Cellulose ester and impact modifier compositions and articles made using these compositions

Abstract

A melt-processable cellulose ester composition having a high heat distortion temperature (HDT) is provided. Cellulose ester compositions containing at least one cellulose ester, at least one impact modifier, and optionally at least one plasticizer are provided. Methods for making the cellulose ester compositions and articles made with these compositions, such as eyeglass frames, automotive parts, and toys, are also provided.

Description

[Technical Field]

[0001]

[0001] This invention is in the field of cellulose ester chemistry, particularly cellulose esters containing an impact modifier and, optionally, a plasticizer. This invention also relates to cellulose ester compositions containing at least one impact modifier and, optionally, at least one plasticizer. Also provided are methods for making these cellulose ester compositions, as well as plastic articles made with these compositions, such as eyeglass frames, automobile parts, and toys. [Background technology]

[0002]

[0002] Cellulose acetate compositions typically have a heat distortion temperature (HDT) of less than 90°C. Commercially available cellulose esters used in thermoforming articles typically contain a significant amount of plasticizer to enable processing and to provide sufficient toughness to the molded article. However, adding a plasticizer has drawbacks because it reduces the HDT compared to the base cellulose ester, limiting the use of the cellulose ester material to applications that can tolerate an HDT below about 90°C. Additionally, molded cellulose ester articles may experience exudation of the plasticizer during use. Summary of the Invention [Problem to be solved by the invention]

[0003] It would be beneficial to provide a melt-processible cellulose ester composition that does not have these drawbacks. [Means for solving the problem]

[0004] It has been surprisingly discovered that cellulose ester compositions having an HDT greater than 95°C can be produced. In some embodiments of the present invention, this can be achieved by reducing the amount of plasticizer, and in some embodiments, by completely eliminating the use of plasticizer in the composition. Eliminating plasticizers can eliminate common problems associated with plasticizer leaching during use. However, reducing or eliminating plasticizers can reduce the toughness of these high HDT cellulose compositions. Surprisingly, it has been discovered that certain materials, called impact modifiers, can restore the toughness of high HDT cellulose compositions, even when added at relatively low levels, for example, about 2 wt. % based on the total weight of the cellulose ester composition.

[0005] In some embodiments, the present invention relates to dispersing an impact modifier in the form of small, discrete particles in a cellulose ester composition in an amount sufficient to improve the mechanical and physical properties of the cellulose ester composition. The impact-modified cellulose esters of the present invention are melt-processable and have the unique property of having a significantly higher HDT than commercially available plasticized cellulose ester thermoplastics, a high modulus, good impact properties, and good resistance to deformation under load.

[0006] In one aspect of the present invention, there is provided a cellulose ester composition comprising at least one cellulose ester, at least one impact modifier, and optionally at least one plasticizer.

[0007] In another aspect of the present invention, at least one cellulose ester, at least A cellulose ester composition is provided that includes both an impact modifier 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, comprising contacting at least one cellulose ester, at least one impact modifier, and optionally at least one plasticizer, and blending the 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 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 the inclusion of the plasticizer.

[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 wt%, or 1 to 15 wt%, or 2 to 10 wt%, or 10 to 30 wt%, or 15 to 30 wt%, of an impact modifier based on the total weight of the cellulose ester composition, and has an HDT value greater than 95°C and a notched Izod impact strength value greater than 80 J / m.

[0010] In another aspect of the present invention, there is provided a plasticizer-free melt-processable cellulose ester composition. In some embodiments, the melt-processable cellulose ester composition contains 1 to 30 wt. %, or 1 to 15 wt. %, or 2 to 10 wt. %, or 10 to 30 wt. %, or 15 to 30 wt. %, based on the total weight of the cellulose ester composition, of an impact modifier, and has an HDT value greater than 95°C, a notched Izod impact strength value greater than 80 J / m, and a hardness of at least 15 inches measured at 240°C. (38.1cm) has a spiral flow value of

[0011] In another embodiment of the present invention, the melt-processable cellulose ester composition comprises 2 wt. % to 15 wt. % of an impact modifier, based on the total weight of the cellulose ester composition, and has an HDT value greater than 95°C, a notched Izod impact strength value greater than 80 J / m, and a tensile strength of 10,000 P at 240°C and 400 rad / sec. (1,000 Pa·s)It has a viscosity of less than 10 ...

[0012]

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

[0013]

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

[0014] In another embodiment of the present invention, the cellulose ester composition comprises 15 wt. % or less of a plasticizer, or 10 wt. % or less of a plasticizer, based on the total weight of the cellulose ester composition; 1 to 30 wt. %, or 1 to 15 wt. %, or 2 to 10 wt. % of an impact modifier, based on the total weight of the cellulose ester composition; and has an HDT value greater than 95°C, a notched Izod impact strength value greater than 80 J / m, and a hardness of at least 15 inches measured at 240°C. (38.1cm) A melt-processible cellulose ester composition is described having a spiral flow value of

[0015] In another embodiment of the present invention, the cellulose ester composition comprises 15 wt. % or less of a plasticizer, or 10 wt. % or less of a plasticizer, based on the total weight of the cellulose ester composition; 1 to 30 wt. %, or 1 to 15 wt. %, or 2 to 10 wt. % of an impact modifier, based on the total weight of the cellulose ester composition; and has an HDT value greater than 95°C, a notched Izod impact strength value greater than 80 J / m, and a tensile strength of 10,000 P at 240°C and 400 rad / sec. (1,000 Pa·s) A melt-processible cellulose ester composition is described having a viscosity of less than 1000 .mu.m.

[0016] In other embodiments, the melt-processible cellulose ester compositions described above optionally contain some plasticizer. In some embodiments, the plasticizer is present in an amount that does not substantially decrease 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 the inclusion of the plasticizer.

[0017]

[0016] In one embodiment of the present invention, a cellulose ester composition is provided that includes at least one cellulose ester, at least one impact modifier, and, optionally, at least one plasticizer. In one embodiment, the cellulose ester is CAP, and the composition includes 0 to 5 wt%, 0 to 2 wt%, 0 to less than 2 wt%, or 0 to 1 wt% of the plasticizer. In one embodiment, the cellulose ester is CAP, and the composition does not include a plasticizer.

[0018]

[0017] In another aspect of the present invention, a cellulose ester composition is provided that includes at least one cellulose ester, at least one impact modifier, and at least one plasticizer. In one aspect, the cellulose ester is CA and the composition includes 1 to 15 wt% of the plasticizer. In some embodiments, the cellulose ester is CA and the composition includes 1 to 10 wt%, or 1 to less than 10 wt%, or 1 to 9 wt% of the plasticizer. DETAILED DESCRIPTION OF THE INVENTION

[0019] In one aspect of the present invention, there is provided a cellulose ester composition comprising at least one cellulose ester, at least one impact modifier, and optionally at least one plasticizer.

[0020] In some embodiments, the cellulose esters used in the present invention can be any known in the art. Cellulose esters that can be used for the present invention generally have the structure:

[0021] [ka]

[0022] (In the formula, R 1 , R 2 , and R 3 are independently selected from the group consisting of hydrogen or straight-chain alkanoyl having 2 to 10 carbon atoms. 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 celluloses have three hydroxyl groups in each AGU unit that can be substituted. The DS contains hydroxyl groups; therefore, the DS can have a value between 0 and 3. However, low molecular weight cellulose mixed esters may have a total degree of substitution slightly higher than 3 due to the contribution of end groups. Natural cellulose is a large polysaccharide with a degree of polymerization of 250 to 5,000, even after pulping and purification, so the assumption that the maximum DS is 3.0 is generally correct. However, as the degree of polymerization decreases, as in low molecular weight cellulose mixed esters, the end groups of the polysaccharide backbone become relatively more significant, resulting in a DS that can range above 3.0. Low molecular weight cellulose mixed esters are discussed in more detail later in this specification. Because DS is a statistical average, a value of 1 does not indicate that all AGUs have a single substituent. In some cases, there may be unsubstituted anhydroglucose units, some with two, and some with three substituents; usually, this value is a non-integer. 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 particular substituent, such as, for example, hydroxyl, acetyl, butyryl, or propionyl.

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

[0024] 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), or the like, or a combination thereof. Examples of such cellulose esters are described in U.S. Patents 1,698,049; 1,683,347; 1,880,808; 1,880,560; 1,984,147; 2,129,052; and 3,617,201 (all of which are incorporated herein by reference to the extent not inconsistent with the teachings 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 is not selected from cellulose acetate (CA).

[0026] In some embodiments of the present invention, the cellulose ester has at least two anhydroglucose rings and may have at least 50 to 5,000 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 may have 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, measured at 25°C for a 0.25 gram sample in 100 mL of a 60 / 40 phenol / tetrachloroethane solution. 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 esters useful in the present invention have a DS / AGU of from about 2 to about 2.99. The substituted esters may include acetyl, propionyl, and butyryl, or any combination thereof. In another embodiment of the invention, the total DS / AGU ranges from about 2 to about 2.99, the acetyl DS / AGU ranges from about 0 to 2.2, and the remainder of the ester groups include propionyl, butyryl, or combinations thereof.

[0027] In another embodiment of the present invention, the total DS / AGU ranges from about 2 to about 2.99, the acetyl DS / AGU ranges from about 0 to about 1.2, and the remainder of the ester groups comprise propionyl, butyryl, or a combination thereof. In another embodiment of the present invention, the total DS / AGU ranges from about 2 to about 2.99, the acetyl DS / AGU ranges from about 0 to 0.5, and the remainder of the ester groups comprise propionyl, butyryl, or a combination thereof.

[0028]

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

[0029] One method for producing cellulose esters is the esterification of cellulose by mixing the cellulose with an appropriate organic acid, an acid anhydride, and a catalyst. The cellulose is then converted to a cellulose triester. The ester is then hydrolyzed by adding a water-acid mixture to the cellulose triester, which can then be filtered to remove gel particles or fibers. Water is then added to the mixture to precipitate the cellulose ester. The cellulose ester can then be washed with water to remove reaction by-products, followed by dehydration and drying.

[0030] The cellulose triester to be hydrolyzed may have three substituents independently selected from alkanoyl groups having 2 to 10 carbon atoms. Examples of cellulose triesters include cellulose triacetate, cellulose tripropionate, and cellulose tributyrate, or mixed triesters of cellulose such as cellulose acetate propionate and cellulose acetate butyrate. These cellulose esters can be prepared by a number of methods known to those skilled in the art. For example, cellulose esters can be prepared by heterogeneous acylation of cellulose in a mixture of a carboxylic acid and anhydride in the presence of a catalyst such as H2SO4. Cellulose triesters can also be prepared by homogeneous acylation of cellulose dissolved in a suitable solvent such as LiCl / DMAc or LiCl / NMP.

[0031] Those skilled in the art will appreciate that the trade term cellulose triester also encompasses cellulose esters that are not fully substituted with acyl groups. For example, cellulose triacetate commercially available from Eastman Chemical Company, Kingsport, Tenn., USA, typically has a DS of about 2.85 to about 2.99.

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

[0033] In one embodiment, the secondary cellulose esters useful in the present invention have an absolute weight average molecular weight (Mw) of about 5,000 to about 400,000 as measured by gel permeation chromatography (GPC) according to ASTM-D6474. To calculate the absolute weight average molecular weight (Mw) values ​​for CE, the following method is used: The solvent is THF stabilized with BHT preservative. The equipment for the THF / cellulose ester procedure consists of the following Agilent 1200 series components: degasser, isocratic pump, autosampler, column oven, UV / Vis detector, and refractive index detector. The test temperature is 30°C, and the flow rate is 1.0 mL / min. A sample solution of 25 mg of cellulose ester in 10 mL of THF with BHT preservative and 10 μL of toluene flow rate marker is prepared. The injection volume is 50 μL. The column set is a Polymer Laboratories 5 μm-PLgel, Guard + Mixed C + Oligopore. Detection is by refractive index. Calibrants are monodisperse polystyrene standards from Polymer Laboratories, Mw = 580-3,220,000. Universal calibration parameters are as follows: PS (K = 0.0001280 and a = 0.7120) and CE (K = 0.00007572 and a = 0.8424). The universal calibration parameters are determined by light scattering and viscosimetry to obtain accurate weight average molecular weights. In further embodiments, Mw is from about 15,000 to about 300,000. In further embodiments, Mw is in the range of from about 10,000 to about 250,000; from about 15,000 to about 200,000; from about 20,000 to about 150,000; from about 50,000 to about 150,000; or from about 70,000 to about 120,000.

[0034] In some embodiments of the present invention, the polymer base resin comprises a cellulose ester having an absolute weight average molecular weight ranging from about 40,000 Da to about 200,000 Da, as measured in accordance with ASTM-D 5296 using tetrahydrofuran as the solvent and a flow rate of 1 mL / min. In some embodiments, the cellulose ester has an absolute weight average molecular weight ranging from about 50,000 Da to about 200,000 Da, or from 50,000 Da to about 170,000 Da, or from 50,000 Da to about 120,000 Da, or from 50,000 Da to about 90,000 Da, or from 60,000 Da to about 200,000 Da, as measured in accordance with ASTM-D 5296 using tetrahydrofuran as the solvent and a flow rate of 1 mL / min. The absolute weight average molecular weight ranges from 0 Da, or from 60,000 Da to about 170,000 Da, or from 60,000 Da to about 120,000 Da, or from 60,000 Da to about 90,000 Da, or from 90,000 Da to about 170,000 Da, or from 90,000 Da to about 120,000 Da, or from 120,000 Da to about 170,000 Da, or from 120,000 Da to about 200,000 Da.

[0035]

[0032] Most commonly, commercial secondary cellulose esters are prepared 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 subjected to hydrolysis until the desired degree of substitution is achieved. After isolation, random secondary cellulose esters are obtained, i.e., the relative degree of substitution (RDS) at each hydroxyl is approximately equal.

[0036] Some examples of cellulose esters that may be useful in the present invention can be prepared using techniques known in the art and are available from Eastman Chemical Company, Kingsport, Tenn., USA, e.g., Eastman® Cellulose Acetate. Propionate CAP482-20, Eastman® Cellulose Acetate Propionate Cellulose Acetate Butyrate CAP141-20, Eastman® Cellulose Acetate Butyrate CAB381-20 , cellulose acetate butyrate CAB171-15, and Eastman® cellulose Acetate CA398-30.

[0037] In some embodiments, the cellulose esters used in the present invention may also contain chemical functional groups, which are herein referred to as either derivatized, modified, or functionalized cellulose esters. Functionalized cellulose esters can be prepared by reacting the free hydroxyl groups of the cellulose ester with a bifunctional reactant having one linking group for grafting onto the cellulose ester and one functional group for providing a new chemical group to the cellulose ester. Examples of such bifunctional reactants include succinic anhydride, which is linked by an ester bond to provide an acid functionality; mercaptosilane, which is linked by an alkoxysilane bond to provide a mercapto functionality; and isocyanatoethyl methacrylate, which is linked by a urethane bond to provide a methacrylate functionality.

[0038] In one aspect of the present invention, functionalized cellulose esters are prepared by reacting the free hydroxyl groups of a cellulose ester with a bifunctional reactant to produce a cellulose ester having at least one functional group selected from the group consisting of unsaturation (double bond), carboxylic acid, acetoacetate, acetoacetate imide, mercapto, melamine, and long alkyl chain.

[0039]

[0036] Difunctional reactants for preparing cellulose esters containing unsaturated (double bond) functional groups are described in U.S. Patents 4,839,230; 5,741,901; 5,871,573; 5,981,738; 4,147,603; 4,758,645; and 4,861,629 (all of which are incorporated herein by reference to the extent they do not contradict the teachings herein). In one embodiment, a cellulose ester containing unsaturation is prepared by reacting a cellulose ester containing residual hydroxyl groups with an acrylic compound and m-isopropienyl-α,α'-dimethylbenzyl isocyanate. The grafted cellulose ester is a urethane-containing product having pendant (meth)acrylate and α-methylstyrene groups. In another embodiment, the cellulose ester containing unsaturation is prepared by reacting maleic anhydride with a cellulose ester in the presence of a catalyst, 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 another embodiment, the cellulose ester containing unsaturation is prepared from the reaction product of (a) at least one cellulose polymer having isocyanate-reactive hydroxyl functionality and (b) at least one hydroxyl-reactive poly(α,β-ethylenically unsaturated) isocyanate.

[0040]

[0037] Bifunctional reactants for preparing cellulose esters containing carboxylic acid functionality are described in U.S. Patents 5,384,163; 5,723,151; and 4,758,645 (all of which are incorporated herein by reference to the extent they do not contradict the teachings herein). In one embodiment, the cellulose ester containing carboxylic acid functionality is prepared by reacting a cellulose ester with a mono- or diester of maleic or fumaric acid to thereby obtain a cellulose derivative having double bond functionality. In another embodiment, the cellulose ester containing carboxylic acid functionality has first and second residues, the first residue being a residue of a cyclic dicarboxylic acid anhydride, and the second residue being a residue of a lipophilic monocarboxylic acid and / or a hydrophilic monocarboxylic acid. In yet another embodiment, the cellulose ester containing carboxylic acid functionality is cellulose acetate phthalate, which can be prepared by reacting cellulose acetate with phthalic anhydride.

[0041]

[0038] Bifunctional reactants for preparing cellulose esters containing acetoacetate functionality are described in U.S. Patent 5,292,877, which is incorporated herein by reference to the extent that it does not contradict the teachings herein. In one embodiment, the cellulose esters containing acetoacetate functionality are prepared by reacting (i) cellulose; (ii) diketene, alkyl acetoacetate; acetate, 2,2,6-trimethyl-4H-1,3-dioxin-4-one, or a mixture thereof; and (iii) a solubilizing amount of a solvent system comprising lithium chloride and a carboxamide selected from the group consisting of 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, or a mixture thereof.

[0042]

[0039] Difunctional reactants for preparing 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 teachings herein). Cellulose esters containing acetoacetate imide functional groups are the reaction product of a cellulose ester and an amine-functional compound containing at least one acetoacetyl group and at least one primary amine.

[0043]

[0040] Bifunctional reactants for preparing cellulose esters containing mercapto functional groups are described in US Patent 5,082,914 (incorporated herein by reference to the extent that they do not contradict the statements herein). In one aspect of the present invention, cellulose esters are grafted with silicon-containing thiol components that can be commercially obtained or prepared by procedures known in the art. Examples of silicon-containing thiol compounds include, but are not limited to, (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)dimethyl-methoxysilane, (3-mercaptopropyl)dimethoxymethylsilane, (3-mercaptopropyl)dimethylchlorosilane, (3-mercaptopropyl)dimethylethoxysilane, (3-mercaptopropyl)diethoxymethylsilane, and (3-mercaptopropyl)triethoxysilane.

[0044]

[0041] Bifunctional reactants for preparing 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 teachings herein). In one embodiment, the cellulose esters containing melamine functional groups are prepared by reacting a cellulose ester with a melamine compound to form a grafted cellulose ester in which the melamine groups are grafted onto the backbone of the anhydroglucose rings of the cellulose ester. In one embodiment, the melamine compound is selected from the group consisting of methylol ethers of melamine and aminoplast resins.

[0045]

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

[0046] In some embodiments of the present invention, the impact modifier may be any material known to increase the impact strength of cellulose ester compositions. In one embodiment, the impact modifier may be any polymeric material classified as an elastomer having a glass transition temperature (Tg) below room temperature. Tg can be measured, for example, according to ASTM-D3418 using a TA2100 thermal analyzer at a scan rate of 20°C / min. Several classes of impact modifiers fit this description.

[0047] In one embodiment, the impact modifier is a class of polyolefins 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 with a Tg below room temperature and reducing the modulus below 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 E419). 3101), EEA, EPDM (examples include Royaltuf 498), and and EPR.

[0048] In one class of these embodiments, the impact modifier is a block copolymer in which at least one segment of the chain has a Tg below room temperature (called the soft segment) and at least one segment of the chain has a Tg or Tm above room temperature (called the hard segment). These block copolymers are also commonly referred to as thermoplastic elastomers (TPEs). Examples of block copolymers in this class include SBS, SEBS, and SIS (e.g., Kraton G1657MS, Kraton FG1901G, and Kraton Styrenic materials such as styrene-based materials (e.g., FG1924G); thermoplastic urethanes (TPUs) (e.g., Elastolan 1170Z, Estane 2355, Estane ALR-CL87A, and Estane ALR-72A); polyester-ether copolymers (e.g., Ecdel 9966 and Hytrel 3078 ), or polyamide-ether copolymers (examples include Pebax 5533).

[0049] In one embodiment, the impact modifier can be selected from the class of emulsion-forming materials known as core-shell impact modifiers. In one embodiment, the impact modifier is an MBS core-shell impact modifier, such as methacrylate-butadiene-styrene, having a core formed from a butadiene-styrene copolymer and a shell formed from a methyl methacrylate-styrene copolymer. In another embodiment, the impact modifier is an acrylic core-shell impact modifier, having a core formed from an acrylic polymer, such as butyl acrylate or styrene butyl acrylate, and a shell formed from polymethyl methacrylate or a styrene methyl methacrylate copolymer.

[0050] In one embodiment of the present invention, the core-shell impact modifier comprises: (A) about 70 to about 85 parts of a core comprising about 15 to about 35 weight percent units derived from at least one vinyl aromatic monomer and about 65 to about 85 weight percent units derived from at least one diolefin monomer; (B) an internal grafting 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) about 0.1 to about 5 parts of an intermediate sealer stage comprising at least one monomer selected from a C1 to C8 alkyl acrylate or a polyunsaturated crosslinker; and (D) about 10 to about 16 parts of an outer shell comprising at least one C1-C4 alkyl (meth)acrylate monomer or at least one vinyl aromatic monomer; The MBS impact modifier may include:

[0051] In some embodiments, the MBS impact modifier may comprise a graft polymer composition comprising 10 to 70 weight percent of a polymer or copolymer of butadiene and a graft of first, methyl (meth)acrylate and a crosslinker, second, styrene, and third, methyl (meth)acrylate and, optionally, a crosslinker.

[0052] Suitable monomers for polymerizing with the conjugated diolefin, preferably butadiene, include alkenyl aromatic compounds, preferably vinyl aromatic compounds, such as styrene, divinyl nylbenzene, α-methylstyrene, vinyltoluene, hydrogenated styrene; lower (CZ-Cu) alkyl acrylates, such as ethyl acrylate, n-propyl acrylate, n-butyl acrylate, Z-methylbutyl acrylate, 3-methylbutyl acrylate, amyl acrylate, n-hexyl acrylate, Z-ethylhexyl acrylate; lower (C2-C 12 ) alkyl (meth)acrylates; acrylonitrile; olefins, and the like; or combinations of any of the above.

[0053]

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

[0054] In one embodiment, the MBS core-shell impact modifier can comprise a copolymer of butadiene and styrene, most preferably a terpolymer of butadiene, styrene, and divinylbenzene. The relative amounts of the monomers comprising the copolymer substrate can vary, but based on 100 parts by weight of butadiene, styrene, and divinylbenzene combined, the butadiene component typically comprises about 30 to 100 parts by weight, the styrene component comprises 0 to about 70 parts by weight, and the divinylbenzene component comprises 0 to about 5 parts by weight. In one embodiment, the copolymer substrate can comprise, 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 include, but are not limited to, those described in patents US-4,446,585, US-5,534,594, and US-6,331,580. MBS core-shell impact modifiers are available 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 embodiment of the present invention, the core-shell impact modifier is an acrylic impact modifier comprising about 25 to 95 weight percent of a first elastomeric phase polymerized from a monomer system comprising about 75 to 99.8 weight percent of a (C1-C6) alkyl acrylate, 0.1 to 5 weight percent of a crosslinking monomer, and 0.1 to 5 weight percent of a graft linking monomer, and about 75 to 5 weight percent of a final rigid thermoplastic phase containing no epoxy groups polymerized in the presence of such elastomeric phase.

[0057] Examples of useful acrylates are methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc. In some embodiments, the acrylates are n-butyl acrylate and ethyl acrylate.

[0058] Graft link monomers are defined as polyethylenically unsaturated monomers having both high and low reactivity double bonds, the high reactivity double bonds tending to polymerize during the polymerization of the first stage monomers, leaving residual double bonds for polymerization during the next stage polymerization, thereby grafting the second stage polymer onto the first stage polymer. In some embodiments, the graft link monomers are allyl methacrylate, allyl acrylate, and diallyl maleate. In one embodiment, the graft link monomer is present at 0.05 to 3% based on the first stage monomer system. Also preferred are A crosslinking monomer is also preferably present, generally in an amount of about 0.05 to 3 weight percent based on the first stage monomer system, and is defined as a polyethylenically unsaturated monomer having at least two double bonds of approximately equal reactivity to cause crosslinking in the first stage polymerization. Representative examples of crosslinking monomers include 1,3-butylene diacrylate, 1,3-butylene dimethacrylate, divinylbenzene, and the like.

[0059] "Epoxy functionality" means epoxy units pendant from the final stage polymer. In some embodiments, epoxy functionality is introduced into the final stage polymer by using epoxy-containing monomers such as glycidyl acrylate or glycidyl methacrylate in the final stage monomer mix.

[0060]

[0057] Examples of acrylic core-shell polymers include, but are not limited to, those described in patents US-3,448,173, US-3,655,825, and US-3,853,968. 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] In one class of this embodiment, the impact modifier is an ABS core-shell 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 impact modifiers include Blendex from Galata Chemicals and Elix from Elix Polymers.

[0062] In one class of this embodiment, the impact modifier is a silicone-acrylic core-shell 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. Examples of silicone-acrylic core-shell impact modifiers include Metablen S from Mitsubishi Chemical Company.

[0063] 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), which is believed to help prevent degradation of the cellulose ester during melt processing of the composition.

[0064] In one particularly useful embodiment, the cellulose ester and impact modifier composition is transparent and has a light transmittance of at least 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%, as measured using 3.2 mm plaques after injection molding in accordance with ASTM-D 1003 at a barrel set point of 249° C. and a 5 minute residence time. In some embodiments, the polymer base resin has a light transmittance of 70% to 95%, or 75% to 95%, or 80% to 95%, or 85% to 95%, or 70% to 90%, or 75% to 90%, or 80% to 90%, or 85% to 90%, as measured using 3.2 mm plaques after injection molding in accordance with ASTM-D 1003 at a barrel set point of 249° C. and a 5 minute residence time. In one class of this embodiment, the cellulose ester compositions containing impact modifiers have a % haze of less than 10%. In some embodiments, the cellulose ester compositions containing impact modifiers have a % haze of less than 8%, or less than 6%, or less than 5%.

[0065] In another embodiment, the refractive index (RI) of the impact modifier is sufficiently close to that of the cellulose ester 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, between about 1.46 and 1.50, providing a clear composition. In some embodiments, The impact modifier component and the cellulose ester component have a refractive index difference, RI(second component) - RI(first component) (e.g., RI of CE - RI of impact modifier), of about 0.006 to about -0.0006, and the immiscible blend has a transmittance of at least 75% and a haze of 10% or less, more preferably 5% or less.

[0066] In one embodiment, the impact modifier may be either a non-reactive impact modifier or a reactive impact modifier, or a combination of both. The impact modifier used may also improve the mechanical and physical properties of the cellulose ester composition.

[0067] In one embodiment, when a non-reactive impact modifier is used, the impact modifier comprises a first polymer chain segment that is chemically or physically more compatible with the cellulose ester than other polymer chain segments. In one embodiment, the first segment comprises a polar functional group that confers compatibility with the cellulose ester, such as, but not limited to, polar functional groups such as ethers, esters, amides, alcohols, amines, ketones, and acetals. Compatibility is defined by preferential interaction of the first polymer chain segment with the cellulose ester polymer relative to the second segment, and can refer to molecular-scale or micro-scale interactions. The first segment can be composed of an oligomer or polymer of the following: cellulose esters; cellulose ethers; polyoxyalkylenes such as polyoxyethylene, polyoxypropylene, and polyoxybutylene; polyglycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; polyesters such as polycaprolactone, polylactic acid, aliphatic polyesters, and aliphatic-aromatic copolyesters; polyacrylates and polymethacrylates; polyacetals; polyvinylpyrrolidone; polyethylene vinyl acetate; polyvinyl acetate; and polyvinyl alcohol. In one embodiment, the first segment is polyethylene vinyl acetate; polyoxyethylene; or polyvinyl alcohol.

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

[0069] The first and second segments of the non-reactive impact modifier may be diblock, triblock, branched, or comb-type. 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] Examples of non-reactive impact modifiers include, but are not limited to, ethoxylated alcohols, ethoxylated alkylphenols, ethoxylated fatty acids, polyethylene vinyl acetate, block polymers of propylene oxide and ethylene oxide, ethylene / propylene terpolymers, functionalized polyolefins, polyglycerol esters, polysaccharide esters, and sorbitan esters. Examples of ethoxylated alcohols include C 11 ~C 15 Secondary alcohol ethoxylates, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and C ethoxylated with ethylene oxide 12 ~C 14 It is a natural linear alcohol. 11 ~C 15 Secondary alcohol ethoxylates are , available from The Dow Chemical Company as Dow Tergitol® 15S Polyoxyethylene cetyl ether and polyoxyethylene stearyl ether are available from ICI Surfactants in their Brij® series of products. C ethoxylated with oxide 12 ~C 14 Natural linear alcohols are available from Hoechst Celanese in the Genapol® series of products. Examples of alkylphenols include octylphenoxypoly(ethyleneoxy)ethanol and nonylphenoxypoly(ethyleneoxy)ethanol. Octylphenoxypoly(ethyleneoxy)ethanol is available from Rhodia as a product in the Igepal® CA series, and nonylphenoxypoly(ethyleneoxy)ethanol is available from Rhodia as a product in the Igepal® CO series or from Dow Chemical Company as Tergitol® NP. Ethoxylated fatty acids include Henkel Examples of suitable polyethylene glycol monostearates or monolaurates include those available from Stepan under the Nopalcol® series of products. Block polymers of propylene oxide and ethylene oxide are available from BASF under the Pluronic® series of products. Polyglycerol esters are available from Stepan under the Drewpol® series of products. Polysaccharide esters are available from Henkel in the Glucopon® series of products, which are alkyl polyglucosides. Sorbitan esters are available from ICI in the Tween® series of products.

[0071] In another embodiment of the present invention, the non-reactive impact modifier is synthesized in situ in the cellulose ester composition by reacting a compound compatible with the cellulose ester. These compounds may be, for example, telechelic oligomers, which are defined as prepolymers capable of initiating further polymerization or other reactions by virtue of their reactive end groups. In one aspect of the invention, these in situ impact modifiers are , may have a higher molecular weight of about 10,000 to about 1,000,000.

[0072] In another embodiment of the present invention, the impact modifier may be reactive. A reactive impact modifier may include a polymer or oligomer that is compatible with one component of the composition and a functional group that can react with another component of the composition. In some embodiments, there are two types of reactive impact modifiers that can be used. The first reactive impact modifier has a hydrocarbon chain that is compatible with the cellulose ester and also has a functional group that can react with the cellulose ester. Such functional groups include, but are not limited to, carboxylic acids, anhydrides, acid chlorides, epoxides, and isocyanates. Specific examples of this type of reactive impact modifier include, but are not limited to, long-chain fatty acids such as stearic acid (octadecanoic acid); long-chain fatty acid chlorides such as stearoyl chloride (octadecanoyl chloride); long-chain fatty acid anhydrides such as stearic anhydride (octadecanoic anhydride); epoxidized fatty esters; styrene-maleic anhydride copolymers; maleic anhydride-grafted polypropylene; copolymers of maleic anhydride with olefins and / or acrylic esters, such as terpolymers of ethylene, acrylic esters, and maleic anhydride; and copolymers of glycidyl methacrylate with olefins and / or acrylic esters, such as terpolymers of ethylene, acrylic esters, and glycidyl methacrylate.

[0073] Reactive impact modifiers include SMA® 3000 styrene maleic anhydride copolymer from Sartomer / Cray Valley, Eastman G-3015® maleic anhydride grafted polypropylene from Eastman Chemical Company, Epolene® E-43 maleic anhydride grafted polypropylene from Westlake Chemical, Lotader® MAH 8200 random copolymer of ethylene, acrylic acid ester, and maleic anhydride from Arkema. Lotade terpolymer of ethylene, acrylic ester, and glycidyl methacrylate ® GMA AX8900 random terpolymer, and ethylene, acrylate, and Lotarder® GMA AX8840 random terpolymer of glycidyl methacrylate.

[0074] Modified polyolefin impact modifiers are available as Lotader, Fusabond, Elvaloy PTW, Lotryl, Elvaloy AC, InterLoy.

[0072] The second type of reactive impact modifier has a polar chain compatible with cellulose esters 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 with olefin or thiol functional groups. Reactive polyethylene glycol impact modifiers with olefin functional groups include, but are not limited to, polyethylene glycol allyl ether and polyethylene glycol acrylate. Examples of reactive polyethylene glycol impact modifiers with thiol functional groups include polyethylene glycol thiols. Examples of reactive cellulose ester impact modifiers include mercaptoacetate cellulose esters.

[0075]

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

[0076] In another embodiment 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 weight percent based on the total cellulose ester composition. Suitable examples of the additional polymer component include, but are not limited to, nylon; polyester; polyamide; polystyrene; other cellulose esters, cellulose ethers; polystyrene copolymers; styrene-acrylonitrile copolymers; polyolefins; polyurethanes; acrylonitrile-butadiene-styrene copolymers; poly(methyl methacrylate); acrylic copolymers; poly(ether-imides); polyphenylene oxides; polyvinyl chloride; polyphenylene sulfide; polyphenylene sulfide / sulfones; poly(ester-carbonates); polycarbonates; polysulfones; polylactic acid; polybutylene succinates; polysulfone ethers; and poly(ether-ketones) of aromatic dihydroxy compounds; or mixtures of any of the above polymers. The blends can be formed by conventional processing techniques known in the art, such as melt blending or solution blending.

[0077] In one embodiment 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 capable of lowering the glass transition temperature and / or melt viscosity of the cellulose ester to improve melt processing properties. The plasticizer can be any suitable plasticizer for use with cellulose esters. The level of plasticizer should be lower than standard (or conventional) plasticizer levels for cellulose esters so that the composition has a higher Tg (or HDT), better toughness, and better flow properties than fully plasticized cellulose ester compositions. In some embodiments, the plasticizer is present in an amount that does not substantially decrease the Tg (or HDT) of the cellulose ester composition compared to a similar composition without the plasticizer. In some embodiments, the Tg (or HDT) does not change (e.g., decrease) by more than 20%, more than 15%, more than 10%, more than 5%, or more than 2% as a result of the inclusion of the plasticizer.

[0078]

[0076] The plasticizer may be either monomeric or polymeric in structure. In one embodiment, the plasticizer is an aromatic phosphate ester plasticizer, an alkyl phosphate ester The plasticizer is at least one selected from the group consisting of a dialkyl ether diester plasticizer, a tricarboxylic acid ester plasticizer, a polymeric polyester plasticizer, a polyglycol diester plasticizer, a polyester resin plasticizer, an aromatic diester plasticizer, an aromatic triester plasticizer, an aliphatic diester plasticizer, a carbonate plasticizer, an epoxidized ester plasticizer, an epoxidized oil plasticizer, a benzoate plasticizer, a polyol benzoate plasticizer, an adipate plasticizer, a phthalate plasticizer, a glycolate ester plasticizer, a citrate ester plasticizer, a hydroxyl-functional plasticizer, or a solid amorphous resin plasticizer.

[0079] In one aspect of the 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] In another aspect of the present invention, the plasticizer may be selected from at least one of the following esters: (i) an acid residue comprising one or more residues of phthalic acid, adipic acid, trimellitic acid, succinic acid, benzoic acid, azelaic acid, terephthalic acid, isophthalic acid, butyric acid, glutaric acid, citric acid, or phosphoric acid; and (ii) an alcohol residue comprising one or more residues of an aliphatic, alicyclic, or aromatic alcohol containing about 20 or fewer carbon atoms.

[0081] In another aspect of the present invention, the plasticizer may be selected from at least one of the following: (i) at least one acid residue selected from the group consisting of phthalic acid, adipic acid, trimellitic acid, succinic acid, benzoic acid, azelaic acid, terephthalic acid, isophthalic acid, butyric acid, glutaric acid, citric acid, or phosphoric acid; and (ii) at least one alcohol residue selected from the group consisting of aliphatic, alicyclic, or aromatic alcohols containing about 20 or fewer carbon atoms.

[0082] In another aspect of the present invention, the plasticizer may comprise an alcohol residue, the alcohol residue being 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] In another aspect of the invention, the plasticizer can be selected from at least one of the following: benzoates, phthalates, phosphates, arylene-bis(diarylphosphates), and isophthalates. In another aspect, the plasticizer comprises diethylene glycol dibenzoate (abbreviated herein as "DEGDB").

[0084] In another embodiment of the present invention, the plasticizer is one of the following: C2-C 10Diacid residues, such as residues of malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid; and C2-C 10 The polyester may be selected from at least one aliphatic polyester containing a diol residue.

[0085] In another embodiment, the plasticizer is selected from the group consisting of the following C2 to C6 10 Diol: Ethylene glycol The copolymer may comprise a diol residue which may be the residue of at least one of 1,2-pentanediol, 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] In another embodiment of the present invention, the plasticizer can include polyglycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol. These can range from low molecular weight dimers and trimers to high molecular weight oligomers and polymers. In one embodiment, the molecular weight of the polyglycols can range from about 200 to about 2000.

[0087] In another embodiment of the present invention, the plasticizer is 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] In another embodiment of the present invention, the plasticizer is (A) from about 5 to about 95 weight percent of a C2-C 12(B) a carbohydrate organic ester (the carbohydrate containing from about 1 to about 3 monosaccharide units); and (B) from about 5 to about 95% by weight of a C2-C 12 In one embodiment, the polyol ester does not include or contain one or more polyol acetates.

[0089]

[0087] In another embodiment, the plasticizer comprises at least one carbohydrate ester, wherein the carbohydrate portion of the carbohydrate ester is derived from one or more compounds selected from the group consisting of glucose, galactose, mannose, xylose, arabinose, lactose, fructose, sorbose, sucrose, cellobiose, cellotriose, and raffinose.

[0090]

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

[0091] In another embodiment, the plasticizer comprises at least one carbohydrate ester, wherein the carbohydrate portion of the carbohydrate ester comprises an α-anomer, a β-anomer, or a mixture thereof.

[0092] In other embodiments, the plasticizer may 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] In another embodiment of the present invention, the plasticizer may be a solid amorphous resin. These resins may contain some aromatic or polar functional groups, which can reduce the melt viscosity of the cellulose ester. In one embodiment of the present invention, the plasticizer may be, for example, rosin; hydrogenated rosin; stabilized rosin and their monofunctional alcohol or polyol esters; maleic and phenolic modified rosin and their esters, etc. The resin may be a solid amorphous compound (resin) such as modified rosin (including, but not limited to, rosins); terpene resins; phenol-modified terpene resins; coumarin-indene resins; phenolic resins; alkylphenol-acetylene resins; and phenol-formaldehyde resins.

[0094] In another embodiment of the invention, the plasticizer is selected from the group consisting of triacetin, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, triethyl citrate, acetyl trimethyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, tributyl-o-acetyl citrate, dibutyl phthalate, diaryl phthalate, diethyl phthalate, dimethyl phthalate, di-2-methoxyethyl phthalate, dioctyl phthalate, dioctyl adipate, dibutyl tartrate, ethyl o-benzoylbenzoate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, n-ethyl Toluenesulfonamide, 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-C 20Dicarboxylic acid esters, dimethyl adipate, dibutyl maleate, dioctyl maleate, resorcinol monoacetate, catechol, catechol esters, phenols, epoxidized soybean oil, castor oil, linseed oil, epoxidized linseed oil, other vegetable oils, other seed oils, polyethylene glycol-based bifunctional glycidyl ethers, gamma-valerolactone, alkyl phosphate esters, aryl phosphate esters, phospholipids, eugenol, cinnamyl alcohol, camphor, methoxyhydroxyacetophenone, vanillin, ethyl vanillin, 2-phenoxyethanol, glycol ethers, glycol esters, glycol ester ethers, polyglycol ethers, polyglycol esters, ethylene glycol ethers, propylene glycol ethers, ethylene glycol esters, propylene glycol and at least one plasticizer selected from the group consisting of methyl 4-hydroxybenzoate, 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] 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, the amount may be about 15 wt % or less based on the weight of the cellulose ester composition. In another embodiment, the amount may be about 10 wt % or less based on the weight of the cellulose ester composition. In other embodiments, the amount may be about 5 wt % or less based on the weight of the cellulose ester composition, or about 3 wt % or less based on the weight of the cellulose ester composition, or less than 2 wt % based on the weight of the cellulose ester composition.

[0096] In another embodiment of the present invention, the cellulose ester composition is free of plasticizers. In one embodiment, the cellulose ester composition comprises a cellulose ester that is CAP and does not contain a plasticizer. In one embodiment, the cellulose ester composition comprises a cellulose ester that is CAB and does not contain a plasticizer.

[0097] In another embodiment of the invention, the composition is melt processable. Melt processability generally refers to the ability of materials to be thermally processed below their decomposition temperature to obtain uniform pellets or plastic articles. For example, the described composition was melt processed in a Werner & Pflerderer 30 mm twin screw extruder using a screw speed of 250 rpm and a barrel temperature of 240° C. at 35 lbs. (15.9 kg) The melt can be extruded at a throughput of 1 / hr in a Toyo 110 injection molding machine at a barrel temperature of 240°C and 160°F. (71.1℃) can be injection molded using a mold temperature of 0.15 with minimal molecular weight or discoloration.

[0098] In one aspect of the invention, a cellulose ester resin containing 1 to 30 wt. %, or 1 to 15 wt. %, or 2 to 10 wt. % impact modifier, and no plasticizer, has a heat distortion temperature (HDT) value of greater than 95°C (measured according to ASTM-D648 at a stress level of 1.82 MPa after conditioning at 70°C for 4 hours), and a notched Izod impact strength value of greater than 80 J / m (measured according to ASTM-D256 at 23°C on 3.2 mm thick bars), and a strength of at least 15 inches at 240°C as measured using the procedures described herein. (38.1cm) A melt-processable cellulose ester composition is provided having a spiral flow value of 120°C or more, as measured at 20°C / min according to ASTM-D3418. In one embodiment, the cellulose ester composition has a Tg value greater than 120°C, as measured at 20°C / min according to ASTM-D3418. Unless otherwise specified, notched Izod impact strength tests were performed at 23°C on molded bars after conditioning at 23°C and 50% RH for 48 hours on 3.2 mm thick bars according to ASTM method D256.

[0099] In another embodiment of the present invention, the composition has a melt rheometer resistance of 10,000 PSI as measured in accordance with ASTM-D4440 using a frequency scan between 1 rad / sec and 400 rad / sec, and a plate-plate melt rheometer such as a Rheometrics Dynamic Analyzer (RDA II) using 25 mm diameter parallel plates, a 1 mm gap, and 10% strain. (1,000 Pa·s) It has the following melt viscosity at 240°C and 400 rad / s:

[0100] In one embodiment, the melt-processable cellulose ester composition comprises 1 to 30 wt % or 1 to 15 wt % of an impact modifier, 0 to 15 wt % of a plasticizer, and has a Tg greater than 90° C. In another embodiment, the melt-processable cellulose ester composition comprises 1 to 30 wt % or 1 to 15 wt % of an impact modifier, 0 to 10 wt % of a plasticizer, and has a Tg greater than 100° C. In yet another embodiment, the melt-processable cellulose ester composition comprises 1 to 10 wt % of an impact modifier, 0 to 10 wt % of a plasticizer, and has a Tg greater than 100° C. In another embodiment, the melt-processable cellulose ester composition comprises 1 to 10 wt % of an impact modifier, 0 to 5 wt % of a plasticizer, and has a Tg greater than 115° C.

[0101] In another embodiment of the present invention, the cellulose ester composition has a Tg or heat distortion temperature (Tg) of about 0.455 psi or less that of the base cellulose ester polymer, with only a few degrees Celsius (e.g., less than 5 degrees Celsius, or less than 2 degrees Celsius) reduction due to the incorporation of an impact modifier and the absence of a plasticizer. (3.13kPa) The impact properties of these compositions can also exceed 80 J / m (notched Izod impact strength at 23°C).

[0102] In some embodiments of the present invention, the polymer base resin is According to 48, a 3.2 mm thick bar was heated to 70°C for 4 hours and subjected to a test of 1.82 MPa. 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) 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, 10 It has a heat distortion temperature (HDT) in the range of 5°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 base resin is 56, measured using 3.2 mm thick bars subjected to 48 hours at 23°C and 50% relative humidity of at least 80 J / m, or at least 90 J / m, or at least 100 J / m, or at least 110 J / m, or at least 120 J / m, or at least 130 J / m, or at least 140 J / m, or at least 150 J / m, or at least 160 J / m, or at least 170 J / m, or at least 180 J / m, or at least 190 J / m, or at least 200 J / m. In some embodiments, the polymer-based resin has a modulus of elasticity 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, or about 150 J / m, as measured according to ASTM-D256 using 3.2 mm thick bars at 23° C. and 50% relative humidity for 48 hours. m ~ about 500J / m, about 100J / m - about 400J / m, about 100J / m - about 300J / m, about 100J / m - about 200J / m, about 120J / m - about 500J / m, Approx. 120J / m~Approx. 400J / m, Approx. 120J / m~Approx. 300J / m, Approx. 120J / m~Approx. 200J / m, Approx. 150J / m~Approx. 500J / m, Approx. 150J / m~Approx. 40 0J / m, about 150J / m to about 300J / m, about 150J / m to about 200J / m, about 170J / m to about 500J / m, about 170J / m to about 400J / m, about 170J / m~Approx. 300J / m, Approx. 170J / m~Approx. 200J / m, 180J / m~Approx. 500J / m, Approx. 180J / m~Approx. 400J / m, Approx. 180J / m~Approx. 300J / m, Approx. It has a notched Izod impact strength in the range of 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.

[0104] In some embodiments of the present invention, the polymer base resin is In some embodiments, the polymer base resin has a flexural modulus of greater than 1800 MPa as measured using 3.2 mm thick bars at 23° C. and 50% relative humidity for 48 hours according to ASTM-D790. In some embodiments, the polymer base 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 3.2 mm thick bars at 23° C. and 50% relative humidity for 48 hours according to 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 according to ASTM-D790 using 3.2 mm thick bars subjected to 48 hours at 23° C. and 50% relative humidity. The flexural modulus is about 1900 to about 2500 MPa, about 1900 to about 2800 MPa, or about 1900 to about 3000 MPa, as measured according to ASTM-D790 using a 3.2 mm thick bar subjected to 23°C and 50% relative humidity for 48 hours.

[0105] In some embodiments of the present invention, the cellulose ester composition comprises from 1 wt % to 30 wt %, or from 2 wt % to 15 wt %, based on the total weight of the cellulose ester composition, of an impact modifier, and has an HDT value greater than 95°C, and a notched Izod impact strength value greater than 80 J / m, or greater than 100 J / m, or greater than 120 J / m, and a hardness of 10,000 P at 240°C and 400 rad / sec. (1,000 Pa·s) It has a viscosity of less than 10 ...

[0106] In some embodiments of the present invention, the cellulose ester composition comprises a cellulose The ester composition comprises from 1 wt % to 30 wt %, or from 2 wt % to 15 wt %, of an impact modifier, based on the total weight of the ester composition, and has an HDT value greater than 95°C, and a notched Izod impact strength value greater than 80 J / m, or greater than 100 J / m, or greater than 120 J / m, and a light transmission value greater than 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%, as measured using 3.2 mm plaques after injection molding according to ASTM-D1003 at a barrel set point of 249°C and a 5 minute residence time.

[0107]

[0105] Cellulose esters containing no or low levels of plasticizers are screened. One problem that can occur during melt processing in a melt-plasticizing injection molding machine is that the screw may have difficulty recovering smoothly (poor screw recovery), resulting in poor material feeding and "squeaking" noises. Surprisingly, it has been found that the addition of impact modifiers according to some embodiments of the present invention can eliminate these problems during injection molding.

[0108] In some embodiments of the present invention, the cellulose ester composition comprises a cellulose The ester composition comprises 1 wt % to 30 wt %, or 2 wt % to 15 wt %, of an impact modifier based on the total weight of the ester composition, has an HDT value greater than 95°C, and a notched Izod impact strength value greater than 80 J / m, or greater than 100 J / m, or greater than 120 J / m, and does not produce squealing or have screw recovery problems during injection molding at a barrel set point of 249°C.

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

[0110] In another embodiment of the present invention, the cellulose ester composition may further comprise an antioxidant, a heat and at least one additive selected from the group consisting of stabilizers, release agents, antistatic agents, brighteners, colorants, flow aids, processing aids, plasticizers, anti-fog additives, inorganics, UV stabilizers, lubricants, chain extenders, nucleating agents, reinforcing fillers, wood or wood flour fillers, glass fiber, carbon fiber, flame retardants, dyes, pigments, colorants, additional resins, and combinations thereof.

[0111] In some embodiments, in addition to the impact modifier (discussed herein), the cell 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 an impact modifier (discussed herein), the cellulose ester composition comprises a secondary antioxidant in the range of about 0.1 to about 0.8 wt %, based on the total weight of the composition. In some embodiments, the cellulose ester composition comprises a secondary antioxidant in the range of about 0.1 to about 0.8 wt %, based on the total weight of the composition. 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 wt %, 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 wt %, based on the total weight of the composition, and an acid scavenger in the range of about 0.2 to about 2.0 wt %. 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 wt %, 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 less than 5 wt. %, or less than 2 wt. %, of any other component, based on the total weight of the composition.

[0112] In some embodiments, the cellulose ester composition comprises a maleic anhydride-modified E It does not contain VA. In some embodiments, the cellulose ester composition does not contain a polyetherester compound. In some embodiments, the cellulose ester composition does not contain an adipic acid compound. In some embodiments, the cellulose ester composition contains, based on the total weight of the cellulose ester composition, 65 to 99 wt % of one or more cellulose esters, 1 to 30 wt % of one or more impact modifiers, and less than 5 wt % in total of other components. In some embodiments, such other components do not contain plasticizers, polyetherester compounds, or adipic acid compounds. In some embodiments, the cellulose ester composition contains a dioctyl adipate (DOA) plasticizer and does not contain other adipic acid compounds.

[0113] In another aspect of the present invention, a method for producing a cellulose ester composition is provided. The method comprises contacting at least one cellulose ester, at least one impact modifier, and optionally at least one plasticizer. The cellulose ester, plasticizer, and impact modifier have been discussed hereinabove. In one embodiment, the cellulose ester, impact modifier, and optional plasticizer can be mixed in any order of addition.

[0114] In another embodiment of the present invention, (a) at least one impact modifier, A method for producing a cellulose ester composition is provided, comprising mixing at least one cellulose ester and, optionally, at least one plasticizer for a time and temperature sufficient to disperse the impact modifier and form the cellulose ester composition. A 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 mixing temperature is limited at the upper end by the processing temperature of the impact modifier and at the lower end by the maximum use temperature of the cellulose ester composition.

[0115]

[0113] The mixing efficiency of two or more viscoelastic materials is 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 specified limits to obtain the appropriate particle size.

[0116] In some embodiments, the impact modifier, cellulose ester, and optionally The mixing of the impact modifier, plasticizer, and optional additives can be carried out by any method known in the art that is suitable for dispersing the impact modifier, plasticizer, and additives in the cellulose ester. Examples of mixing devices include a Banbury mixer and a Brabender mixer. The shear energy during mixing is determined by the combination of the device, blade design, rotation speed (rpm) and mixing time. The shear energy must be sufficient to disperse the impact modifier throughout the cellulose ester.

[0117] In some embodiments, the cellulose ester, impact modifier, plasticizer, and The additives and additives can be mixed in any order during the process. In one embodiment, the cellulose ester is premixed with the impact modifier and / or plasticizer. Then, the cellulose ester containing the impact modifier and / or plasticizer is mixed with the additives. In another embodiment of the present invention, when a reactive impact modifier is used, the reactive impact modifier can be mixed with the cellulose ester first, and then the other ingredients are added.

[0118] The compositions of the present invention can be used as molded plastic parts or as solid plastic articles. The compositions are useful as plastics, films, fibers, and sheets. The compositions are suitable for use in any application where a hard, transparent plastic is desired. Examples of such parts include disposable knives, forks, spoons, plates, cups, straws, as well as eyeglass frames, toothbrush handles, toys, automobile trim, tool handles, camera parts, electronic device parts, razor parts, ink pen barrels, disposable syringes, bottles, and the like. In one embodiment, the compositions of the present invention are useful as plastics, films, fibers, and sheets. In one embodiment, the compositions are useful as plastics for making bottles, bottle caps, eyeglass frames, cutlery, disposable cutlery, cutlery handles, shelves, shelf dividers, electronic device housings, electronic device cases, computer monitors, printers, keyboards, pipes, automotive parts, automotive interior parts, automotive trim, signs, thermoformed letters, siding, toys, thermally conductive plastics, ophthalmic lenses, tools, tool handles, and household items. In another embodiment, the compositions of the present invention are suitable for use as films, sheeting, fibers, molded articles, medical devices, packaging, bottles, bottle caps, eyeglass frames, cutlery, disposable cutlery, cutlery handles, shelving, shelf dividers, furniture parts, electronic device housings, electronic device cases, computer monitors, printers, keyboards, pipes, toothbrush handles, automotive parts, automotive interior parts, automotive trim, signs, outdoor signs, skylights, multilayer films, thermoformed letters, siding, toys, toy parts, thermally conductive plastics, ophthalmic lenses and frames, tools, tool handles, and household products, health care products, commercial food service products, boxes, films for graphic arts applications, and plastic films for plastic-glass laminates.

[0119] The cellulose ester compositions can be used in a variety of applications, including fibers, films, molded articles, and sheets. The cellulose ester compositions are useful for forming films, shaped articles, and sheetings. Methods for forming the cellulose ester compositions into fibers, films, shaped articles, and sheetings can be based on methods known in the art. Examples of possible shaped articles include, without limitation, medical devices, medical packaging, health care products, commercial food service products such as food pans, tumblers, and storage boxes, bottles, food processors, blenders, and mixer bowls, household items, water bottles, crisper trays, washing machine fronts, vacuum cleaner parts, and toys. Other possible shaped articles include ophthalmic lenses and frames.

[0120] The present invention further provides one or more compositions comprising the cellulose ester compositions described herein. In some embodiments, the films and / or sheets of the present invention may be of any thickness apparent to one of ordinary skill in the art.

[0121] The present invention further provides one or more of the films and / or sheets described herein. The method of forming the cellulose ester composition into one or more films and / or sheets can be any method known in the art. Examples of films and / or sheets include, but are not limited to, one or more extruded films and / or sheets, one or more calendered films and / or sheets, one or more compression molded films and / or sheets, and one or more solution cast films and / or sheets. Methods for producing films and / or sheets include, but are not limited to, extrusion, calendering, compression molding, wet blocking, dry blocking, and solution casting.

[0122] The present invention further relates to shaped articles as described herein. Methods for forming the composition into a shaped article include methods known in the art. Examples of shaped articles 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. Methods for producing shaped articles include, but are not limited to, injection molding, extrusion, injection-blow molding, injection-stretch-blow molding, and extrusion-blow molding. Methods of the present invention may 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 typical description of an injection blow molding (IBM) 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 the desired final shape around the preform and closing the blow mold around the preform; (4) blowing air into the preform to stretch and expand it to fill the mold; (5) cooling the molded article; and (6) removing the article from the mold.

[0124] The present invention can be used in any injection stretch blow molding manufacturing process known in the art. Without limitation, a typical 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 the desired final shape around the preform and closing the blow mold around the preform; (4) stretching the preform with an internal stretch rod and blowing air into the preform to stretch and expand it 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 typical description of an extrusion blow molding manufacturing process involves (1) melting the 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 the desired final shape around the parison; (4) blowing air into the parison to stretch and expand the extrudate to fill the mold; (5) cooling the molded article; (6) removing the article from the mold; and (7) removing excess plastic (commonly called flash) from the article.

[0126] The present invention can be further illustrated by the following examples of preferred embodiments thereof, it being understood that these examples are included for illustrative purposes only and are not intended to limit the scope of the invention unless otherwise specifically indicated. 10~12 are examples included in the present invention, Comparative Examples 1 and 2 are comparative examples not included in the present invention, and Examples 1-9 and 13-30 is equivalent to a reference example. [Example]

[0127] Examples 1-25 in Tables 1-5 were prepared as follows: First, cellulose powder was mixed with KaneAce B564-MBS impact modifier from Kaneka Corporation or KaneAce ECO100 acrylic impact modifier from Kaneka Corporation together with 1% epoxidized octyl tallate stabilizer in a drum tumbler. (Refractive index: approx. 1.47, particle size: approx. 1.5 μm) It was premixed with either

[0128] The premixed material was then extruded in a Werner & Pflerderer 30 mm twin screw extruder at 35 lbs. (15.9 kg) / hr throughput, a screw speed of 250 rpm, and a barrel temperature of 220°C for the CAP482-based compositions and 240°C for the CA and CAP141-20-based compositions.

[0129] Next, the mixed material was placed in a Toyo 110-ton injection molding machine and heated to 240°C. The mixture was injection molded into 3.2 mm thick x 12.8 mm wide bars using a cast temperature of 100°C and a mold temperature of 70°C.

[0130] The cellulose ester materials used in the examples were selected from Eastman products CAP 482-20, CAP-482-0.5, and CAP 141-20. Heat distortion temperature (HDT) was determined on the bars. Samples were conditioned by placing them in a 70°C oven for 5 hours prior to HDT testing. Molded bars were notched and then tested for notched Izod impact strength according to ASTM method D256 after conditioning for 48 hours at 23°C and 50% RH.

[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. A review of Tables 1-5 shows that Examples 1-25 all have higher toughness than Comparative Examples 1 and 2, which do not contain any impact modifier.

[0132] [Table 1]

[0133] [Table 2]

[0134] [Table 3]

[0135] [Table 4]

[0136] [Table 5]

[0137] Melt processability of Example 12: The flow behavior of Example 12 from Table 2 above was compared to that of conventional plastic materials using a spiral flow test. The spiral flow test was performed using a Toyo 110 ton injection molding machine at 1000 psi (6.89 MPa) injection pressure, 1.0 in. (2.54cm) / sec injection rate, 10 sec fill time, 150 rpm screw speed, 100 psi (689kPa) back pressure, 22 seconds cooling time, 0.5 inch wide (1.27cm) × 0.125 inch thick (0.318cm) The flow length is the length of the spiral formed by molding each material at a specific barrel temperature under the same molding conditions.

[0138] First, spiral flow was performed to determine the flow length values ​​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: Comparative Example 3 was prepared from Eastman® cellulose acetate propionate 482-20 (88 wt %) and dioctyl adipate plasticizer (12 wt %) by adapting the procedure described above.

[0140] In addition to the materials discussed above, for Example 12 and Comparative Example 3, a spiral These materials were tested at the processing temperatures shown in Table 6.

[0134]

[0141] [Table 6]

[0142]

[0135] Examining Table 6, flow length values ​​for commercial materials range from 10 to 30 inches. (25.4~76.2cm) It can be seen that the spiral flow length is between 0.01 and 0.1. The spiral flow of Example 12 shows that this composition has very good flowability (comparable to ABS and SAN, and better than PC), indicating that the inventive examples can be melt processed in injection molding and other processes. Comparative Example 3 (fully plasticized with CAP but no impact modifier) ​​had the highest spiral flow length.

[0143] Light transmittance of Comparative Example 1 and Example 12: The pellets of Comparative Example 1 and Example 12 were mixed in a 150 ton Toyo injection molding machine with a 6.7 oz barrel capacity at 1 inch (2.54cm)Two 4-inch x 4-inch x 0.126 (10.2 cm x 10.2 cm x 0.32 cm) plaques per shot were injection molded at an injection rate of 1 / sec, a nominal barrel temperature of 249°C (480°F), a dwell time of 2 or 5 minutes, and a mold temperature of 80°C. Light transmission was measured according to ASTM-D1003a for plaques molded at 2 and 5 minutes (dwell time). The results are shown in Table 7 below.

[0144] [Table 7]

[0145] In Examples 26-30, cellulose ester compositions were prepared by blending CAP 482-20 with several block copolymer thermoplastic elastomers and additional impact modifiers, such as ABS core-shell impact modifiers. The blending of the cellulose ester compositions was carried out in a Leistritz 18 mm (50:1 L / D ratio) twin-screw extruder at 18 lbs. (8.16kg) The blending was carried out at a throughput of 1 / hr, a screw speed of 250 rpm, and a barrel temperature of 220°C. For the blending of the CA and CAP 141-20 based compositions, the barrel temperature was 230°C. The blended materials were then injection molded into 3.2 mm thick x 12.8 mm wide bars in a Toyo 110 ton injection molding machine using a barrel temperature of 240°C and a mold temperature of 70°C. Properties for these compositions are compared to Comparative Example 1 in Table 8.

[0146] Heat the sample from -110°C at a heating rate of 20°C / min. ASTM Method D34 Glass transition temperatures (Tg) were measured according to 18. DSC scans of blends of materials may show multiple Tg transitions. If more than one Tg transition is observed during a scan, the glass transition of the matrix is ​​defined as the highest Tg measured during the scan.

[0147] For a 3.2 mm thick extruded bar, the bar was heated at 230°C and 50% RH. After conditioning for 48 hours, notched Izod impact strength testing was performed at 23°C after notching according to ASTM method D256.

[0148] [Table 8]

[0149] The above detailed description of several aspects of the present invention will enable those skilled in the art to practice the present invention. It is the intention to describe various aspects of the invention in sufficient detail to enable the reader to understand the present invention. Other embodiments may be utilized, and changes may be made, without departing from the scope of the invention. Accordingly, the above detailed description is not to be construed in a limiting sense. The scope of the present invention is defined solely by the claims set forth in a subsequent regular utility model application, along with the full scope of equivalents to which such claims are entitled.

[0150]

[0141] As used herein, a reference to "one embodiment," "an embodiment," or "embodiments" means that one or more associated features are included in at least one embodiment of the present technology. Separate references to "one embodiment," "an embodiment," or "embodiments" herein do not necessarily refer to the same embodiment and are not mutually exclusive unless so stated and / or apparent to one skilled in the art from the description. For example, a feature, step, etc. described in one embodiment may also be included in other embodiments, but are not necessarily included. Thus, the present invention can encompass various combinations and / or integrations of the embodiments described herein. The present invention includes the following embodiments. (1) A cellulose ester composition comprising 55 to 99 wt. % of at least one cellulose ester, 1 to 30 wt. % of at least one impact modifier, and 0 to 15 wt. % of at least one plasticizer, based on the total weight of the composition, wherein the composition has an HDT value greater than 95°C and a notched Izod impact strength value greater than 80 J / m, measured according to ASTM-D256 at 23°C on a 3.2 mm thick bar after conditioning the bar at 230°C and 50% RH for 48 hours. (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 modifier, and 0 to 15% by weight of the plasticizer. (3) The cellulose ester composition according to (1), wherein the composition contains 70 to 99% by weight of the cellulose ester, 1 to 30% by weight of the impact modifier, and does not contain a plasticizer. (4) The cellulose ester composition according to (3), wherein the composition contains 85 to 99% by weight of the cellulose ester, 1 to 15% by weight of the impact modifier, 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), and cellulose tributyrate (CTB). (6) The cellulose ester composition according to any one of (1) to (2), wherein the cellulose ester is selected from cellulose acetate propionate (CAP) or cellulose acetate butyrate (CAB), and the composition contains 0 to less than 2% by weight of a plasticizer. (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 comprises a plasticizer selected from the group consisting of a phosphate plasticizer, a benzoate plasticizer, an adipate plasticizer, a phthalate plasticizer, a glycolate ester plasticizer, a carbonate plasticizer, a citrate ester plasticizer, and a hydroxyl-functional plasticizer, or a solid amorphous resin plasticizer, or a combination thereof. (10) The cellulose ester composition according to any one of (1) to (9), wherein the impact modifier is a core-shell type impact modifier. (11) The cellulose ester composition according to any one of (1) to (10), wherein the impact modifier is selected from an acrylic core-shell type impact modifier, an ABS core-shell type impact modifier, or an MBS core-shell type impact modifier. (12) The cellulose ester composition according to any one of (1) to (11), wherein the impact modifier 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 modifier has a particle size of 0.01 to 2.0 μm. (14) A thermoplastic, melt-processable cellulose ester composition comprising: 70 to 99% by weight of cellulose esters including one or more of cellulose acetate propionate (CAP) and cellulose acetate butyrate (CAB); 0 to less than 2% by weight of plasticizers; and 1 to 15 wt. % of a core-shell impact modifier having a particle size of 0.01 to 2.0 μm; Includes; The composition has an HDT value greater than 95°C, a notched Izod impact strength value greater than 80 J / m as measured at 23°C on a 3.2 mm thick bar according to ASTM-D256, and a viscosity of 10,000 P (1,000 Pa·s) or less at 400 rad / s 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 antioxidants, heat stabilizers, release agents, antistatic agents, brighteners, colorants, plasticizers, inorganic substances, UV stabilizers, lubricants, nucleating agents, reinforcing fillers, glass fibers, carbon fibers, flame retardants, dyes, pigments, colorants, additional resins, and combinations thereof. (18) An article of manufacture 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 of (18), wherein the article of manufacture 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. 1. An injection molding cellulose ester composition comprising greater than 90 wt % to 99 wt % of a cellulose ester and 1 to less than 10 wt % of at least one impact modifier, based on the total weight of the composition, and no plasticizer, wherein the composition has an HDT value (heat distortion temperature) of greater than 95°C measured at 1.82 MPa using a 3.2 mm thick bar subjected to 70°C for 4 hours according to ASTM-D648, and an HDT value of greater than 95°C measured at 1.82 MPa using a 3.2 mm thick bar subjected to 70°C for 4 hours according to ASTM-D256. cellulose ester composition having a notched Izod impact strength value of greater than 80 J / m as measured at 23°C for a bar of cellulose acetate propionate (CAP) after conditioning the bar for 48 hours at 230°C and 50% RH, wherein the composition contains only cellulose acetate propionate (CAP) as the cellulose ester, and the impact modifier is an acrylic core-shell impact modifier having a refractive index of 1.46 to 1.50 and a particle size of 0.01 to 2.0 μm.

2. 2. The cellulose ester composition of claim 1, wherein the cellulose ester has a total degree of substitution (DS) / anhydroglucose unit (AGU) in the range of 2 to 2.99, an acetyl DS / AGU in the range of greater than 0 to 0.5, and the remainder of the ester groups are propionyl.

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

4. 2. The cellulose ester composition of claim 1, wherein the CAP has an absolute weight average molecular weight of 70,000 to 120,000.

5. 5. The cellulose ester composition according to claim 1, having a notched Izod impact strength value of greater than 100 J / m, measured according to ASTM-D256 on a 3.2 mm thick bar at 23°C after conditioning the bar at 230°C and 50% RH for 48 hours.

6. 6. The cellulose ester composition according to claim 1, wherein the composition is transparent and has a light transmittance of at least 70% as measured using a 3.2 mm plaque after injection molding according to ASTM-D1003 at a barrel set point of 249°C and a residence time of 5 minutes.

7. 1. A thermoplastic, melt-processable, injection-molding cellulose ester composition comprising: greater than 90% by weight but not greater than 99% by weight of cellulose acetate propionate (CAP); and 1 to less than 10% by weight of an acrylic core-shell impact modifier having a refractive index of 1.46 to 1.50 and a particle size of 0.01 to 2.0 μm; Including; Contains no plasticizers; The composition has an HDT value (heat distortion temperature) of greater than 95°C as measured at 1.82 MPa using 3.2 mm thick bars subjected to 70°C for 4 hours according to ASTM-D648, a notched Izod impact strength value of greater than 100 J / m as measured at 23°C on 3.2 mm thick bars according to ASTM-D256 after conditioning the bars at 230°C and 50% RH for 48 hours, and a viscosity of less than or equal to 10,000 P (1,000 Pa s) at 400 rad / sec and 240°C, and the composition comprises only cellulose acetate propionate (CAP) as the cellulose ester.

8. The cellulose ester composition of claim 7, wherein the cellulose ester has a total degree of substitution (DS) / anhydroglucose unit (AGU) in the range of 2 to 2.99, an acetyl DS / AGU in the range of greater than 0 to 0.5, and the remainder of the ester groups are propionyl.

9. 9. The cellulose ester composition of claim 7, wherein the composition is transparent and has a light transmittance of at least 70% as measured using a 3.2 mm plaque after injection molding according to ASTM-D1003 at a barrel set point of 249°C and a residence time of 5 minutes.

10. 10. The cellulose ester composition according to claim 1, further comprising at least one additive selected from the group consisting of antioxidants, heat stabilizers, release agents, antistatic agents, brighteners, colorants, inorganics, UV stabilizers, lubricants, nucleating agents, reinforcing fillers, glass fibers, carbon fibers, flame retardants, dyes, pigments, colorants, additional resins, and combinations thereof.

11. An injection molded article comprising the cellulose ester composition of any one of claims 1 to 10, said composition having a notched Izod impact strength of at least 150 J / m.

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