunctional reactants for producing cellulose esters containing unsaturated (double bond) functional groups are described in U.S. Pat. Nos. 4,839,230; 5,741,901; 5,871,573; 5,981,738; 4,147,603; 4,758,645; and 4,861,629 (all of which are incorporated herein by reference to the extent not inconsistent with the description herein). In one aspect, a cellulose ester containing unsaturation is produced by reacting a cellulose ester containing residual hydroxyl groups with an acrylic compound and m-isopropenyl-α,α'-dimethylbenzyl isocyanate. The grafted cellulose ester is a urethane-containing product having pendant (meth)acrylate and α-methylstyrene groups. In other aspects, a cellulose ester containing unsaturation is produced by reacting maleic anhydride with a cellulose ester in the presence of a catalyst of an alkaline earth metal or ammonium salt of a lower alkyl monocarboxylic acid and at least one saturated monocarboxylic acid having 2 to 4 carbon atoms. In other aspects, a cellulose ester containing unsaturation is produced from the reaction product of (a) at least one cellulose polymer having isocyanate-reactive hydroxyl functional groups and (b) at least one hydroxyl-reactive poly(α,β-ethylenically unsaturated) isocyanate.

[0040]

[0037] Bifunctional reactants for producing cellulose esters containing carboxylic acid functional groups are described in U.S. Pat. Nos. 5,384,163; 5,723,151; and 4,758,645 (all of which are incorporated herein by reference to the extent not inconsistent with the description herein). In one aspect, 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, thereby obtaining a cellulose derivative having a double bond functional group. In another aspect, a cellulose ester containing a carboxylic acid functional group has a first and a second residue, the first residue being a residue of a cyclic dicarboxylic anhydride, and the second residue being a residue of a lipophilic monocarboxylic acid and / or a residue of a hydrophilic monocarboxylic acid. In yet another aspect, a cellulose ester containing a carboxylic acid functional group is cellulose acetate phthalate, which can be produced by reacting cellulose acetate with phthalic anhydride.

[0041]

[0038] Bifunctional reactants for producing cellulose esters containing acetoacetate functional groups are described in U.S. Pat. No. 5,292,877 (incorporated herein by reference to the extent not inconsistent with the description herein). In one aspect, a cellulose ester containing an acetoacetate functional group is produced by contacting (i) cellulose; (ii) diketene, alkyl acetoacetate, 2,2,6-trimethyl-4H-1,3-dioxin-4-one, or a mixture thereof; and (iii) lithium chloride with a solubilizing amount of a solvent system comprising a carboxamide selected from the group consisting of 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, or a mixture thereof.

[0042]

[0039] The bifunctional reactants for producing cellulose esters containing acetoacetate imide functional groups are described in U.S. Patent 6,369,214 (incorporated herein by reference to the extent not inconsistent with the description herein). Cellulose esters containing acetoacetate imide functional groups are reaction products of a cellulose ester, and at least one acetoacetyl group, and an amine-functional compound containing at least one primary amine.

[0043]

[0040] The bifunctional reactants for producing cellulose esters containing mercapto functional groups are described in U.S. Patent 5,082,914 (incorporated herein by reference to the extent not inconsistent with the description herein). In one aspect of the present invention, a silicon-containing thiol component that is commercially available or can be produced by procedures known in the art is grafted onto the cellulose ester. 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.

[0044]

[0041] The bifunctional reactants for producing cellulose esters containing melamine functional groups are described in U.S. Patent 5,182,379 (incorporated herein by reference to the extent not inconsistent with the description herein). In one aspect, cellulose esters containing melamine functional groups are 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 backbone of the anhydrous glucose ring of the cellulose ester. In one aspect, the melamine compound is selected from the group consisting of methylol ethers of melamine and aminoplast resins.

[0045]

[0042] Bifunctional reactants for producing cellulose esters containing long-chain alkyl chain functional groups are described in U.S. Patent 5,750,677 (incorporated herein by reference to the extent not inconsistent with the description herein). In one embodiment, a cellulose ester containing a long-chain alkyl chain functional group is produced by reacting cellulose in a carboxamide diluent or a urea-based diluent with an acylating agent using a titanium-containing species. The cellulose ester containing a long-chain alkyl chain functional group can be selected from the group consisting of cellulose acetate hexanoate, cellulose acetate nonanoate, cellulose acetate laurate, cellulose palmitate, cellulose acetate stearate, cellulose nonanoate, cellulose hexanoate, cellulose hexanoate propionate, and cellulose nonanoate propionate.

[0046]

[0043] In some embodiments of the present invention, the impact modifier can be any material that has been found to increase the impact strength of the cellulose ester composition. In one embodiment, the impact modifier can be any polymeric material classified as an elastomer having a glass transition temperature (Tg) lower than room temperature. The Tg can be measured, for example, in accordance with ASTM-D3418 using a TA2100 thermal analyzer at a scanning rate of 20 °C / min. Several classes of impact modifiers meet this description.

[0047]

[0044] In one aspect, the impact modifier can be selected from the class of materials known as modified polyolefins. In this class, olefins are copolymerized with additional monomers that limit the crystallization of the polymer, increasing the amount of chains having a Tg lower than room temperature and decreasing the elastic modulus to less than 500 MPa. Examples of modified olefins include EMA (examples include Elvaloy 4051, Lotader 3410, and Lotader 8900), EBA, EVA (examples include Levamelt 500, Levamelt 600, Levamelt 700, Levamelt 800, Elvax 40W, Evatane 28-40, Evatane 40-55, Evatane 18-150, Bynel E418, and Bynel 3101), EEA, EPDM (example includes Royaltuf 498), and EPR.

[0048]

[0045] In one class of these aspects, the impact modifier is 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 (TPE). Examples of block copolymers of this class include styrenic materials such as SBS, SEBS, and SIS (examples include Kraton G1657MS, Kraton FG1901G, and Kraton FG1924G); thermoplastic urethane (TPU) (examples include Elastolan 1170Z, Estane 2355, Estane ALR-CL87A, and Estane ALR-72A); polyester-ether copolymers (examples include Ecdel 9966 and Hytrel 3078), or polyamide-ether copolymers (example includes Pebax 5533).

[0049]

[0046] In one aspect, the impact modifier can be selected from the class of emulsion-forming materials known as core-shell impact modifiers. In one aspect, the impact modifier is an MBS core-shell impact modifier such as methacrylate-butadiene-styrene having a core formed of a butadiene-styrene copolymer and a shell formed of a methyl methacrylate-styrene copolymer. In other aspects, the impact modifier is an acrylic core-shell impact modifier having a core formed of an acrylic polymer such as butyl acrylate or styrene butyl acrylate, and a shell formed of a polymethyl methacrylate or styrene methyl methacrylate copolymer.

[0050]

[0047] In one aspect of the present invention, the core-shell impact modifier (A) a core comprising from about 70 to about 85 parts of units derived from at least one vinyl aromatic monomer of from about 15 to about 35% by weight and units derived from at least one diolefin monomer of from about 65 to about 85% by weight; (B) an internal graft stage comprising from about 8 to about 14 parts of at least one vinyl aromatic monomer or at least one C1-C4 alkyl methacrylate monomer; (C) an intermediate sealant stage comprising from about 0.1 to about 5 parts of at least one monomer selected from C1-C8 alkyl acrylates or polyunsaturated crosslinking agents; and (D) an outer shell comprising from about 10 to about 16 parts of at least one C1-C4 alkyl (meth)acrylate monomer or at least one vinyl aromatic monomer; which may be an MBS impact modifier.

[0051]

[0048] In some embodiments, the MBS impact modifier can include a polymer or copolymer of butadiene in an amount of 10 to 70% by weight, and first, a graft polymer composition including methyl (meth)acrylate and a crosslinking agent, second, styrene, and third, a graft including methyl (meth)acrylate and optionally a crosslinking agent.

[0052]

[0049] Suitable monomers for polymerizing with a conjugated diolefin, preferably butadiene, include alkenyl aromatic compounds, preferably vinyl aromatic compounds such as styrene, divinylbenzene, α-methylstyrene, vinyltoluene, hydrogenated styrene; lower (C2-C12) alkyl acrylates such as ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, 3-methylbutyl acrylate, amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate; lower (C2-C 12 ) alkyl (meth)acrylates; acrylonitrile; olefins; etc.; or combinations of any of the above.

[0053]

[0050] Suitable crosslinking agents include divinylbenzene; di(meth)acrylate; diacrylate such as diacrylate of mono-, di-, or polyethylene glycol; their (meth)acrylates; divinyl sulfide; divinyl ether; vinyl acrylate; vinyl (meth)acrylate; trivinylbenzene; trimethylolpropane; tri(meth)acrylate; triallyl cyanurate and triallyl isocyanurate.

[0054]

[0051] In one aspect, the MBS core-shell type impact modifier can include a copolymer of butadiene and styrene, most preferably a terpolymer of butadiene, styrene, and divinylbenzene. The relative amounts of the monomers constituting the copolymer substrate may vary, but based on 100 parts by weight in total of butadiene, styrene, and divinylbenzene, the butadiene component usually constitutes about 30 to 100 parts by weight, the styrene component constitutes 0 to about 70 parts by weight, and the divinylbenzene component constitutes 0 to about 5 parts by weight. In one aspect, the copolymer substrate can include, 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.

[0055]

[0052] Examples of methacrylate-butadiene-styrene core-shell polymers are those described in U.S. Patents US-4,446,585, US-5,534,594, and US-6,331,580, but are not limited thereto. The MBS core-shell type impact modifier 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.

[0056]

[0053] In one aspect 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 elastomeric phase polymerized from a monomer system containing about 75 to 99.8% by weight of (C1-C6) alkyl acrylate, 0.1 to 5% by weight of a crosslinkable monomer, and 0.1 to 5% by weight of a graft-linkable monomer, and about 75 to 5% by weight of a final rigid thermoplastic phase polymerized in the presence of such an elastomeric phase and containing no epoxy groups.

[0057]

[0054] Examples of useful acrylates include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc. In some embodiments, the acrylates are n-butyl acrylate and ethyl acrylate.

[0058]

[0055] The graft-linkable monomer is defined as a polyethylenically unsaturated monomer having both a highly reactive double bond and a less reactive double bond, wherein the highly reactive double bond polymerizes during the polymerization of the first-stage monomer, leaving residual double bonds for polymerization during the next-stage polymerization, thereby having a tendency to graft-bond the second-stage polymer to the first-stage polymer. In some embodiments, the graft-linkable monomers are allyl methacrylate, allyl acrylate, and diallyl maleate. In one embodiment, 0.05 to 3% of the graft-linkable monomer is present based on the first-stage monomer system. Also preferably, a crosslinkable monomer is generally present in an amount of about 0.05 to 3 wt% based on the first-stage monomer system, which is defined as a polyethylenically unsaturated monomer having at least two double bonds of approximately equal reactivity so as to cause crosslinking in the first-stage polymerization. Examples of representative crosslinkable monomers include 1,3-butylene diacrylate, 1,3-butylene dimethacrylate, divinylbenzene, etc.

[0059]

[0056] The "epoxy functional group" means an epoxy unit pendant from the final-stage polymer. In some embodiments, the epoxy functional group is introduced into the final-stage polymer by using an epoxy-containing monomer such as glycidyl acrylate or glycidyl methacrylate in the final-stage monomer mixture.

[0060] Examples of acrylic core-shell polymers are those described in U.S. Patents US-3,448,173, US-3,655,825, and US-3,853,968, but are not limited thereto. Examples of suitable acrylic impact modifiers are Kane Ace ECO100 from Kaneka, Durastrength from Arkema, Elvaloy and Elvaloy HP from DuPont, Metablen W from Mitsubishi Chemical, and Paraloid from Dow.

[0061]

[0058] 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.

[0062]

[0059] In one class of this embodiment, the impact modifier is a silicone-acrylic core-shell type impact modifier having a core formed from a silicone-acrylic rubber and a shell formed from a PMMA copolymer or a methyl methacrylate-styrene copolymer. An example of a silicone-acrylic core-shell type impact modifier is Metablen S from Mitsubishi Chemical Company.

[0063]

[0060] In one embodiment, the impact modifier has a relatively neutral pH (e.g., a pH between 6 and 8, preferably between 6.5 and 7.5). This is thought to help prevent the cellulose ester from decomposing during melt processing of the composition.

[0064]

[0061] In one particular useful embodiment, the composition of the cellulose ester and the impact modifier is transparent and has a light transmittance of at least 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%, as measured using a 3.2 mm plaque after injection molding at a barrel set point of 249 °C and a residence time of 5 minutes in accordance with ASTM-D1003. In some embodiments, the polymer-based resin has a light transmittance of 70% - 95%, or 75% - 95%, or 80% - 95%, or 85% - 95%, or 70% - 90%, or 75% - 90%, or 80% - 90%, or 85% - 90%, as measured using a 3.2 mm plaque after injection molding at a barrel set point of 249 °C and a residence time of 5 minutes in accordance with ASTM-D1003. In one class of this embodiment, the cellulose ester composition containing the impact modifier has a haze percentage of less than 10%. In some embodiments, the cellulose ester composition containing the impact modifier has a haze percentage of less than 8%, or less than 6%, or less than 5%.

[0065]

[0062] In other embodiments, the refractive index (RI) of the impact modifier is close to that of the cellulose ester, sufficient to provide a composition with high transmittance and low haze. In one embodiment, the acrylic impact modifier has an RI close to that of the cellulose ester of about 1.46 - 1.50, providing a transparent composition. In some embodiments, the impact modifier component 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 impact modifier), and the immiscible blend has a transmittance percentage of at least 75% and a haze of 10% or less, more preferably 5% or less.

[0066]

[0063] In one embodiment, the impact modifier may be either a non-reactive impact modifier, or a reactive impact modifier, or a combination of both. The impact modifier used can also improve the mechanical and physical properties of the cellulose ester composition.

[0067]

[0064] In one aspect, when using a non-reactive impact modifier, the impact modifier includes a first polymer chain segment that is more compatible, chemically or physically, with the cellulose ester than other polymer chain segments. In one aspect, the first segment includes polar functional groups such as (but not limited to) polar functional groups that confer compatibility with the cellulose ester, such as ethers, esters, amides, alcohols, amines, ketones, and acetals. Compatibility is defined by the interaction of the first polymer chain segment, which is preferential with respect to the second segment, with the cellulose ester polymer, and can mean molecular-scale or micro-scale interactions. The first segment can consist of oligomers or polymers of the following: cellulose esters; cellulose ethers; polyoxyalkylenes, such as polyoxyethylene, polyoxypropylene, polyoxybutylene; polyglycols, such as polyethylene glycol, polypropylene glycol, polybutylene glycol; polyesters, such as polycaprolactone, polylactic acid, aliphatic polyesters, aliphatic-aromatic copolyesters; polyacrylates and polymethacrylates; polyacetals; polyvinylpyrrolidone; polyethylene vinyl acetate; polyvinyl acetate; and polyvinyl alcohol. In one aspect, the first segment is polyethylene vinyl acetate; polyoxyethylene, or polyvinyl alcohol.

[0068]

[0065] In some aspects, the second segment can be a saturated or unsaturated hydrocarbon group, or can include both saturated and unsaturated hydrocarbon groups. The second segment can be an oligomer or a polymer. In one aspect of the invention, the second segment of the non-reactive impact modifier is selected from the group consisting of polyolefins, polydienes, 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 a styrene / butadiene copolymer.

[0069]

[0066] The first and second segments of the non-reactive impact modifier may have a diblock, triblock, branched, or comb structure. The molecular weight of the non-reactive impact modifier may range from about 300 to about 20,000, or from about 500 to about 10,000, or from about 1,000 to about 5,000. The segment ratio of the non-reactive impact modifier may range from about 15 to about 85% polar first segment / about 15 to about 85% non-polar second segment.

[0070]

[0067] 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 ethoxylated with ethylene oxide 12 ~C 14 natural linear alcohols. C 11 ~C 15 ~C 12 secondary alcohol ethoxylates can be obtained from The Dow Chemical Company as Dow Tergitol® 15S. Polyoxyethylene cetyl ether and polyoxyethylene stearyl ether can be obtained from ICI Surfactants as products of the Brij® series. C ethoxylated with ethylene oxide 14Natural linear alcohols are available from Hoechst Celanese as products of the Genapol® series. Examples of ethoxylated alkylphenols include octylphenoxypoly(ethyleneoxy)ethanol and nonylphenoxypoly(ethyleneoxy)ethanol. Octylphenoxypoly(ethyleneoxy)ethanol is available from Rhodia as products of the Igepal® CA series, and nonylphenoxypoly(ethyleneoxy)ethanol is available from Rhodia as products of the Igepal CO series or from Dow Chemical Company as Tergitol® NP. Examples of ethoxylated fatty acids include polyethylene glycol monostearate or monolaurate, which are available from Henkel as products of the Nopalcol® series. Block polymers of propylene oxide and ethylene oxide are available from BASF as products of the Pluronic® series. Polyglycerol esters are available from Stepan as products of the Drewpol® series. Polysaccharide esters are available from Henkel as products of the Glucopon® series (which are alkyl polyglucosides). Sorbitan esters are available from ICI as products of the Tween® series.

[0071]

[0068] In another aspect of the present invention, the non-reactive impact modifier can be synthesized in situ in the cellulose ester composition by reacting a cellulose ester-compatible compound. These compounds can be, for example, telechelic oligomers defined as prepolymers that can initiate further polymerization or other reactions by their reactive end groups. In one aspect of the present invention, these in situ impact modifiers can have a higher molecular weight of from about 10,000 to about 1,000,000.

[0072]

[0069] In another aspect of the present invention, the impact modifier may be reactive. The reactive impact modifier can include a polymer or oligomer compatible with one component of the composition and a functional group capable of reacting with another component of the composition. In some aspects, there are two types of reactive impact modifiers that can be used. The first reactive impact modifier has a hydrocarbon chain compatible with the cellulose ester and also has a functional group capable of reacting with the cellulose ester. Such functional groups include, but are not limited to, carboxylic acids, anhydrides, acid chlorides, epoxides, and isocyanates. Specific examples of this type of reactive impact modifier include long-chain fatty acids such as stearic acid (octadecanoic acid); long-chain fatty acid chlorides such as stearoyl chloride (octadecanoyl chloride); long-chain fatty acid anhydrides such as stearic anhydride (octadecanoic anhydride); epoxidized oil esters; styrene maleic anhydride copolymers; maleic anhydride grafted polypropylene; copolymers of maleic anhydride and olefins and / or acrylic esters such as terpolymers of ethylene, acrylic esters, and maleic anhydride; and copolymers of glycidyl methacrylate and olefins and / or acrylic esters such as terpolymers of ethylene, acrylic esters, and glycidyl methacrylate, but are not limited thereto.

[0073]

[0070] The reactive impact modifier can be obtained as the SMA® 3000 styrene maleic anhydride copolymer from Sartomer / Cray Valley, the Eastman G-3015® maleic anhydride grafted polypropylene from Eastman Chemical Company, the Epolene® E-43 maleic anhydride grafted polypropylene obtained from Westlake Chemical, the Lotader® MAH 8200 random terpolymer of ethylene, acrylate ester, and maleic anhydride obtained from Arkema, the Lotader® GMA AX8900 random terpolymer of ethylene, acrylate ester, and glycidyl methacrylate, and the Lotader® GMA AX8840 random terpolymer of ethylene, acrylate ester, and glycidyl methacrylate.

[0074]

[0071] The modified polyolefin impact modifier can be obtained as Lotader, Fusabond, Elvloy PTW, Lotryl, Elvaloy AC, InterLoy.

[0072] The second type of reactive impact modifier has a polar chain compatible with the cellulose ester and also has a functional group capable of reacting with the cellulose ester. Examples of these types of reactive impact modifiers include cellulose esters or polyethylene glycols having an olefin functional group or a thiol functional group. Examples of the reactive polyethylene glycol impact modifier having an olefin functional group include, but are not limited to, polyethylene glycol allyl ether and polyethylene glycol acrylate. An example of the reactive polyethylene glycol impact modifier having a thiol functional group is polyethylene glycol thiol. An example of the reactive cellulose ester impact modifier is mercaptoacetate cellulose ester.

[0075]

[0073] In some embodiments of the present invention, the amount of the impact modifier in the cellulose ester composition is about 1 wt% to about 30 wt%, or about 1 wt% to about 15 wt%, or about 5 wt% to about 10 wt%, or about 10 wt% to about 30 wt%, or about 15 wt% to about 30 wt% based on the weight of the cellulose ester composition.

[0076]

[0074] 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 wt% based on the total cellulose ester composition. Suitable examples of the additional polymer component include nylon; polyester; polyamide; polystyrene; other cellulose esters, cellulose ethers; polystyrene copolymers; styrene acrylonitrile copolymers; polyolefins; polyurethanes; acrylonitrile butadiene styrene copolymers; poly(methyl methacrylate); acrylic copolymers; poly(ether-imide); polyphenylene oxide; polyvinyl chloride; polyphenylene sulfide; polyphenylene sulfide / sulfone; poly(ester-carbonate); polycarbonate; polysulfone; polylactic acid; polybutylene succinate; polysulfone ether; and poly(ether-ketone) of aromatic dihydroxy compounds; or mixtures of any of the above polymers, but are not limited thereto. The blend can be formed by conventional processing techniques known in the art such as melt blending or solution blending.

[0077]

[0075] In one aspect of the present invention, a plasticizer can be included in the composition. The plasticizer used in the present invention can be any known in the art that can lower the glass transition temperature and / or the melt viscosity of the cellulose ester to improve the melt processing characteristics. The plasticizer can be any plasticizer suitable for use with the cellulose ester. The level of the plasticizer should be lower than the standard (or normal) plasticizer level for the cellulose ester; the composition should have a higher Tg (or HDT), good toughness, and good fluidity than a fully plasticized cellulose ester composition. In some aspects, the plasticizer is present in an amount that does not substantially reduce the Tg (or HDT) of the cellulose ester composition compared to a similar composition without the plasticizer. In some aspects, the Tg (or HDT) 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.

[0078]

[0076] The plasticizer can be either a monomeric structure or a polymeric structure. In one aspect, 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, polymeric polyester plasticizers, polyglycol diester plasticizers, polyester resin plasticizers, aromatic diester plasticizers, aromatic triester plasticizers, aliphatic diester plasticizers, carbonate plasticizers, epoxidized ester plasticizers, epoxidized oil plasticizers, benzoate plasticizers, polyol benzoate plasticizers, adipate plasticizers, phthalate plasticizers, glycolic acid ester plasticizers, citrate ester plasticizers, hydroxyl-functional plasticizers, or solid amorphous resin plasticizers.

[0079]

[0077] In one aspect 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.

[0080]

[0078] In another aspect of the present invention, the plasticizer can be selected from at least one of the following esters: (i) an acid residue containing one or more residues of phthalic acid, adipic acid, trimellitic acid, succinic acid, benzoic acid, azelaic acid, terephthalic acid, isophthalic acid, butyric acid, glutaric acid, citric acid, or phosphoric acid; and (ii) an alcohol residue containing one or more residues of an aliphatic, alicyclic, or aromatic alcohol containing about 20 or fewer carbon atoms.

[0081]

[0079] In another aspect of the present invention, the plasticizer can be selected from at least one of the following esters: (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 an aliphatic, alicyclic, or aromatic alcohol containing about 20 or fewer carbon atoms.

[0082]

[0080] In another aspect of the present invention, the plasticizer may contain an alcohol residue, and the alcohol residue is at least one selected from the following: stearyl alcohol, lauryl alcohol, phenol, benzyl alcohol, hydroquinone, catechol, resorcinol, ethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, and diethylene glycol.

[0083]

[0081] In another aspect of the present invention, the plasticizer can be selected from at least one of the following: benzoate, phthalate, phosphate, arylene-bis(diaryl phosphate), and isophthalate. In another aspect, the plasticizer contains diethylene glycol dibenzoate (abbreviated herein as "DEGDB").

[0084]

[0082] In another aspect of the present invention, the plasticizer is the following: C2-C 10 a diacid residue, such as a residue 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 of aliphatic polyesters containing a diol residue.

[0085]

[0083] In another aspect, the plasticizer is the following C2-C 10 diol: It may contain a diol residue which is at least one residue of ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,5-pentylene glycol, triethylene glycol, and tetraethylene glycol.

[0086]

[0084] In another aspect of the present invention, examples of the plasticizer include polyglycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol. These may range from low molecular weight dimers and trimers to high molecular weight oligomers and polymers. In one aspect, the molecular weight of the polyglycol may range from about 200 to about 2000.

[0087]

[0085] In another aspect 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).

[0088]

[0086] In another aspect of the present invention, the plasticizer is (A) about 5 to about 95% by weight of a C2 - C 12 carbohydrate organic ester (the carbohydrate contains about 1 to about 3 monosaccharide units); and (B) about 5 to about 95% by weight of one or more of a C2 - C 12 polyol ester (the polyol is derived from a C5 or C6 carbohydrate). In one aspect, the polyol ester does not contain or is free of one or more polyol acetates.

[0089]

[0087] In another aspect, the plasticizer contains at least one carbohydrate ester, and the carbohydrate moiety 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.

[0090]

[0088] In another aspect of the present invention, the plasticizer includes at least one type of carbohydrate ester, and the carbohydrate portion of the carbohydrate ester includes one or more of α-glucose pentaacetate, β-glucose pentaacetate, α-glucose pentapropionate, β-glucose pentapropionate, α-glucose pentabutyrate, and β-glucose pentabutyrate.

[0091]

[0089] In another aspect, the plasticizer includes at least one type of carbohydrate ester, and the carbohydrate portion of the carbohydrate ester includes an α-anomer, a β-anomer, or a mixture thereof.

[0092]

[0090] In another aspect, the plasticizer can be selected from at least one of the following: propylene glycol dibenzoate, glyceryl tribenzoate, diethylene glycol dibenzoate, triethylene glycol dibenzoate, dipropylene glycol dibenzoate, and polyethylene glycol dibenzoate.

[0093]

[0091] In another aspect of the present invention, the plasticizer may be a solid amorphous resin. These resins may contain a small amount of aromatic or polar functional groups and can reduce the melt viscosity of the cellulose ester. In one aspect of the present invention, the plasticizer may be, for example, rosin; hydrogenated rosin; stabilized rosin, and their monofunctional alcohol esters or polyol esters; modified rosins such as maleic acid and phenol-modified rosin and their esters (but not limited to these); terpene resins; phenol-modified terpene resins; coumarin-indene resins; phenol resins; alkylphenol-acetylene resins; and phenol-formaldehyde resins; and other solid amorphous compounds (resins).

[0094]

[0092] In another aspect of the present invention, the plasticizer is triacetin, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, triethyl citrate, acetyltrimethyl citrate, acetyltriethyl citrate, acetyltributyl citrate, tributyl-o-acetyl citrate, dibutyl phthalate, diaryl phthalate, diethyl phthalate, dimethyl phthalate, di-2-methoxyethyl phthalate, dioctyl phthalate, dioctyl adipate, dibutyl tartrate, ethyl o-benzoylbenzoate, ethyl phthalylethyl glycolate, methyl phthalylethyl glycolate, n-ethyltoluene sulfonamide, o-cresyl p-toluenesulfonate, aromatic diol, substituted aromatic diol, aromatic ether, tripropionin, tribenzoin, polycaprolactone, glycerin, glycerin ester, diacetin, glycerol acetate benzoate, polyethylene glycol, polyethylene glycol ester, polyethylene glycol diester, di-2-ethylhexyl polyethylene glycol ester, triethylene glycol bis-2-ethylhexanoate, glycerol ester, diethylene glycol, polypropylene glycol, polyglycol diglycidyl ether, dimethyl sulfoxide, N-methylpyrrolidinone, C1 to C 20At least one plasticizer selected from the group consisting of dicarboxylic acid esters, dimethyl adipate, dibutyl maleate, dioctyl maleate, resorcinol monoacetate, catechol, catechol esters, phenols, epoxidized soybean oil, castor oil, linseed oil, epoxidized linseed oil, other vegetable oils, other seed oils, polyethylene glycol-based difunctional glycidyl ether, γ-butyrolactone, alkyl phosphate esters, aryl phosphate esters, phospholipids, eugenol, cinnamyl alcohol, camphor, methoxyhydroxyacetophenone, vanillin, ethyl vanillin, 2-phenoxyethanol, glycol ethers, glycol esters, glycol ester ethers, polyglycol ethers, polyglycol esters, ethylene glycol 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, butylated hydroxytoluene, butylated hydroxyanisole, sorbitol, xylitol, ethylenediamine, piperidine, piperazine, hexamethylenediamine, triazine, triazole, pyrrole, and any combination thereof.

[0095]

[0093] The amount of plasticizer in the cellulose ester composition may range from 0 to about 15 wt% based on the weight of the cellulose ester composition. In one embodiment, this amount may range from about 15 wt% or less based on the weight of the cellulose ester composition. In other embodiments, this amount may range from about 10 wt% or less based on the weight of the cellulose ester composition. In other embodiments, this amount may be about 5 wt% or less, or about 3 wt% or less, or less than 2 wt% based on the weight of the cellulose ester composition.

[0096]

[0094] In other embodiments of the present invention, the cellulose ester composition does not contain a plasticizer. In one embodiment, the cellulose ester composition contains a cellulose ester that is CAP and does not contain a plasticizer. In one embodiment, the cellulose ester composition contains a cellulose ester that is CAB and does not contain a plasticizer.

[0097]

[0095] In other embodiments of the present invention, the composition is melt processable. Melt processability generally refers to the ability to thermally process materials at temperatures below their decomposition temperatures to obtain uniform pellets or plastic articles. For example, the described composition can be melt extruded at a throughput of 35 pounds per hour using a screw speed of 250 rpm and a barrel temperature of 240 °C in a Werner & Pflerderer 30 mm twin screw extruder, and injection molded with a minimum molecular weight or discoloration using a barrel temperature of 240 °C and a mold temperature of 160 °F in a Toyo 110 injection molding machine. (15.9 kg) / hour and can be injection molded with a minimum molecular weight or discoloration using a barrel temperature of 240 °C and a mold temperature of 160 °F in a Toyo 110 injection molding machine. (71.1℃) of the mold temperature.

[0098]

[0096] In one embodiment of the present invention, it contains 1 to 30% by weight, or 1 to 15% by weight, or 2 to 10% by weight of an impact modifier and does not contain a plasticizer, and has a heat distortion temperature (HDT) value higher than 95 °C (measured at a stress level of 1.82 MPa after conditioning at 70 °C for 4 hours according to ASTM-D648), and a notched Izod impact strength value higher than 80 J / m (measured at 23 °C for a bar with a thickness of 3.2 mm according to ASTM-D256), and at least 15 inches at 240 °C measured using the procedure described herein. (38.1 cm) A melt-processable cellulose ester composition having a spiral flow value of is provided. In one embodiment, the cellulose ester composition has a Tg value higher than 120 °C measured at 20 °C / min according to ASTM-D3418. Unless otherwise specified, the notched Izod impact strength test was carried out at 23 °C on a molded bar after notching after conditioning at 23 °C and 50% RH for 48 hours for a bar with a thickness of 3.2 mm according to ASTM method D256.

[0099]

[0097] In another embodiment of the present invention, the composition is measured using a frequency scan between 1 rad / second and 400 rad / second according to ASTM-D4440 and has a melt viscosity at 240 °C and 400 rad / second 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% of 10,000 P (1,000 Pa·s) or less.

[0100]

[0098] In one aspect, the melt-processable cellulose ester composition contains 1 to 30 wt% or 1 to 15 wt% of an impact modifier and 0 to 15 wt% of a plasticizer, and has a Tg higher than 90 °C. In other aspects, the melt-processable cellulose ester composition contains 1 to 30 wt% or 1 to 15 wt% of an impact modifier and 0 to 10 wt% of a plasticizer, and has a Tg higher than 100 °C. In still other aspects, the melt-processable cellulose ester composition contains 1 to 10 wt% of an impact modifier and 0 to 10 wt% of a plasticizer, and has a Tg higher than 100 °C. In other aspects, the melt-processable cellulose ester composition contains 1 to 10 wt% of an impact modifier and 0 to 5 wt% of a plasticizer, and has a Tg higher than 115 °C.

[0101]

[0099] In other aspects of the present invention, the cellulose ester composition introduces an impact modifier and does not introduce a plasticizer, resulting in only a slight decrease (e.g., less than 5 °C, or less than 2 °C) and having a Tg or heat distortion temperature (HDT at 0.455 psi (3.13 kPa) equivalent to that of the base cellulose ester polymer. The impact properties of these compositions can also exceed 80 J / m (notched Izod impact strength at 23 °C).

[0102]

[0100] In some embodiments of the present invention, the polymer-based resin has a heat distortion temperature (HDT) that is higher than 90 °C or higher than 95 °C, as measured at 1.82 MPa using a 3.2 mm thick bar heated to 70 °C for 4 hours in accordance with ASTM-D648. In some embodiments, the polymer-based resin has a heat distortion temperature (HDT) of at least 95 °C, at least 100 °C, at least 105 °C, or at least 110 °C, or at least 115 °C. In some embodiments, the polymer-based resin has a heat distortion temperature (HDT) in the range of 90 °C to 140 °C, 90 °C to 130 °C, 90 °C to 120 °C, 90 °C to 110 °C, 95 °C to 140 °C, 95 °C to 130 °C, 95 °C to 120 °C, 95 °C to 110 °C, 95 °C to 105 °C, 100 °C to 140 °C, 100 °C to 130 °C, 100 °C to 120 °C, 100 °C to 110 °C, 105 °C to 140 °C, 105 °C to 130 °C, 105 °C to 120 °C, 105 °C to 115 °C, 105 °C to 110 °C, 110 °C to 140 °C, 110 °C to 130 °C, 110 °C to 125 °C, 110 °C to 120 °C, 110 °C to 115 °C, 115 °C to 140 °C, 115 °C to 130 °C, 120 °C to 140 °C, 120 °C to 130 °C, or 120 °C to 125 °C.

[0103] In some embodiments of the present invention, the polymer-based resin has a notched Izod impact strength of at least 80 J / m, or at least 90 J / m, or at least 100 J / m, or at least 110 J / m, or at least 120 J / m, or at least 130 J / m, or at least 140 J / m, or at least 150 J / m, or at least 160 J / m, or at least 170 J / m, or at least 180 J / m, or at least 190 J / m, or at least 200 J / m, as measured using a 3.2 mm thick bar conditioned at 50% relative humidity at 23 °C for 48 hours in accordance with ASTM-D256. In some embodiments, the polymer-based resin has a notched Izod impact strength in the range of about 80 J / m to about 500 J / m, about 80 J / m to about 400 J / m, about 80 J / m to about 300 J / m, about 80 J / m to about 200 J / m, about 100 J / m to about 500 J / m, about 100 J / m to about 400 J / m, about 100 J / m to about 300 J / m, about 100 J / m to about 200 J / m, about 120 J / m to about 500 J / m, about 120 J / m to about 400 J / m, about 120 J / m to about 300 J / m, about 120 J / m to about 200 J / m, about 150 J / m to about 500 J / m, about 150 J / m to about 400 J / m, about 150 J / m to about 300 J / m, about 150 J / m to about 200 J / m, about 170 J / m to about 500 J / m, about 170 J / m to about 400 J / m, about 170 J / m to about 300 J / m, about 170 J / m to about 200 J / m, 180 J / m to about 500 J / m, about 180 J / m to about 400 J / m, about 180 J / m to about 300 J / m, about 180 J / m to about 200 J / m, 190 J / m to about 500 J / m, about 190 J / m to about 400 J / m, about 190 J / m to about 300 J / m, about 190 J / m to about 200 J / m, 200 J / m to about 500 J / m, about 200 J / m to about 400 J / m, or about 200 J / m to about 300 J / m, as measured using a 3.2 mm thick bar conditioned at 50% relative humidity at 23 °C for 48 hours in accordance with ASTM-D256.

[0104]

[0102] In some embodiments of the present invention, the polymer-based resin has a flexural modulus higher than 1800 MPa as measured using a 3.2 mm thick bar at 23°C and 50% relative humidity for 48 hours in accordance with ASTM-D790. 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 as measured using a 3.2 mm thick bar at 23°C and 50% relative humidity for 48 hours in accordance with ASTM-D790. In some embodiments, the polymer-based resin has a flexural modulus of about 1800 to about 3500 MPa, about 1900 to about 3500 MPa, about 2000 to about 3500 MPa, about 2100 to about 3500 MPa, about 2200 to about 3500 MPa, about 2300 to about 3500 MPa, about 2400 to about 3500 MPa, or about 2500 to about 3500 MPa as measured using a 3.2 mm thick bar at 23°C and 50% relative humidity for 48 hours in accordance with ASTM-D790. In some embodiments, the polymer-based resin has a flexural modulus of about 1900 to about 2500 MPa, about 1900 to about 2800 MPa, or about 1900 to about 3000 MPa as measured using a 3.2 mm thick bar at 23°C and 50% relative humidity for 48 hours in accordance with ASTM-D790.

[0105]

[0103] In some embodiments of the present invention, the cellulose ester composition contains 1 wt% to 30 wt%, or 2 wt% to 15 wt% of an impact modifier based on the total weight of the cellulose ester composition, has an HDT value higher than 95°C, and a notched Izod impact strength value higher than 80 J / m, or higher than 100 J / m, or higher than 120 J / m, and has a viscosity of less than 10,000 P at 240°C and 400 rad / sec. (1,000 Pa·s) Has a viscosity of less than.

[0106]

[0104] In some embodiments of the present invention, the cellulose ester composition comprises an impact modifier in an amount of 1 wt% to 30 wt%, or 2 wt% to 15 wt% based on the total weight of the cellulose ester composition, has an HDT value higher than 95 °C, and a notched Izod impact strength value higher than 80 J / m, or higher than 100 J / m, or higher than 120 J / m, and, as measured using a 3.2 mm plaque after injection molding at a barrel set point of 249 °C and a residence time of 5 minutes in accordance with ASTM-D1003, has a light transmittance value higher than 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%.

[0107]

[0105] One problem that can occur when melt processing a cellulose ester that does not contain a plasticizer or contains a low level of plasticizer in a screw plastifying injection molding machine is that it is difficult for the screw to recover smoothly (poor screw recovery), which can result in poor material feeding and a "screeching" sound. Surprisingly, it has been found that by adding an impact modifier according to some embodiments of the present invention, these problems during injection molding can be eliminated.

[0108]

[0106] In some embodiments of the present invention, the cellulose ester composition comprises an impact modifier in an amount of 1 wt% to 30 wt%, or 2 wt% to 15 wt% based on the total weight of the cellulose ester composition, has an HDT value higher than 95 °C, and a notched Izod impact strength value higher than 80 J / m, or higher than 100 J / m, or higher than 120 J / m, and does not generate a screeching sound during injection molding at a barrel set point of 249 °C or have a screw recovery problem.

[0109] In some embodiments of the present invention, the cellulose ester composition contains 1 wt% to 30 wt%, or 2 wt% to 15 wt% of an acrylic core-shell type impact modifier based on the total weight of the cellulose ester composition, has an HDT value higher than 95°C, a notched Izod impact strength value higher than 150 J / m, does not generate a squeaking sound during injection molding at a barrel set point of 249°C, or does not have a screw recovery problem.

[0110] In other embodiments of the present invention, the cellulose ester composition further comprises at least one additive selected from the group consisting of antioxidants, heat stabilizers, release agents, antistatic agents, brightening 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.

[0111] In some embodiments, in addition to the impact modifier (discussed herein), the cellulose ester composition comprises a stabilizer selected from the group consisting of a secondary antioxidant, an acid scavenger, or a combination thereof. In some embodiments, in addition to the impact modifier (discussed herein), the cellulose ester composition comprises a secondary antioxidant in the range of about 0.1% to about 0.8% by weight, based on the total weight of the composition. In some embodiments, in addition to the impact modifier (discussed herein), the cellulose ester composition comprises an acid scavenger in the range of about 0.2% to about 2.0% by weight, based on the total weight of the composition. In one embodiment, in addition to the impact modifier (discussed herein), the cellulose ester composition comprises a secondary antioxidant in the range of about 0.1% to about 0.8% by weight and an acid scavenger in the range of 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 a salt stabilizer, for example, 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, impact modifier, and stabilizer (discussed herein), the cellulose ester composition comprises any other components in a total amount of less than 5% by weight, or less than 2% by weight, based on the total weight of the composition.

[0112]

[0110] In some embodiments, the cellulose ester composition does not contain maleic anhydride-modified EVA. In some embodiments, the cellulose ester composition does not contain a polyether ester compound. In some embodiments, the cellulose ester composition does not contain an adipic acid compound. 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 30% by weight of one or more impact modifiers, and other components in a total amount of less than 5% by weight. In some embodiments, such other components do not include a plasticizer, a polyether ester compound, or an adipic acid compound. In some embodiments, the cellulose ester composition contains a dioctyl adipate (DOA) plasticizer and does not contain other adipic acid compounds.

[0113]

[0111] In another embodiment of the present invention, a method for producing a cellulose ester composition is provided. The method includes contacting at least one cellulose ester, at least one impact modifier, and optionally at least one plasticizer. The cellulose ester, plasticizer, and impact modifier are discussed above herein. In one embodiment, the cellulose ester, impact modifier, and optional plasticizer can be mixed in any order of addition.

[0114]

[0112] In another embodiment of the present invention, there is provided a method for producing a cellulose ester composition, which includes (a) mixing at least one impact modifier, at least one cellulose ester, and optionally at least one plasticizer at a time and temperature sufficient to disperse the impact modifier to form 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 at the upper limit by the processing temperature of the impact modifier and at the lower limit by the maximum use temperature of the cellulose ester composition.

[0115]

[0113] The mixing efficiency of two or more types of viscoelastic materials may be determined by the ratio of the viscosities of the viscoelastic materials. In one aspect, for a given mixing device and shear rate range, the viscosity ratio of the dispersed phase (impact modifier) to the continuous phase (cellulose ester) must be within a defined limit in order to obtain an appropriate particle size.

[0116]

[0114] In some aspects, the mixing of the impact modifier, cellulose ester, and optional plasticizer, and any additives can be carried out by any method known in the art suitable for dispersing the impact modifier, plasticizer, and additives in the cellulose ester. Examples of mixing devices include, but are not limited to, Banbury mixers, Brabender mixers, roll mills, and extruders (single - screw or twin - screw). The shear energy during mixing is determined by the combination of the device, blade design, rotational speed (rpm), and mixing time. The shear energy must be sufficient to disperse the impact modifier throughout the cellulose ester.

[0117]

[0115] In some aspects, the cellulose ester, impact modifier, plasticizer, and additives can be mixed in any order during the process. In one aspect, the cellulose ester is premixed with the impact modifier and / or plasticizer. Next, the cellulose ester containing the impact modifier and / or plasticizer is mixed with the additives. In another aspect of the present invention, when using a reactive impact modifier, first the reactive impact modifier can be mixed with the cellulose ester, and then other components are added.

[0118]

[0116] The composition of the present invention is useful as a molded plastic part or as a solid plastic article. The present 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 spectacle frames, the handles of toothbrushes, toys, automotive trims, the handles of tools, camera parts, parts of electronic devices, parts of razors, the barrels of ink pens, disposable syringes, bottles, etc. In one aspect, the composition of the present invention is useful as plastics, films, fibers, and sheets. In one aspect, the present composition is for bottles, bottle caps, spectacle frames, cutlery, disposable cutlery, the handles of cutlery, shelves, shelf dividers, electronic device housings, electronic device cases, computer monitors, printers, keyboards, pipes, automotive parts, automotive interior parts, automotive trims, signboards, thermoformed letters, siding, toys, thermally conductive plastics, ophthalmic lenses, tools, the handles of tools, and plastics for manufacturing household items. In other aspects, the composition of the present invention is suitable for use as films, seatings, fibers, molded articles, medical devices, packaging materials, bottles, bottle caps, spectacle frames, cutlery, disposable cutlery, the handles of cutlery, shelves, shelf dividers, furniture parts, electronic device housings, electronic device cases, computer monitors, printers, keyboards, pipes, the handles of toothbrushes, automotive parts, automotive interior parts, automotive trims, signboards, outdoor signboards, skylights, multilayer films, thermoformed letters, siding, toys, toy parts, thermally conductive plastics, ophthalmic lenses and frames, tools, the handles of tools, and household items, healthcare items, products for commercial food and beverage services, boxes, films for graphic art applications, and plastic films for plastic-glass laminates.

[0119]

[0117] This cellulose ester composition is useful for forming fibers, films, molded articles, and seatings. The method of forming the cellulose ester composition into fibers, films, molded articles, and seatings can follow methods known in the art. Examples of possible molded articles include, without limitation, medical devices, medical packaging materials, healthcare products, commercial foodservice products such as food pans, tumblers, and storage boxes, bottles, food processors, blenders, and mixing bowls, household goods, water barrels, crisper trays, washing machine fronts, vacuum cleaner parts, and toys. Other possible molded articles can include ophthalmic lenses and frames.

[0120]

[0118] The present invention further relates to a manufactured article comprising one or more films and / or sheets comprising the cellulose ester composition described herein. In some embodiments, the films and / or sheets of the present invention can be of any thickness apparent to those skilled in the art.

[0121]

[0119] The present invention further relates to one or more films and / or sheets described herein. Examples of methods for forming the cellulose ester composition into one or more films and / or sheets can include methods known in the art. Examples of one or more films and / or sheets of the present invention include, but are not limited to, one or more extruded films and / or sheets, one or more calendered films and / or sheets, one or more compression molded films and / or sheets, one or more solution cast films and / or sheets. Methods for manufacturing films and / or sheets include, but are not limited to, extrusion, calendering, compression molding, wet block processing, dry block processing, and solution casting.

[0122]

[0120] The present invention further relates to a molded article described in this specification. Examples of methods for molding a cellulose ester composition into a molded article include methods known in the art. Examples of the molded article of the present invention include, but are not limited to, injection molded articles, extrusion molded articles, injection blow molded articles, injection stretch blow molded articles, and extrusion blow molded articles. Examples of methods for manufacturing a molded article include, but are not limited to, injection molding, extrusion, injection blow molding, injection stretch blow molding, and extrusion blow molding. Examples of the method of the present invention include any blow molding process known in the art such as, but not limited to, extrusion blow molding, extrusion stretch blow molding, injection blow molding, and injection stretch blow molding.

[0123]

[0121] The present invention encompasses any injection blow molding manufacturing process known in the art. Without limitation, a representative description of an injection blow molding (IBM) manufacturing process involves: (1) melting the composition in a reciprocating screw extruder; (2) injecting the molten composition into an injection mold to form a partially cooled tube (i.e., a preform) closed at one end; (3) transferring the preform into a blow mold having a desired final shape around the preform and closing the blow mold around the preform; (4) blowing air into the preform to stretch and expand the preform to fill the mold; (5) cooling the molded article; (6) removing the article from the mold.

[0124]

[0122] The present invention encompasses any injection stretch blow molding manufacturing process known in the art. Without limitation, a representative description of an injection stretch blow molding (ISBM) manufacturing process 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) closed at one end; (3) transferring the preform into a blow mold having a desired final shape around the preform and closing the blow mold around the preform; (4) stretching the preform using an internal stretching rod and blowing air into the preform to stretch and expand the preform to fill the mold; (5) cooling the molded article; and (6) removing the article from the mold.

[0125]

[0123] The present invention encompasses any extrusion blow molding manufacturing process known in the art. Without limitation, a representative description of an extrusion blow molding manufacturing process 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) clamping a mold having a desired final shape around the parison; (4) blowing air into the parison to stretch and expand the extrudate to fill the mold; (5) cooling the molded article; (6) removing the article from the mold; and (7) removing excess plastic (usually called flash) from the article.

[0126]

[0124] The present invention can be further illustrated by the following examples of its preferred embodiments, which are included for illustrative purposes only and are not intended to limit the scope of the invention unless specifically indicated otherwise. Note that the examples 1 to 3, 10 to 12, 18, and 19 are equivalent to the examples included in the present invention, Comparative Examples 1 and 2 are equivalent to the comparative examples not included in the present invention, and the examples 4 to 9, 13 to 17, and 20 to 30 are equivalent to reference examples.

Examples

[0127]

[0125] Examples 1 to 25 in Tables 1 to 5 were prepared as follows. First, in a drum tumbler, cellulose powder was premixed with 1% epoxidized octyltallate stabilizer and either KaneAce B564-MBS impact modifier from Kaneka Corporation or KaneAce ECO100 acrylic impact modifier from Kaneka Corporation.

[0128]

[0126] Next, the premixed materials were mixed in a Werner & Pflerderer 30mm twin-screw extruder at a throughput of 35 pounds (15.9 kg) / hour, a screw speed of 250 rpm, and a barrel temperature of 220 °C for CAP482-based compositions and 240 °C for CA and CAP141-20-based compositions.

[0129]

[0127] Next, the mixed materials were injection molded into bars with a thickness of 3.2 mm × width of 12.8 mm using a Toyo 110-ton injection molding machine at a barrel temperature of 240 °C and a mold temperature of 70 °C.

[0130]

[0128] The cellulose ester materials used in the examples were selected from CAP 482-20, CAP-482-0.5, and CAP 141-20 of Eastman products. According to ASTM method D648, the heat distortion temperature (HDT) of the molded bars was determined. The samples were conditioned by placing them in an oven at 70 °C for 5 hours before the HDT test. After conditioning the molded bars at 23 °C and 50% RH for 48 hours, a notched Izod impact strength test was performed according to ASTM method D256 after notching.

[0131]

[0129] The compositions and properties of the materials for Examples 1 to 25 and Comparative Examples 1 and 2 are shown in Tables 1 to 5. Examination of Tables 1 to 5 shows that all of Examples 1 to 25 have higher toughness than Comparative Examples 1 and 2 which do not contain an impact modifier.

[0132]

Table 1

[0133]

Table 2

[0134]

Table 3

[0135]

Table 4

[0136]

Table 5

[0137] Melt processability of Example 12:

[0130] Using the spiral flow test, the flow behavior of Example 12 from the above Table 2 was compared with that of a normal plastic material. The spiral flow test was carried out using a Toyo 110-ton injection molding machine with an injection pressure of 1000 psi (6.89 MPa) , an injection speed of 1.0 inch (2.54 cm) / second, a filling time of 10 seconds, a screw speed of 150 rpm, a back pressure of 100 psi (689 kPa) , and a cooling time of 22 seconds. The molten material was filled into a spiral flow mold with a width of 0.5 inch (1.27 cm) × thickness of 0.125 inch (0.318 cm) . The flow length is the length of the spiral of each material molded at a specific barrel temperature under the same molding conditions.

[0138]

[0131] First, a spiral flow was carried out to determine the values of the flow lengths of several polymer materials. The materials used were Makrolon 2458 polycarbonate (PC) from Covestro, Lustran SAN31 (styrene-acrylonitrile or SAN) from INEOS, and Terluran GP22NR-ABS from INEOS. These materials were tested at the processing temperatures shown in Table 6 below.

[0139] Comparative Example 3:

[0132] Comparative Example 3 was prepared by conforming to the procedure described above from Eastman (registered trademark) cellulose acetate propionate 482-20 (88 wt%) and dioctyl adipate plasticizer (12 wt%).

[0140]

[0133] In addition to the materials discussed above, the spiral flow was determined for Example 12 and Comparative Example 3. These materials were tested at the processing temperatures shown in Table 6.

[0134]

[0141]

Table 6

[0142]

[0135] Examining Table 6, it can be seen that the values of the flow lengths of the commercial materials are between 10 and 30 inches. (25.4 to 76.2 cm) The spiral flow of Example 12 indicates that this composition has very good fluidity (equivalent to ABS and SAN and better than PC), and it is shown that the examples of the present invention can be melt processed in injection molding and other processes. The spiral flow length of Comparative Example 3 (fully plasticized with CAP but no impact modifier used) was the highest.

[0143] Light transmittance of Comparative Example 1 and Example 12:

[0136] The pellets of Comparative Example 1 and Example 12 were placed in a 150-ton Toyo injection molding machine with a barrel capacity of 6.7 ounces, at 1 inch (2.54 cm)At an injection speed of / second, using an apparent barrel temperature of 249 °C (480 °F), a residence time of 2 minutes or 5 minutes, and a mold temperature of 80 °C, injection molding was performed into two 4-inch × 4-inch × 0.126 (10.2 cm × 10.2 cm × 0.32 cm) plaques per shot. For the plaques molded at 2 minutes and 5 minutes (residence time), the light transmittance was measured according to ASTM-D1003a. The results are shown in Table 7 below.

[0144]

Table 7

[0145]

[0137] In Examples 26 to 30, the cellulose ester composition was prepared by mixing CAP 482-20 with several block copolymer thermoplastic elastomers and further impact modifiers such as an ABS core-shell type impact modifier. The mixing of the cellulose ester composition was carried out in a Leistritz 18 mm (L / D ratio of 50:1) twin-screw extruder at a throughput of 18 pounds (8.16 kg) / hour, a screw speed of 250 rpm, and a barrel temperature of 220 °C. For the mixing of CA and CAP 141-20 based compositions, the barrel temperature was 230 °C. Next, the mixed material was injection molded into a rod having a thickness of 3.2 mm × a width of 12.8 mm using a Toyo 110-ton injection molding machine at a barrel temperature of 240 °C and a mold temperature of 70 °C. In Table 8, the properties of these compositions are compared with Comparative Example 1.

[0146]

[0138] The glass transition temperature (Tg) was measured according to ASTM standard method D3418 in which the sample was heated from -110 °C at a heating rate of 20 °C / min. DSC scans of blends of multiple materials may show multiple Tg transitions. If more than one Tg transition is found during the scan, the glass transition of the matrix is defined as the highest Tg measured during the scan.

[0147]

[0139] For a formed bar with a thickness of 3.2 mm, after conditioning the bar at 230 °C and 50% RH for 48 hours, a notched Izod impact strength test was carried out at 23 °C after notching in accordance with ASTM method D256.

[0148]

Table 8

[0149]

[0140] The above detailed description of the various aspects of the present invention is intended to describe the various forms of the present invention in sufficient detail to enable those skilled in the art to practice the present invention. Other aspects can be used and modifications can be made without departing from the scope of the invention. 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 application, together with the full scope of equivalents to which the claims are entitled.

[0150]

[0141] 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 so stated and / or obvious to one 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 various aspects described herein. The present invention includes the following embodiments. (1) A cellulose ester composition comprising 55 to 99% by weight of at least one cellulose ester, 1 to 30% by weight of at least one impact resistance improver, and 0 to 15% by weight of at least one plasticizer, based on the total weight of the composition, wherein the composition has an HDT value higher than 95°C and a notched Izod impact strength value higher than 80 J / m when measured for a bar having a thickness of 3.2 mm at 23°C after conditioning the bar at 230°C and 50% RH for 48 hours in accordance with ASTM-D256. (2) The cellulose ester composition according to (1), wherein the composition comprises 70 to 99% by weight of the cellulose ester, 1 to 15% by weight of the impact resistance improver, and 0 to 15% by weight of the plasticizer. (3) The cellulose ester composition according to (1), wherein the composition comprises 70 to 99% by weight of the cellulose ester, 1 to 30% by weight of the impact resistance improver, and does not contain a plasticizer. (4) The cellulose ester composition according to (3), wherein the composition comprises 85 to 99% by weight of the cellulose ester, 1 to 15% by weight of the impact resistance improver, 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 one or more of cellulose propionate (CP), cellulose butyrate (CB), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose propionate butyrate (CPB), cellulose tripropionate (CTP), or cellulose tributyrate (CTB). (6) The cellulose ester is selected from cellulose acetate propionate (CAP) or cellulose acetate butyrate (CAB), and the composition contains a plasticizer in an amount of less than 0 to 2% by weight. The cellulose ester composition according to any one of (1) to (2). (7) The cellulose ester composition according to (6), wherein the CAP or CAB has an absolute weight average molecular weight of 15,000 to 300,000. (8) The cellulose ester composition according to (6), wherein the CAP or CAB has an absolute weight average molecular weight of 70,000 to 120,000. (9) The cellulose ester composition according to any one of (1) to (8), wherein the composition contains a plasticizer selected from the group consisting of phosphate plasticizers, benzoate plasticizers, adipate plasticizers, phthalate plasticizers, glycolate ester plasticizers, carbonate plasticizers, citrate ester plasticizers, and hydroxyl-functional plasticizers, or solid amorphous resin plasticizers, or combinations thereof. (10) The cellulose ester composition according to any one of (1) to (9), wherein the impact resistance improver is a core-shell type impact resistance improver. (11) The cellulose ester composition according to any one of (1) to (10), wherein the impact resistance improver is selected from an acrylic core-shell type impact resistance improver, an ABS core-shell type impact resistance improver, or an MBS core-shell type impact resistance improver. (12) The cellulose ester composition according to any one of (1) to (11), wherein the impact resistance improver has a refractive index of 1.46 to 1.50. (13) The cellulose ester composition according to any one of (1) to (12), wherein the impact resistance improver has a particle size of 0.01 to 2.0 μm. (14) A thermoplastic and melt-processable cellulose ester composition, 70 to 99% by weight of a cellulose ester containing one or more of cellulose acetate propionate (CAP) and cellulose acetate butyrate (CAB); 0 to less than 2% by weight of a plasticizer; and 1 to 15% by weight of a core-shell type impact resistance improver having a particle size of 0.01 to 2.0 μm; comprising; The composition has an HDT value higher than 95°C, a notched Izod impact strength value higher than 80 J / m measured at 23°C for a bar with a thickness of 3.2 mm according to ASTM-D256, and a viscosity of 10,000 P (1,000 Pa·s) or less at 400 rad / second and 240°C. (15) The cellulose ester composition according to (14), wherein the impact modifier is a non-reactive impact modifier. (16) The cellulose ester composition according to (14), wherein the impact modifier is a reactive impact modifier. (17) The cellulose ester composition according to any one of (1) to (13), further comprising at least one additive selected from the group consisting of an antioxidant, a heat stabilizer, a release agent, an antistatic agent, a brightening agent, a colorant, a plasticizer, an inorganic substance, a UV stabilizer, a lubricant, a nucleating agent, a reinforcing filler, glass fiber, carbon fiber, a flame retardant, a dye, a pigment, a colorant, a further resin, and combinations thereof. (18) A manufactured article comprising the cellulose ester composition according to any one of (1) to (13), wherein the composition has a notched Izod impact strength of at least 150 J / m. (19) The article according to (18), wherein the manufactured article is formed by injection molding. (20) A film or sheet comprising the cellulose ester composition according to any one of (1) to (13).

Claims

1. A cellulose ester composition for injection molding, comprising at least one cellulose ester in an amount of more than 90% by weight and not more than 99% by weight based on the total weight of the composition, and at least one impact resistance improver in an amount of 1 to 9% by weight, not containing a plasticizer. The composition has an HDT value higher than 95°C as measured at 1.82 MPa using a 3.2 mm thick bar heated at 70°C for 4 hours according to ASTM-D648, and a notched Izod impact strength value higher than 80 J / m as measured at 23°C for a 3.2 mm thick bar conditioned at 230°C and 50% RH for 48 hours according to ASTM-D256. The cellulose ester is selected from cellulose acetate propionate (CAP) or cellulose acetate butyrate (CAB), and the impact resistance improver is selected from an acrylic core-shell type impact resistance improver, an ABS core-shell type impact resistance improver, or an MBS core-shell type impact resistance improver.

2. The cellulose ester composition according to claim 1, wherein the CAP or CAB has an absolute weight average molecular weight of 15,000 to 300,000.

3. The cellulose ester composition according to claim 1, wherein the CAP or CAB has an absolute weight average molecular weight of 70,000 to 120,000.

4. The cellulose ester composition according to any one of claims 1 to 3, wherein the impact resistance improver is an acrylic core-shell type impact resistance improver.

5. A thermoplastic and melt-processable cellulose ester composition for injection molding, a cellulose ester selected from cellulose acetate propionate (CAP) or cellulose acetate butyrate (CAB) in an amount of more than 90% by weight and not more than 99% by weight; and 1 to 9% by weight of a core-shell impact modifier selected from an acrylic core-shell impact modifier, an ABS core-shell impact modifier, or an MBS core-shell impact modifier having a particle size of 0.01 to 2.0 μm; comprising; free of plasticizer; The composition has an HDT value higher than 95 °C measured at 1.82 MPa using a 3.2 mm thick bar conditioned at 70 °C for 4 hours according to ASTM-D648, a notched Izod impact strength value higher than 100 J / m measured at 23 °C for a 3.2 mm thick bar conditioned at 230 °C and 50% RH for 48 hours according to ASTM-D256, and a viscosity of 10,000 P (1,000 Pa·s) or less at 400 rad / s and 240 °C.

6. The cellulose ester composition according to claim 5, wherein the core-shell impact modifier is an acrylic core-shell impact modifier.

7. The cellulose ester composition according to any one of claims 1 to 6, further comprising at least one additive selected from the group consisting of antioxidants, heat stabilizers, release agents, antistatic agents, brightening 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.

8. An injection molded article comprising the cellulose ester composition according to any one of claims 1 to 7, wherein the composition has a notched Izod impact strength of at least 150 J / m.

Images