Anti-scratch compositions and articles comprising the same

Abstract

A composition includes particular amounts of a poly(methyl methacrylate), a poly(carbonate-siloxane), an acrylic impact modifier, a polyethylene, and a siloxane-containing anti-scratch additive. The composition can exhibit a desirable combination of good mechanical properties and scratch resistance. Methods of making the composition and articles comprising the composition are also disclosed.

Description

ANTI-SCRATCH COMPOSITIONS AND ARTICLES COMPRISING THE SAMECROSS REFERENCE TO RELATED APPLICATIONSThis application claims priority to and the benefit of European Patent Application No. 23202147.7, filed on October 6, 2023, the entire content of which is incorporated by reference herein.BACKGROUND

[0001] Poly (methyl methacrylate) (PMMA) is useful for scratch resistant and transparent or high gloss thermoplastic compositions. However, due to its low impact strength PMMA is not generally well-suited for demanding applications such as automotive components or consumer electronics (e.g., consumer electronic housings). Polycarbonate (PC) has excellent impact strength and transparency but tends to lack scratch-resistant properties.

[0002] Efforts to improve scratch resistance include, for example, hard-coating the compositions. This approach may not be desirable in all applications. For example, an expensive additional processing step is introduced to the manufacturing process for the hard- coating. Addition of impact modifiers has been explored to improve impact strength; however, impact modifiers can negatively affect scratch visibility (e.g., by making scratches appear whiter).

[0003] Accordingly, there remains a continuing need in the art for improved scratchresistant compositions. It would be a further advantage to provide scratch-resistant compositions also having improved impact strength.SUMMARY

[0004] A composition comprises 40 to 79.4 weight percent of a poly(methyl methacrylate); 10 to 25 weight percent of a poly(carbonate-siloxane) having a siloxane content of 30 to 70 weight percent, preferably 35 to 65 weight percent, based on the total weight of the poly(carbonate-siloxane); 10 to 25 weight percent of an acrylic impact modifier; 0.1 to less than 3 weight percent of a polyethylene; and 0.5 to 5 weight percent of a siloxane-containing antiscratch additive; wherein the weight percent of each component is based on the total weight of the composition, wherein a molded sample of the composition exhibits: a notched Izod impact strength of greater than 50 J / m, preferably greater than 60 J / m, at 23 °C, 5.5 Ibf, as measured in accordance with ASTM D256, and a scratch line roughness Ra of less than 0.2, preferably less than 0.15, determined using Keyence Laser Scanning Confocal Microscopy.

[0005] A method of making the composition comprises melt-mixing the components of the composition, and, optionally, extruding the composition.

[0006] An article comprising the composition represents another aspect of the present disclosure.

[0007] The above described and other features are exemplified by the following detailed description.BRIEF DESCRIPTION OF THE DRAWINGS

[0008] The following figures are exemplary embodiments.

[0009] FIG. 1 is a laser scanning confocal microscopy image of scratches in compositions according to various examples.

[0010] FIG. 2 shows delamination testing results for select examples.DETAILED DESCRIPTION

[0011] Provided herein is a composition having a combination of good scratch resistance and impact strength. The composition includes particular amounts of a poly(methyl methacrylate), a poly (carbonate- siloxane), an acrylic impact modifier, a polyethylene, and a siloxane-containing anti-scratch additive. The present inventors have unexpectedly determined that compositions including the particular components described herein possess a synergy due to use of polyethylene at low concentrations and a siloxane-containing anti-scratch additive. The resulting composition can avoid processing issues (for example, delamination) and exhibit the desired combination of physical performance and compatibility.

[0012] Accordingly, an aspect of the present disclosure is a composition comprising a poly(methyl methacrylate), a poly(carbonate-siloxane), an acrylic impact modifier, a polyethylene, and a siloxane-containing anti-scratch additive.

[0013] Any suitable poly (methyl methacrylate) polymer or a copolymer thereof can be used. In an aspect, the poly(methyl methacrylate) can be a homopolymer, obtained by polymerization (e.g., free radical polymerization) of a methyl methacrylate monomer. In an aspect, the poly(methyl methacrylate) can be a copolymer, obtained by polymerization (e.g., free radical polymerization) of a methyl methacrylate monomer and at least one additional monomer suitable for copolymerization with methyl methacrylate. Suitable comonomers can be readily determined by one of skill in the art. For example, copolymerizable monomers can include, but are not limited to, C2-10 alkyl(meth)acrylate monomers such as ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, or 2-ethylhexyl (meth)acrylate; (meth)acrylates derived from unsaturated alcohols such as oleyl (meth)acrylate, 2-propynyl (meth)acrylate, allyl (meth)acrylate or vinyl (meth)acrylate; aryl (meth)acrylates, such as benzyl (meth)acrylate or phenyl (meth)acrylate, wherein in each case the aryl can be substituted or unsubstituted; cycloalkyl (meth)acrylates, such as 3- vinylcyclohexyl (meth)acrylate, or bornyl (meth) acrylate; hydroxyalkyl (meth)acrylates, such as 3-hydroxypropyl (meth)acrylate, 3,4-dihydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, or 2-hydroxypropyl (meth)acrylate; 1 ,4-butanediol (meth)acrylate; tetrahydrofurfuryl (meth)acrylate; vinyloxyethoxyethyl (meth)acrylate; ethylsulphinylethyl (meth)acrylate; 4-thiocyanatobutyl (meth)acrylate; ethylsulphonylethyl (meth)acrylate; thiocyanatomethyl (meth)acrylate; methylsulphinylmethyl (meth)acrylate; bis((meth)acryloyloxyethyl) sulphide; or trimethyloylpropane tri(meth)acrylate. In an aspect, the copolymerizable monomers can include amides of or nitrile derivatives of (meth)acrylic acid, such as N-(3-dimethylaminopropyl) (meth)acrylamide or (meth)acrylonitrile. In an aspect, the copolymerizable monomers can include 1 -alkenes, such as 1 -hexene, 1 -heptene, or butene; branched alkenes, such as vinylcyclohexane, 3,3 dimethyl- 1 -propene, 3 -methyl- 1 -diisobutylene, or 4-methyl-l -pentene; vinyl esters, such as vinyl acetate; styrene, o-methylstyrene or o- ethylstyrene; substituted styrenes having Ci-4 alkyl or halogen substituent(s), such as vinyltoluene, p-methylstyrene, mono-chlorostyrenes, dichlorostyrenes, tribromostyrenes, or tetrabromostyrenes; heterocyclic vinyl compounds, such as 2-vinylpyridine, 3-vinylpyridine, 2- methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2- methyl-l-vinylimidazole, N- vinyl-pyrrolidone, 2- vinylpyrrolidone, N-vinylpyrrolidine, 3 vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxolane, vinylfuran, vinylthiophene, vinylthiolane, vinylthiazoles, hydrogenated vinylthiazoles, vinyloxazoles or hydrogenated vinyloxazoles; vinyl ethers; isoprenyl ethers; maleic acid derivatives, such as maleic anhydride, methylmaleic anhydride, maleimide, or methylmaleimide; or dienes, such as divinylbenzene. Combinations of any of the foregoing copolymerizable monomers can also be used.

[0014] In an aspect, the poly(methyl methacrylate) can have a methyl methacrylate content of at least 70 weight percent, or at least 80 weight percent, or at least 90 weight percent, or at least 95 weight percent, based on the total weight of the poly(methyl methacrylate) polymer. In an aspect, the poly(methyl methacrylate) comprises 100 weight percent methyl methacrylate repeating units (i.e., is a methyl methacrylate homopolymer).

[0015] In an aspect, the poly(methyl methacrylate) can include a combination of different poly(methyl methacrylate) homopolymers or copolymers (e.g., as a blend), for example poly(methyl methacrylate)s having different molecular weights or comprising different repeating unit compositions.

[0016] In an aspect, the weight average molecular weight of the poly(methyl methacrylate) can be, for example, 10,000 to 1,000,000 grams per mole (g / mol), or 20,000 to 1,000,000 g / mol, or 50,000 to 500,000 g / mol or 80,000 to 300,000 g / mol. Weight average molecular weight can be determined by gel permeation chromatography relative to poly(methyl methacrylate) standards.

[0017] In an aspect, the poly(methyl methacrylate) can have a melt volume flow rate of 7 to 12 cubic centimeters per 10 minutes (cm3 / 10 mins) at 240 °C, 2.16 kilogram (kg), 300 seconds (s), as measured in accordance with ISO 1133.

[0018] Poly(methyl methacrylate)s are commercially available as, for example, ACRYLITE™ POQ66 from Evonik, or PLEXIGLAS™ V920A or ALTUGLAS™ V825T, both available from Arkema.

[0019] In an aspect, the poly(methyl methacrylate) can be derived from post-consumer recycled or post-industrial recycled materials or can be produced from at least one monomer derived from bio-based or plastic waste feedstock.

[0020] The poly(methyl methacrylate) can be present in the composition in an amount of 40 to 79.4 weight percent, based on the total weight of the composition. Within this range, the poly(methyl methacrylate) can be present in an amount of 45 to 75 weight percent, or 50 to 75 weight percent, or 55 to 75 weight percent, or 57 to 72 weight percent, or 60 to 70 weight percent, each based on the total weight of the composition.

[0021] In addition to the poly (methyl methacrylate), the composition further comprises a poly(carbonate-siloxane). The poly(carbonate-siloxane) comprises polycarbonate blocks comprising repeating units according to Formula (1)and polysiloxane blocks. In Formula (1), at least 60 percent of the total number of R1groups contain aromatic moieties and the balance thereof are aliphatic, alicyclic, or aromatic. In an aspect, each R1is a Ce-30 aromatic group, that is, contains at least one aromatic moiety. R1can be derived from an aromatic dihydroxy compound of the formula HO-R^OH, in particular of formula (Hwherein each of A1and A2is a monocyclic divalent aromatic group and Y1is a single bond or a bridging group having one or more atoms that separate A1from A2. In an aspect, one atom separates A1from A2. Preferably, each R1can be derived from a bisphenol of formula (3)wherein Raand Rbare each independently a halogen, C1-12 alkoxy, or C1-12 alkyl, and p and q are each independently integers of 0 to 4. It will be understood that when p or q is less than 4, the valence of each carbon of the ring is filled by hydrogen. Also in formula (3), Xais a bridging group connecting the two hydroxy-substituted aromatic groups, where the bridging group and the hydroxy substituent of each Ce arylene group are disposed ortho, meta, or para (preferably para) to each other on the Ce arylene group. In an aspect, the bridging group Xais single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, or a Ci-60 organic group. The organic bridging group can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous. The Ci-60 organic group can be disposed such that the Ce arylene groups connected thereto are each connected to a common alkylidene carbon or to different carbons of the Ci-eo organic bridging group. In an aspect, p and q are each 1, and Raand Rbare each a C1-3 alkyl group, preferably methyl, disposed meta to the hydroxy group on each arylene group.

[0022] The polysiloxane blocks comprise repeating diorganosiloxane units as in formula(4)wherein each R is independently a C1-13 monovalent organic group. For example, R can be a Ci- 13 alkyl, Ci-13 alkoxy, C2-13 alkenyl, C2-13 alkenyloxy, C3-6 cycloalkyl, C3-6 cycloalkoxy, Ce-14 aryl, Ce-io aryloxy, C7-13 arylalkylene, C7-13 arylalkylenoxy, C7-13 alkylarylene, or C7-13 alkylaryleneoxy. The foregoing groups can be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof. In an aspect, where a transparent poly(carbonate-siloxane) is desired, R is unsubstituted by halogen. Combinations of the foregoing R groups can be used in the same copolymer.

[0023] The value of E in formula (4) can vary widely depending on the type and relative amount of each component in the composition, the desired properties of the composition, andlike considerations. Generally, E has an average value of 2 to 1,000, preferably 2 to 500, 2 to 200, or 2 to 125, 5 to 80, or 10 to 70. In an aspect, E has an average value of 10 to 80 or 10 to 40, and in still another aspect, E has an average value of 40 to 80, or 40 to 70. Where E is of a lower value, e.g., less than 40, it can be desirable to use a relatively larger amount of the poly(carbonate-siloxane). Conversely, where E is of a higher value, e.g., greater than 40, a relatively lower amount of the poly(carbonate-siloxane) can be used. A combination of a first and a second (or more) poly(carbonate-siloxane)s can be used, wherein the average value of E of the first copolymer is less than the average value of E of the second copolymer.

[0024] In an aspect, the polysiloxane blocks are of formula (5)wherein E and R are as defined if formula (4); each R can be the same or different and is as defined above; and Ar can be the same or different and is a substituted or unsubstituted Ce-30 arylene, wherein the bonds are directly connected to an aromatic moiety. Ar groups in formula (5) can be derived from a Ce-30 dihydroxyarylene compound, for example a dihydroxyarylene compound of formula (3) or an aromatic dihydroxy compound of formula (6)wherein each Rhis independently a halogen atom, Ci-io hydrocarbyl group such as a Ci-io alkyl, a halogen-substituted Ci-io alkyl, a Ce-io aryl, or a halogen-substituted Ce-io aryl, and n is 0 to 4. The halogen is usually bromine. Particular dihydroxy arylene compounds are 1 ,l-bis(4- hydroxyphenyl) methane, l,l-bis(4-hydroxyphenyl) ethane, 2,2-bis(4-hydroxyphenyl) propane, 2,2-bis(4-hydroxyphenyl) butane, 2,2-bis(4-hydroxyphenyl) octane, l,l-bis(4-hydroxyphenyl) propane, l,l-bis(4-hydroxyphenyl) n-butane, 2,2-bis(4-hydroxy-l -methylphenyl) propane, 1,1- bis(4-hydroxyphenyl) cyclohexane, bis(4-hydroxyphenyl sulfide), and l,l-bis(4-hydroxy-t- butylphenyl) propane.

[0025] In another aspect, polysiloxane blocks are of formula (7)wherein R and E are as described above, and each R2is independently a divalent C1-30 organic group, and wherein the polymerized polysiloxane unit is the reaction residue of its corresponding dihydroxy compound. In a specific aspect, the polysiloxane blocks are of formula (8)wherein R and E are as defined above. R2in formula (8) is a divalent C2-8 aliphatic group. Each M in formula (8) can be the same or different, and can be a halogen, cyano, nitro, Ci-s alkylthio, C1-8 alkyl, C1-8 alkoxy, C2-8 alkenyl, C2-8 alkenyloxy, C3-8 cycloalkyl, C3-8 cycloalkoxy, Ce-io aryl, Ce-io aryloxy, C7-12 aralkyl, C7-12 aralkoxy, C7-12 alkylaryl, or C7-12 alkylaryloxy, wherein each n is independently 0, 1, 2, 3, or 4.

[0026] In an aspect, M is bromo or chloro, an alkyl such as methyl, ethyl, or propyl, an alkoxy such as methoxy, ethoxy, or propoxy, or an aryl such as phenyl, chlorophenyl, or tolyl; R2is a dimethylene, trimethylene or tetramethylene; and R is a C1-8 alkyl, haloalkyl such as trifluoropropyl, cyanoalkyl, or aryl such as phenyl, chlorophenyl or tolyl. In another aspect, R is methyl, or a combination of methyl and trifluoropropyl, or a combination of methyl and phenyl. In still another aspect, R is methyl, M is methoxy, n is one, and R2is a divalent C1-3 aliphatic group. Specific polysiloxane blocks are of the formulaor a combination thereof, wherein E has an average value of 2 to 200, 2 to 125, 5 to 125, 5 to 100, 5 to 50, 20 to 80, or 5 to 20.

[0027] Blocks of formula (9) can be derived from the corresponding dihydroxy polysiloxane, which in turn can be prepared effecting a platinum-catalyzed addition between the siloxane hydride and an aliphatically unsaturated monohydric phenol such as eugenol, 2- alkylphenol, 4-allyl-2-methylphenol, 4-allyl-2-phenylphenol, 4-allyl-2-bromophenol, 4-allyl-2-t- butoxyphenol, 4-phenyl-2-phenylphenol, 2-methyl-4-propylphenol, 2-allyl-4,6-dimethylphenol, 2-allyl-4-bromo-6-methylphenol, 2-allyl-6-methoxy-4-methylphenol and 2-allyl-4,6-dimethylphenol. The poly(carbonate-siloxane)s can then be manufactured, for example, by the synthetic procedure of European Patent Application Publication No. 0 524 731 Al of Hoover, page 5, Preparation 2.

[0028] Transparent poly(carbonate-siloxane)s comprise carbonate units (1) derived from bisphenol A, and repeating siloxane units (9a), (9b), (9c), or a combination thereof (preferably of formula 9a), wherein E has an average value of 4 to 50, preferably 5 to 15, more preferably 6 to 15, and still more preferably 7 to 10. The transparent copolymers can be manufactured using one or both of the tube reactor processes described in U.S. Patent Application No. 2004 / 0039145A1 or the process described in U.S. Patent No. 6,723,864 can be used to synthesize the poly(carbonate-siloxane)s.

[0029] The poly(carbonate-siloxane) has a siloxane content of 30 to 70 wt%, based on the total weight of the poly(carbonate-siloxane). Within this range, the poly(carbonate-siloxane) can have a siloxane content of greater than 30 to 70 weight percent, or 35 to 70 weight percent, or 35 to 65 weight percent. As used herein, “siloxane content” of a poly(carbonate-siloxane) refers to the content of siloxane units based on the total weight of the poly(carbonate-siloxane).

[0030] In an aspect, the poly(carbonate-siloxane) can be derived from post-consumer recycled or post-industrial recycled materials or can be produced from at least one monomer derived from bio-based or plastic waste feedstock.

[0031] In an aspect, the poly(carbonate-siloxane) can have a weight average molecular weight of 17,000 to 50,000 g / mol. Within this range, the weight average molecular weight can be 17,000 to 45,000 g / mol, or 20,000 to 45,000 g / mol, or 30,000 to 45,000 g / mol, or 32,000 to 36,000 g / mol, or 30,000 to 45,000 g / mol, or 32,000 to 45,000 g / mol, or 35,000 to 45,000 g / mol, or 35,000 to 40,000 g / mol, or 32,000 to 40,000 g / mol. In an aspect, the poly(carbonate-siloxane) can have a weight average molecular weight of 26,000 to 45,000 g / mol, or 30,000 to 45,000 g / mol, or 35,000 to 40,000 g / mol. The weight average molecular weight can be determined by gel permeation chromatography using a crosslinked styrene-divinyl benzene column, at a sample concentration of 1 milligram per milliliter, and as calibrated using polystyrene standards and calculated for polycarbonate.

[0032] The poly(carbonate-siloxane)s can have a melt volume flow rate, measured at 300 °C / 1.2 kg, of 1 to 50 cubic centimeters per 10 minutes (cc / 10 min), preferably 2 to 30 cc / 10 min. Combinations of the poly(carbonate-siloxane)s of different flow properties can be used to achieve the overall desired flow property.

[0033] The poly(carbonate-siloxane) can be present in the composition in an amount effective to provide a total siloxane content of 1 to 25 weight percent, or 3 to 22 weight percentor 3 to 15 weight percent, or 3 to 10 weight percent, or 5 to 10 weight percent, each based on the total weight of the composition.

[0034] In an aspect, the composition can have a total siloxane content of 6 to 10 weight percent, and the weight average molecular weight of the poly (carbonate- siloxane) can be greater than 21,000 g / mol. In an aspect, the composition can have a total siloxane content that is 6 to 10 weight percent, and the weight average molecular weight of the polycarbonate-siloxane copolymer can be greater than 25,000 to less than 45,000 g / mol. In an aspect, the composition can have a total siloxane content that is 6 to 10 weight percent, and the weight average molecular weight of the poly(carbonate-siloxane) can be greater than 30,000 to less than 40,000 g / mol.

[0035] The poly(carbonate-siloxane) can be present in the composition in an amount of 10 to 25 weight percent, based on the total weight of the composition. Within this range, the poly(carbonate-siloxane) can be present in an amount of 10 to 20 weight percent, or 10 to 18 weight percent, or 12 to 18 weight percent, each based on the total weight of the composition.

[0036] In an aspect, the composition comprises less than or equal to 5 weight percent or less than or equal to 1 weight percent, or less than or equal to 0.1 weight percent of an auxiliary poly(carbonate-siloxane) comprising greater than 70 to 98 weight percent, more preferably 75 to 97 weight percent of carbonate units and less than 30 weight percent, or 2 to less than 30 weight percent, or 3 to 25 weight percent siloxane units. In an aspect, an auxiliary polycarbonatesiloxane) copolymer can be excluded from the composition. Stated another way, in an aspect, the composition can minimize (e.g., include less than 5 weight percent, or less than 1 weight percent, or less than 0.1 weight percent) or exclude a poly(carbonate-siloxane) having a siloxane content of less than 30 weight percent, based on the total weight of the poly(carbonate-siloxane).

[0037] In addition to the poly(methyl methacrylate) and the poly(carbonate-siloxane), the composition further comprises an acrylic impact modifier. The acrylic impact modifiers can be in the form of homopolymers or copolymers, including random, block, radial block, graft, and core-shell copolymers. Combinations of acrylic impact modifiers can be used.

[0038] In an aspect, exemplary acrylic impact modifiers can include an acrylic copolymer-containing impact modifier can comprise acrylonitrile-butadiene-styrene polymer (ABS) such as bulk polymerized ABS (BABS), an acrylonitrile-styrene-butyl acrylate (ASA) polymer, a methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) polymer, a methyl methacrylate-butadiene-styrene (MBS) polymer, and an acrylonitrile-ethylene-propylene-diene- styrene (AES) polymer, or a combination thereof.

[0039] In an aspect, the impact modifier can be a multilayer impact modifier comprising a core and one or more shells. As described above, the core can be elastomeric and the shell can be rigid. In an aspect, the multilayer impact modifier can comprise butyl acrylate as a rubber component. In an aspect, the multilayer impact modifier can comprise methyl methacrylate polymer as the rigid component. In an aspect, the multilayer impact modifier can have a core- shell-shell structure in which a core (C) is surrounded by a first shell (SI) which is in turn surrounded by a second shell (S2). The core and first shell (e.g., the inner shell) can be elastomeric and the second shell (e.g., the outer shell) can be rigid. In an aspect, the weight ratio of C:(S1+S2) can be 10:90 to 40:60. The core and the first shell can contain an elastomeric (i.e., rubbery) polymer phase having a glass transition temperature (Tg) of less than 10°C, or less than -10°C, or -40 to -80°C. The second shell can contain a rigid polymeric superstrate grafted to the elastomer phase. In an aspect, the core can contain a first butyl acrylate polymer. In an aspect, the first shell can contain a second butyl acrylate polymer. In an aspect, the second shell can contain at least 50 weight percent of a methyl methacrylate polymer based on the total weight of the second shell. In an aspect, the multilayer impact modifier can have a particle size of 100 to 1000 nanometers (nm), for example 150 to 500 nm, or 175 to 250 nm. In an aspect, the number average particle diameter of the multilayer impact modifier can be 30 to 400 nm. Particle size can be determined by methods which are generally known, for example light scattering methods.

[0040] In an aspect, the core of the multilayer impact modifier can comprise a core polymer comprising 40 to 99.9 weight percent, or 55 to 90 weight percent of alkyl methacrylate repeat units, alkyl acrylate repeat units or styrenic repeat units; 0 to 59.9 weight percent of a copolymerizable monomer other than the alkyl methacrylate, alkyl acrylate, or styrenic repeat units; and 0.1 to 5 weight percent of a polyfunctional monomer, based on the total weight of the core. In an aspect, the core polymer can be a butyl acrylate polymer.

[0041] In an aspect, the first shell of the multilayer impact modifier can comprise a first shell polymer comprising 50 to 99.9 weight percent, preferably 70 to 99 weight percent of a (C2- 8 alkyl) acrylate; 0 to 49.9 weight percent, preferably 0 to 29 weight percent of a copolymerizable vinyl monomer that is not an alkyl acrylate; and 0.1 to 10 weight percent, preferably 0.1 to 5 weight percent of a polyfunctional monomer, based on the total weight of the first shell. Polymerization of the monomers for the first shell in the presence of the core polymers can result in the core polymer being mainly distributed at the center portion of the impact modifier. In an aspect, the first shell polymer can be a butyl acrylate polymer.

[0042] In an aspect, the second shell of the multilayer impact modifier can be a graft component. In an aspect, second shell can contain homopolymer or a copolymer derived from astyrenic compound, (meth)acrylonitrile, (meth)acrylic acid, a (Ci-6 alkyl) (meth)acrylate, or a combination thereof. In an aspect, the second shell can contain, 50 to 100 weight percent, preferably 80 to 100 weight percent of methyl methacrylate repeat units; and 0 to 50 weight percent, preferably 0 to 20 weight percent of a copolymerizable vinyl monomer other than the methyl methacrylate, based on the total weight of the outer shell. In an aspect, the outer shell polymer can be a methyl methacrylate polymer.

[0043] In an aspect, the multilayer impact modifier can have a refractive index of 1.45 to 1.55, or 1.47 to 1.51, or about 1.49, or at least any one of, equal to any one of, or between any two of 1.45, 1.46, 1.47, 1.48, 1.49, 1.5, 1.50, 1.51, 1.52, 1.53, 1.54, and 1.55. In an aspect, the ratio of refractive indexes of the poly(methyl methacrylate) and the multilayer impact modifier can be 1.05:1 to 1:1.05.

[0044] In an aspect, the rubber content of the impact modifier can be 30 to 90 weight percent. Impact modifiers can be as described, for example, in U.S. Publication No. 2013 / 0184375. In an aspect, the impact modifier can be a powder product with having a multilayer structure which comprises butyl acrylate as a rubber component, such as KANE ACE™ M-210 available from Kaneka.

[0045] The acrylic impact modifier can be included in the composition in an amount of 10 to 25 weight percent, based on the total weight of the composition. Within this range, the impact modifier can be present in an amount of 12 to 25 weight percent, or 10 to 20 weight percent, or 12 to 18 weight percent, or 13 to 17 weight percent, each based on the total weight of the composition.

[0046] In addition to the poly(methyl methacrylate), the poly(carbonate-siloxane), and the acrylic impact modifier, the composition further comprises a polyethylene. The polyethylene can be a low density polyethylene (LDPE), a high density polyethylene (HDPE), or a combination thereof. In an aspect, a polyethylene having a medium-to-high melt volume flow rate can be preferred. For example, the polyethylene can preferably have a melt-volume flow rate of greater than 6 g / 10 minutes, preferably greater than 15 g / 10 minutes, more preferably greater than 20 g / 10 minutes, as determined according to ISO 1133 at 290°C and 2.16 kilograms.

[0047] In an aspect, the composition can comprise a low density polyethylene (LDPE). LDPE is a branched polyethylene. LDPE generally has decreased crystallinity and lower density. For example, the density of LDPE can be less than 0.940 g / cm3, or 0.91 to 0.93 g / cm3, for example as determined according to ASTM D792. LDPE can be prepared at hightemperatures and pressures, which results in complex branched molecular structures. The amount of branching and the density can be controlled by the polymerization conditions.

[0048] In an aspect, the composition can comprise a high density polyethylene (HDPE). HDPE has little branching in the polyethylene structure. HDPE generally has an increased crystallinity and a higher density (e.g., as compared to LDPE). For example, the density of HDPE can be greater than or equal to 0.940 g / cm3, or 0.94 to 0.97 g / cm3, for example as determined according to ASTM D792.

[0049] The polyethylene can be present in the composition in an amount of 0.1 to less than 3 weight percent, based on the total weight of the composition. Within this range, the first anti-scratch additive can be present in an amount of 0.5 to 2.5 weight percent, or 0.5 to 2.25 weight percent, or 0.75 to 2.25 weight percent, or 1 to 2.5 weight percent, or 1 to 2 weight percent, each based on the total weight of the composition.

[0050] The composition further comprises a siloxane-containing anti-scratch additive. The siloxane-containing anti-scratch additive can be an organomodified polysiloxane, for example according to the formulawherein R3is independently at each occurrence a Ci-ii alkyl group, preferably a Ci-4 alkyl group, more preferably a methyl group; R4is independently at each occurrence an R3group or a polyester moiety; R5is independently at each occurrence an R3group, a polyester moiety, or a C12-36 hydrocarbyl group; and n, m, and p are independently 0 to 58, provided that n+m+p+2 is 15 to 75, preferably 20 to 50. Additionally, when m and p are 0, R4is not R3and when R4is R3, at least one of m and p is not 0. When R5is R3, then R4is not R3. When R4is R3, then at least one R5is not R3. In an aspect, p=0.

[0051] If R4or R5are polyester moieties, the polyester moieties comprise 3 to 30, or 8 to 25, or 15 to 25 ester repeating units. The polyester moieties can have, as starter alcohols, those alcohol moieties which derive from primary unsaturated alcohols. The polyester moieties preferably have the structure -Rq-(Rr)zH, wherein Rqis -(CH2)X-O- and Rris -C(=O)-(CH2)y-O- and x is an integer from 2 to 10, preferably 3 to 7, more preferably 5 to 7, y is an integer from 2 to 10, preferably 3 to 8, more preferably 4 to 5, and z is an integer from 3 to 30, preferably 8 to 25, more preferably 15 to 25.

[0052] The polyester moieties can be derived from the same or different starting molecules. In an aspect, the polyester moieties are derived from identical starting molecules. Preferred polyester moieties include those obtained by, for example, ring-opening polyesterification of lactones. In an aspect, the polyester moieties are those obtained via polyesterification of caprolactone or valerolactone, in particular of e-caprolactone, 3,5,5- trimethylcaprolactone or 8-valerolactone. In an aspect, the polyester moiety can be derived from e-caprolactone.

[0053] In an aspect, R4and / or R5are polyester moieties, wherein the polyester moiety comprises repeating units (e.g., 3 to 30 repeating units) derived from e-caprolactone. In an aspect, each R4is an identical polyester moiety.

[0054] In an aspect, in addition to R4comprising a polyester moiety, it can be preferred for at least one R5to also be a polyester moiety. When R4and R5each comprise a polyester moiety, the polyester moieties can preferably be identical (i.e., have the same number of repeating units derived from the same starting molecule).

[0055] In an aspect, if all of the moieties R4are R3, where R3is preferably a methyl group, R5is preferably a C12-36 hydrocarbon moiety, preferably a C20-30 hydrocarbon moiety. In this aspect, n+m+p+2 is preferably greater than or equal to 30, preferably from 40 to 50, wherein p is preferably 0, and m is preferably from 30 to 48.

[0056] In an aspect, if one or more of the moieties R4and / or R5is a polyester moiety, then n+m+p+2 is preferably from 10 to 45, preferably from 20 to 30 and particularly preferably from 20 to less than 30. If the R5moieties are polyester moieties, p is preferably 0, and the value of m is from 1 to 10, preferably from 2 to 5.

[0057] The siloxane-containing anti-scratch compounds can be obtained by the known processes via reaction of corresponding hydrosiloxanes with unsaturated hydrocarbons or unsaturated alcohols and subsequent (poly)esterification, or via direct reaction of unsaturated polyesters with hydrosiloxanes. The reaction can be carried out as described in European Patent Application Publication No. 1 640 418 via hydrosilylation or via dehydrogenative hydrosilylation. The production of polysiloxanes having polyester moieties can be found by way of example in European Patent Application Publication No. 0 208 734.

[0058] Examples of suitable siloxane-containing compounds can include TEGOMER™ H-Si 6441 P, TEGOMER™ H-Si 6444 P, and TEGOMER™ M-Si 2650, each commercially available from Evonik.

[0059] In an aspect, the siloxane-containing additive can comprise an ultra-high molecular weight (UHMW) polysiloxane in a polymer matrix. As used herein, “ultra-highmolecular weight” means that the polysiloxane has a number average molecular weight greater than 40,000 grams per mole, or greater than or equal to 100,000 grams per mole, or greater than or equal to 200,000 grams per mole. The polymer matrix can comprise a thermoplastic polymer, for example low density polyethylene, polycarbonate, a styrene-acrylonitrile copolymer, or a polycarbonate / acrylonitrile-butadiene-styrene blend.

[0060] Exemplary UHMW polysiloxane additives can include those available under the tradename MULTIBASE™, available from Dupont.

[0061] The siloxane-containing anti-scratch additive is present in the composition in an amount of 0.5 to 5 weight percent, based on the total weight of the composition. Within this range, the second anti-scratch additive can be present in an amount of 0.5 to 4.5 weight percent, or 0.5 to 4 weight percent, or 0.75 to 4.5 weight percent, or 0.75 to 4 weight percent, or 1 to 4.5 weight percent, or 1 to 4 weight percent, each based on the total weight of the composition.

[0062] The composition can further optionally comprise an additive composition. The additive composition can include various additives ordinarily incorporated into polymer compositions of this type, with the proviso that the additive(s) are selected so as to not significantly adversely affect the desired properties of the composition, in particular scratch resistance and impact strength. Such additives can be mixed at a suitable time during the mixing of the components for forming the composition. Additives include processing aids, fillers, reinforcing agents, antioxidants, heat stabilizers, light stabilizers, ultraviolet (UV) light stabilizers, plasticizers, lubricants, mold release agents, antistatic agents, colorants such as such as titanium dioxide, carbon black, and organic dyes, surface effect additives, radiation stabilizers, flame retardant, hydrostabilizers, epoxy resins, and anti-drip agents. A combination of additives can be used, for example a combination of one or more of a processing aid, a heat stabilizer, an ultraviolet light stabilizer, and a colorant.

[0063] In general, the additives are used in the amounts generally known to be effective. For example, the total amount of the additives (other than any impact modifier, filler, or reinforcing agents) can be 0.01 to 2 weight percent, or 0.1 to 2 weight percent, or 0.2 to 2 weight percent, or 0.2 to 1 weight percent, each based on the total weight of the composition.

[0064] The composition of the present disclosure can optionally exclude other components not specifically described here. For example, the composition can exclude thermoplastic polymers other than the poly (methyl methacrylate), the poly (carbonate- siloxane), the impact modifier, and the polyethylene. The composition can optionally exclude impact modifiers other than the acrylic impact modifier. The composition can optionally exclude apolyolefin other than the polyethylene. The composition can optionally exclude an anti-scratch additive other than the polyethylene and the siloxane-containing anti-scratch additive.

[0065] It will be understood that the total amount of the combined components sum to 100 weight percent.

[0066] The composition can exhibit good scratch resistance and impact strength when a particular combination of poly (methyl methacrylate), poly (carbonate- siloxane), acrylic impact modifier, polyethylene, and siloxane-containing anti-scratch additives are present in the composition, each in particular amounts.

[0067] A molded sample of the composition including particular amounts of the components described herein can exhibit one or both of improved scratch resistance and impact strength, preferably both improved scratch resistance and impact strength. Without wishing to be bound by theory, it is believed that the unexpected combination of scratch resistance and impact strength is achieved by careful selection of the components of the compositions including the selection of weight percent of the siloxane units in the poly(carbonate-siloxane), loading of the polyethylene, and loading of the siloxane-containing anti-scratch additive. A molded sample of the composition exhibits a notched Izod impact strength of greater than 50 J / m, preferably greater than 60 J / m, at 23 °C, 5.5 Ibf, as measured in accordance with ASTM D256, and a scratch line roughness Ra of less than 0.2, preferably less than 0.15, determined using Keyence Laser Scanning Confocal Microscopy

[0068] In an aspect, a molded sample of the composition can exhibit good impact strength. For example, a molded sample of the composition can exhibit a notched Izod impact strength of greater than 50 Joules per meter (J / m), preferably greater than 60 J / m, at 23 °C, 5.5 Ibf, as measured in accordance with ASTM D256.

[0069] A molded sample of the composition can also exhibit good scratch resistance. For example, a molded sample of the composition can exhibit a hardness of greater than 350 Newtons per square millimeter (N / mm2), preferably greater than 400 N / mm2, as measured in accordance with the Erichsen scratch hardness test at a force of 2 Newton (N).

[0070] A molded sample of the composition can also exhibit a scratch line roughness Ra of less than 0.2, preferably less than 0.15, determined using Keyence Laser Scanning Confocal Microscopy.

[0071] In an aspect, a molded sample of the composition exhibits a notched Izod impact strength of greater than 50 J / m, a hardness of greater than 350 N / mm2, and a scratch line roughness Ra of less than 0.2.

[0072] In a specific aspect, the composition can comprise 60 to 70 weight percent of the poly(methyl methacrylate); 10 to 20 weight percent of the poly(carbonate-siloxane); 10 to 20 weight percent of the acrylic impact modifier; and 1 to 2.5 weight percent of the polyethylene; and 0.5 to 4.5 weight percent of the siloxane-containing anti-scratch additive. The poly(methyl methacrylate) can be a poly(methyl methacrylate) homopolymer. The poly(carbonate-siloxane) can have a weight average molecular weight of 25,000 to 45,000 g / mol. The poly(carbonate- siloxane) can have a siloxane content of 35 to 65 weight percent based on the total weight of the poly(carbonate-siloxane). The acrylic impact modifier can be a core-shell impact modifier having a multilayer structure, The siloxane-containing anti-scratch additive can be an organo- modified polysiloxane. A molded sample of the composition can exhibit: a notched Izod impact strength of greater than 50 J / m, preferably greater than 60 J / m, at 23 °C, 5.5 Ibf, as measured in accordance with ASTM D256; and a hardness of greater than 350 N / mm2, preferably greater than 400 N / mm2, as measured in accordance with the Erichsen scratch hardness test at a force of 2 Newton (N); and a scratch line roughness Ra of less than 0.2, preferably less than 0.15, determined using Keyence Laser Scanning Confocal Microscopy.

[0073] The composition can be manufactured by various methods known in the art. For example, poly(methyl methacrylate) and poly(carbonate-siloxane) and other components can be first blended, optionally with any fillers, in a high speed mixer or by hand-mixing. The blend is then fed into the throat of a twin screw extruder via a hopper. Alternatively, at least one of the components can be incorporated into the composition by feeding it directly into the extruder at the through and / or downstream through a side stuffer, or by being compounded into a masterbatch with a desired polymer and fed into the extruder. The extruder is generally operated at a temperature higher than that necessary to cause the composition to flow. The extrudate can be immediately quenched in a water bath and pelletized. The pellets so prepared can be one- fourth inch long or less as desired. Such pellets can be used for subsequent molding, shaping, or forming.

[0074] Shaped, formed, casted, or molded articles comprising the composition are also provided. The composition can be molded into useful shaped articles by a variety of methods, such as injection molding, extrusion, rotational molding, blow molding, and thermoforming. The article can be a molded article, a thermoformed article, an extruded film, an extruded sheet, a honeycomb structure, one or more layers of a multi-layer article, a substrate for a coated article, or a substrate for a metallized article.

[0075] Articles comprising the composition can be used in various consumer products. In an aspect, the article can be an automotive component. In an aspect, the article can be a consumer electronic component, for example a housing for a consumer electronic device.

[0076] Articles can include, but are not limited to, exterior automobile components (e.g., grill, mirror housing, pillar, spoiler, logo, roof rail, bezel, trim, fender), interior automobile components (e.g., decorative parts, electronic housings, instrument panel components, navigation system, housing frames), storage boxes, a personal equipment part, a home appliance component, furniture, appliance housings (e.g., robot cleaners, drones), and consumer electronics devices (e.g., device housings or components for laptops, phones, tablets, batteries, wireless charging, AR / VR goggles).

[0077] In an aspect the article can be an automotive bumper, an automotive exterior component, an automobile mirror housing, an automobile wheel cover, an automobile instrument panel or trim, an automobile glove box, an automobile door hardware or other interior trim, an automobile exterior light, an automobile part within the engine compartment, an agricultural tractor or device part, a window or a component thereof, a construction equipment vehicle or device part, a marine or personal water craft part, an all-terrain vehicle or all-terrain vehicle part, plumbing equipment, a valve or pump, an air conditioning heating or cooling part, a furnace or heat pump part, a computer housing, a computer housing or business machine housing or part, a housing or part for monitors, a computer router, a desk top printer, a large office / industrial printer, an electronics part, a projector part, an electronic display part, a copier part, a scanner part, an electronic printer toner cartridge, a handheld electronic device housing, a housing for a hand-held device, a hair drier, an iron, a coffee maker, a toaster, a washing machine or washing machine part, a microwave, an oven, a power tool, an electric component, an electric enclosure, a lighting part, a component for a lighting fixture, a dental instrument, a medical instrument, a medical or dental lighting part, an aircraft part, a train or rail part, a seating component, a sidewall, a ceiling part, cookware, a medical instrument tray, an animal cage, fibers, a laser welded medical device, fiber optics, a lens (auto and non-auto), a cell phone part, a greenhouse component, a sun room component, a fire helmet, a safety shield, safety glasses, a gas pump part, a humidifier housing, a thermostat control housing, an air conditioner drain pan, an outdoor cabinet, a telecom enclosure or infrastructure, a Simple Network Detection System (SNIDS) device, a network interface device, a smoke detector, a component or device in a plenum space, a medical scanner, X-ray equipment, a component for a medical application or a device, an electrical box or enclosure, and an electrical connector, a construction or agricultural equipment, and a turbine blade.

[0078] In an aspect the article can be a component of an aircraft interior or a train interior, an access panel, access door, air flow regulator, air gasper, air grille, arm rest, baggage storage door, balcony component, cabinet wall, ceiling panel, door pull, door handle, duct housing, enclosure for an electronic device, equipment housing, equipment panel, floor panel, food cart, food tray, galley surface, handle, housing for television, light panel, magazine rack, telephone housing, partition, part for trolley cart, seat back, seat component, railing component, seat housing, shelve, side wall, speaker housing, storage compartment, storage housing, toilet seat, tray table, tray, trim panel, window molding, window slide, a balcony component, baluster, ceiling panel, cover for a life vest, cover for a storage bin, dust cover for a window, layer of an electrochromic device, lens for a television, electronic display, gauge, or instrument panel, light cover, light diffuser, light tube, light pipes, mirror, partition, railing, refrigerator door, shower door, sink bowl, trolley cart container, trolley cart side panel, or window

[0079] This disclosure is further illustrated by the following examples, which are nonlimiting.EXAMPLES

[0080] Materials used in the following examples are described in Table 1.Table 1

[0081] The compositions of the following examples were prepared by blending the components together and extruding on a 37 mm twin-screw extruder. The compositions were subsequently injection molded at a temperature of 210 to 240°C, though it will be recognized by one skilled in the art that the method is not limited to these temperatures. Extrusion and molding conditions are shown in Tables 2 and 3, respectively.Table 2Table 3

[0082] Physical measurements were made using the following test methods. Samples were pre-dried at 75°C for 6 hours prior to melt volume rate (MVR) testing. For all other testing, samples were pre-conditioned for 48 hours at 23 °C and 50% relative humidity.

[0083] Notched and Unnotched Izod impact Strength (Nil and UNII, respectively) was determined in accordance with ASTMD256 or ASTMD4812 under a load of 5.5 Ibf at a temperature of 23°C on 80 x 10 x 4 mm bars.

[0084] Melt volume rate (MVR) was determined in accordance with ISO1133 under a load of 2.16 kg at 240 °C with a dwell time of 300 seconds.

[0085] Tensile properties were measured in accordance with ISO 527 at 50 mm / min at a temperature of 23 °C on standard ISO tensile bars.

[0086] Hardness was determined using an Erichsen scratch test at 2N.

[0087] Scratch topography including scratch line roughness was characterized using a Keyence laser scanning confocal microscope.

[0088] Scratch whitening tests were carried out on molded plaques. Three scratches were generated on the plaques at 1.5N, 2N and 4N. The surface of the plaque was visually inspected for signs of scratch-whitening. Scratch- whitening is defined as a white line or color change visible (by eye) at all angles. A score of 0 means the scratches are visible at all loads (1.5N, 2N and 4N). A score of 1 means scratch is lightly visible at 1.5N load but visible at 2N and 4N. A score of 2 means scratch is barely visible at 1.5N and 2N loads but visible 4N. A score of 3 means scratch is barely visible at 1.5N, lightly visible at 2N loads but visible 4N. A score of 4 means scratch is invisible at 1.5N, barely visible at 2N loads but visible at 4N.

[0089] Compositions and results are shown in Table 4. In Table 4, the amount of each component is provided in weight percent, based on the total weight of the composition.Table 4'Additives includes a mixture of comprising stabilizers, mold release agents, colorantsTable 4 (cont.)'Additives includes a mixture of comprising stabilizers, mold release agents, colorants

[0090] Molded parts of the compositions described in Table 4 were tested for mechanical properties. The results are summarized in Table 5.Table 5Table 5 (cont.)

[0091] It would be advantageous to maintain impact performance of the compositions of the examples E1-E18 within 10% of that of the comparative composition CE1. As shown in Table 5, the compositions of examples El -El 8 achieved the desired impact properties.

[0092] Scratch performance of the compositions was also evaluated. Three circular scratches were generated on a MAI disk (0 = 100 mm, thickness = 3 mm) at 1.5N, 2N and 4N with an Erichsen scratcher equipped with a conical tip with an 18 pm diameter. The surface of the plaque was visually inspected for signs of scratch-whitening. Scratch-whitening is defined as a white line or color change visible, by eye, at all angles, and a rating of 0-4 was assigned based on the criteria described above. Microscopic analysis of the scratches was also done to determine scratch dimensions (e.g., scratch width, scratch depth, pileup height, and scratch roughness). Smooth and invisible to lowly visible scratches for the naked eye show a smooth scratch in microscopic visualization tool. Visible and white scratches tend to have a rougherprofile. Line roughness measurement (Ra) measured across the scratches correlates with scratch visibility: scratches with higher Ra values scatter light more and hence are more visible than smooth scratches with lower Ra values.

[0093] In general, it would be desirable to provide a composition which exhibits the following scratch performance: a whiteness rating of greater than or equal to 3, preferably greater than or equal to 4; a line roughness Ra of less than 0.2, preferably less than 0.15; a scratch width of less than 120 micrometers; a pile up height of less than 10 micrometers, preferably less than 5 micrometers; a residual depth of less than 10 micrometers, preferably less than 5 micrometers; a total groove height of less than 20 micrometers, preferably less than 5 micrometers; and an Erichsen Hardness of greater than 350 N / m2, preferably greater than 400 N / m2.

[0094] Scratch performance is summarized in Table 6.Table 6Table 6 (cont.)

[0095] An important scratch performance indicator is line scratch roughness (Ra), especially when it comes to scratch visibility (i.e., scratch whiteness). The formulations with lowest scratch roughness (i.e., close to the reference CE1 formulation) show good scratch whiteness performance. Other parameters such as scratch width, depth, pile-up height show the resistance of the material against the scratch. As shown in Table 6, the whiteness rating indicates the level of scratch visibility to the eye at a force of 2N, where a rating of 0 to 4 is given. As described above, a rating of 0 indicates a very white and visible scratch, whereas scratch whiteness score of 4 indicates a barely visible scratch. As seen in Table 6, the whiteness ratings correlate to the objective analysis of line roughness.

[0096] Further as shown in Table 6, the compositions of examples E1-E10 show a better scratch visibility (line roughness) and better scratch resistance compared to CE1 as indicated by scratch dimensions. Formulations El, E5 and E6 show comparable performance to the reference CE1. The composition according to example E12 shows better scratch performance compared to the reference CE1 formulation. Microscope images of scratch evaluations on molded parts of different compositions are also shown in FIG. 1.

[0097] The blackness and the gloss of various compositions was also assessed. Gloss was determined according to ISO2813. Blackness was determined from a color measurement according to ASTM E308. The results for select compositions are shown in Table 7. Table 7

[0098] It would be desirable to provide a composition that has a high blackness (e.g., greater than 230) and a high glass (e.g., a gloss at 20° of greater than 70), particularly for applications in automotive applications. As seen in Table 7, various compositions according tothe present disclosure exhibit this combination of properties in addition to the desired scratch performance and mechanical properties described above.

[0099] Delamination of various compositions was also tested. Delamination can be assessed according to ASTM D3359 using the tape test. Compositions that do not exhibit any delamination (i.e., 0% removed from the surface in a tape test) are assigned a rating of 5B. Compositions exhibiting less than 5% removal were assigned a rating of 4B. Compositions exhibiting 5 to 15% removal were assigned a rating of 3B. Compositions exhibiting 15 to 35% removal were assigned a rating of 2B. Compositions exhibiting 35 to 65% removal were assigned a rating of IB. Compositions exhibiting greater than 65% removal were assigned a rating of OB.

[0100] The composition according to CE1 exhibited delamination in the tape test. In contrast, compositions according to the present disclosure generally obtained ratings of 4B or 5B, with less than 5% delamination observed. Exemplary tape test results for select compositions are shown in FIG. 2. Specifically, as shown in FIG. 2, the composition according to CE1 obtained a delamination rating of 2B. In contrast, the compositions according to El and E12 each achieved a delaminating rating of 5B.

[0101] Accordingly, as shown in the present examples, the present inventors have advantageously identified that anti-scratch compositions which also retain desired physical and mechanical properties can be provided using a specific combination of an anti-scratch additive comprising polyethylene and a second anti-scratch additive. The compositions according to the present disclosure desirably include low amounts (i.e., less than 3 weight percent) of polyethylene, which can avoid compatibility issues that result in delamination, and further include a low amount of a second anti-scratch additive to improve the scratch performance. Thus the present inventors have identified a synergy between the use of polyethylene at low concentrations that avoids processing issues such as delamination and use of a second antiscratch additive to provide the desired combination of physical performance and compatibility / processing

[0102] Accordingly, a significant improvement in scratch-resistant compositions is provided by the present disclosure.

[0103] This disclosure further encompasses the following aspects.

[0104] Aspect 1: A composition comprising: 40 to 79.4 weight percent of a poly (methyl methacrylate); 10 to 25 weight percent of a poly(carbonate-siloxane) having a siloxane content of 30 to 70 weight percent, preferably 35 to 65 weight percent, based on the total weight of the poly(carbonate-siloxane); 10 to 25 weight percent of an acrylic impact modifier; 0.1 to less than3 weight percent of a polyethylene; and 0.5 to 5 weight percent of a siloxane-containing antiscratch additive; wherein the weight percent of each component is based on the total weight of the composition, wherein a molded sample of the composition exhibits a notched Izod impact strength of greater than 50 J / m, preferably greater than 60 J / m, at 23 °C, 5.5 Ibf, as measured in accordance with ASTM D256, and a scratch line roughness Ra of less than 0.2, preferably less than 0.15, determined using Keyence Laser Scanning Confocal Microscopy.

[0105] Aspect 2: The composition of aspect 1, wherein a molded sample of the composition exhibits a hardness of greater than 350 N / mm2, preferably greater than 400 N / mm2, as measured in accordance with the Erichsen scratch hardness test at a force of 2 Newton (N).

[0106] Aspect 3: The composition of aspect 1 or 2, wherein the poly(methyl methacrylate) is a poly(methyl methacrylate) homopolymer.

[0107] Aspect 4: The composition of any of aspects 1 to 3, wherein the poly(carbonate- siloxane) comprises bisphenol A carbonate repeating units and poly(dimethyl siloxane) repeating units.

[0108] Aspect 5: The composition of any of aspects 1 to 4, wherein the poly(carbonate- siloxane) has a weight average molecular weight of 21,000 to 50,000 g / mol, or 25,000 to 45,000 g / mol, or 30,000 to 45,000 g / mol, or 32,000 to 43,000 g / mol, or 35,000 to 40,000 g / mol, as determined by gel permeation chromatography using a crosslinked styrene-divinyl benzene column, at a sample concentration of 1 milligram per milliliter, and as calibrated using polystyrene standards and calculated for polycarbonate.

[0109] Aspect 6: The composition of any of aspects 1 to 5, wherein the composition is free of a poly (carbonate- siloxane) having a siloxane content that is less than 30 weight percent, or less than 20 weight percent, or less than 10 weight percent, each based on the total weight of the poly(carbonate-siloxane).

[0110] Aspect 7: The composition of any of aspects 1 to 6, wherein the acrylic impact modifier is a core-shell impact modifier having a multilayer structure.

[0111] Aspect 8: The composition of any of aspects 1 to 7, wherein the siloxane- containing additive comprises an organo-modified polysiloxane, preferably wherein the organo- modified polysiloxane is: a polyester-modified polysiloxane; or a C12-36 hydrocarbyl-modified polysiloxane.

[0112] Aspect 9: The composition of any of aspects 1 to 8, wherein the siloxane- containing additive comprises an ultra-high molecular weight polysiloxane in a polymer matrix, preferably wherein the polymer matrix comprises low density polyethylene, polycarbonate, a styrene-acrylonitrile copolymer, or a polycarbonate / acrylonitrile-butadiene-styrene blend,preferably wherein the ultra-high molecular weight polysiloxane has a number average molecular weight greater than 40,000 grams per mole, or greater than or equal to 100,000 grams per mole, or greater than or equal to 200,000 grams per mole.

[0113] Aspect 10: The composition of any of aspects 1 to 9, wherein the polyethylene has a melt-volume flow rate of greater than 6 g / 10 minutes, preferably greater than 15 g / 10 minutes, more preferably greater than 20 g / 10 minutes, as determined according to ISO 1133 at 290°C and 2.16 kilograms, preferably wherein the polyethylene comprises a low density polyethylene, a high density polyethylene, or a combination thereof.

[0114] Aspect 11: The composition of any of aspects 1 to 10, wherein the composition further comprises 0.01 to 2 weight percent, based on the total weight of the composition, of an additive composition.

[0115] Aspect 12: The composition of aspect 1, comprising: 60 to 70 weight percent of the poly(methyl methacrylate); 10 to 20 weight percent of the poly(carbonate-siloxane); 10 to 20 weight percent of the acrylic impact modifier; 1 to 2.5 weight percent of the polyethylene; and 0.5 to 4.5 weight percent of the siloxane-containing anti-scratch additive.

[0116] Aspect 13: The composition of aspect 12, wherein the poly(methyl methacrylate) is a poly(methyl methacrylate) homopolymer; the poly(carbonate-siloxane) has a weight average molecular weight of 25,000 to 45,000 g / mol; the poly(carbonate-siloxane) has a siloxane content of 35 to 65 weight percent based on the total weight of the poly(carbonate-siloxane); the acrylic impact modifier is a core-shell impact modifier having a multilayer structure; and the siloxane- containing anti-scratch additive is an organo-modified polysiloxane; and wherein a molded sample of the composition exhibits: a notched Izod impact strength of greater than 50 J / m, preferably greater than 60 J / m, at 23 °C, 5.5 Ibf, as measured in accordance with ASTM D256; and a hardness of greater than 350 N / mm2, preferably greater than 400 N / mm2, as measured in accordance with the Erichsen scratch hardness test at a force of 2 Newton (N); and a scratch line roughness Ra of less than 0.2, preferably less than 0.15, determined using Keyence Laser Scanning Confocal Microscopy.

[0117] Aspect 14: A method of making the composition of any of aspects 1 to 12, the method comprising melt-mixing the components of the composition, and, optionally, extruding the composition.

[0118] Aspect 15: An article comprising the composition of any of aspects 1 to 12, preferably wherein the article is: an automotive component or a consumer electronic component; or an automotive body panel, an automotive instrument panel, an automotive console,automotive trim, an automotive visor; or an electrical or lighting cover, an electrical or lighting housing, an electrical or lighting enclosure; or a personal electronic device or a home appliance.

[0119] The compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed. The compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any materials (or species), steps, or components, which are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.

[0120] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. “Combinations” is inclusive of blends, mixtures, alloys, reaction products, and the like. The terms “first,” “second,” and the like, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The terms “a” and “an” and “the” do not denote a limitation of quantity, and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. “Or” means “and / or” unless clearly stated otherwise. Reference throughout the specification to “an aspect” means that a particular element described in connection with the aspect is included in at least one aspect described herein, and may or may not be present in other aspects. The term “combination thereof’ as used herein includes one or more of the listed elements, and is open, allowing the presence of one or more like elements not named. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various aspects.

[0121] Unless specified to the contrary herein, all test standards are the most recent standard in effect as of the filing date of this application, or, if priority is claimed, the filing date of the earliest priority application in which the test standard appears.

[0122] Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this application belongs. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference.

[0123] Compounds are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valency filled by a bond as indicated, or a hydrogen atom. A dash that is not between two letters or symbols is usedto indicate a point of attachment for a substituent. For example, -CHO is attached through carbon of the carbonyl group.

[0124] As used herein, the term “hydrocarbyl,” whether used by itself, or as a prefix, suffix, or fragment of another term, refers to a residue that contains only carbon and hydrogen. The residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. However, when the hydrocarbyl residue is described as substituted, it may, optionally, contain heteroatoms over and above the carbon and hydrogen members of the substituent residue. Thus, when specifically described as substituted, the hydrocarbyl residue can also contain one or more carbonyl groups, amino groups, hydroxyl groups, or the like, or it can contain heteroatoms within the backbone of the hydrocarbyl residue. The term "alkyl" means a branched or straight chain, saturated aliphatic hydrocarbon group, e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n- pentyl, s-pentyl, and n- and s-hexyl. “Alkenyl” means a straight or branched chain, monovalent hydrocarbon group having at least one carbon-carbon double bond (e.g., ethenyl (-HC=CH2)). “Alkoxy” means an alkyl group that is linked via an oxygen (i.e., alkyl-O-), for example methoxy, ethoxy, and sec-butyloxy groups. "Alkylene" means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH2-) or propylene (-(CH2)3- )). “Cycloalkylene” means a divalent cyclic alkylene group, -CnH2n-x, wherein x is the number of hydrogens replaced by cyclization(s). “Cycloalkenyl” means a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" means an aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl. “Arylene” means a divalent aryl group. “Alkylarylene” means an arylene group substituted with an alkyl group. “Arylalkylene” means an alkylene group substituted with an aryl group (e.g., benzyl). The prefix "halo" means a group or compound including one more of a fluoro, chloro, bromo, or iodo substituent. A combination of different halo atoms (e.g., bromo and fluoro), or only chloro atoms can be present. The prefix “hetero” means that the compound or group includes at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatom(s)), wherein the heteroatom(s) is each independently N, O, S, Si, or P. “Substituted” means that the compound or group is substituted with at least one (e.g., 1, 2, 3, or 4) substituents that can each independently be a C1-9 alkoxy, a C1-9 haloalkoxy, a nitro (-NO2), a cyano (-CN), a C1-6 alkyl sulfonyl (-S(=O)2-alkyl), a C6-12 aryl sulfonyl (-S(=O)2-aryl), a thiol (-SH), a thiocyano (-SCN), a tosyl (CH3C6H4SO2-), a C3-12 cycloalkyl, a C2-12 alkenyl, a C5-12 cycloalkenyl, a C6-12 aryl, a C7-13 arylalkylene, a C4-12 heterocycloalkyl, and a C3-12 heteroaryl instead of hydrogen, provided that the substituted atom’s normal valence is not exceeded. The number of carbon atoms indicated in a group is exclusive of any substituents. For example -CH2CH2CN is a C2 alkyl group substituted with a nitrile.

[0125] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.

Claims

CLAIMS1. A composition comprising:40 to 79.4 weight percent of a poly(methyl methacrylate);10 to 25 weight percent of a poly(carbonate-siloxane) having a siloxane content of 30 to 70 weight percent, preferably 35 to 65 weight percent, based on the total weight of the poly(carbonate-siloxane) ;10 to 25 weight percent of an acrylic impact modifier;0.1 to less than 3 weight percent of a polyethylene; and0.5 to 5 weight percent of a siloxane-containing anti-scratch additive; wherein the weight percent of each component is based on the total weight of the composition, wherein a molded sample of the composition exhibits: a notched Izod impact strength of greater than 50 J / m, preferably greater than 60 J / m, at23 °C, 5.5 Ibf, as measured in accordance with ASTM D256, and a scratch line roughness Ra of less than 0.2, preferably less than 0.15, determined using Keyence Laser Scanning Confocal Microscopy.

2. The composition of claim 1, wherein a molded sample of the composition exhibits: a hardness of greater than 350 N / mm2, preferably greater than 400 N / mm2, as measured in accordance with the Erichsen scratch hardness test at a force of 2 Newton (N); and3. The composition of claim 1 or 2, wherein the poly (methyl methacrylate) is a poly (methyl methacrylate) homopolymer.

4. The composition of any of claims 1 to 3, wherein the poly(carbonate-siloxane) comprises bisphenol A carbonate repeating units and poly(dimethyl siloxane) repeating units.

5. The composition of any of claims 1 to 4, wherein the poly(carbonate-siloxane) has a weight average molecular weight of 21,000 to 50,000 g / mol, or 25,000 to 45,000 g / mol, or 30,000 to 45,000 g / mol, or 32,000 to 43,000 g / mol, or 35,000 to 40,000 g / mol, as determined by gel permeation chromatography using a crosslinked styrene-divinyl benzene column, at a sampleconcentration of 1 milligram per milliliter, and as calibrated using polystyrene standards and calculated for polycarbonate.

6. The composition of any of claims 1 to 5, wherein the composition is free of a poly(carbonate-siloxane) having a siloxane content that is less than 30 weight percent, or less than 20 weight percent, or less than 10 weight percent, each based on the total weight of the poly(carbonate-siloxane) .

7. The composition of any of claims 1 to 6, wherein the acrylic impact modifier is a coreshell impact modifier having a multilayer structure.

8. The composition of any of claims 1 to 7, wherein the siloxane-containing additive comprises an organo-modified polysiloxane, preferably wherein the organo-modified poly siloxane is: a polyester- modified polysiloxane; or a C12-36 hydrocarbyl-modified polysiloxane.

9. The composition of any of claims 1 to 8, wherein the siloxane-containing additive comprises an ultra-high molecular weight polysiloxane in a polymer matrix, preferably wherein the polymer matrix comprises low density polyethylene, polycarbonate, a styrene-acrylonitrile copolymer, or a polycarbonate / acrylonitrile-butadiene-styrene blend, preferably wherein the ultra-high molecular weight polysiloxane has a number average molecular weight greater than 40,000 grams per mole, or greater than or equal to 100,000 grams per mole, or greater than or equal to 200,000 grams per mole.

10. The composition of any of claims 1 to 9, wherein the polyethylene has a melt-volume flow rate of greater than 6 g / 10 minutes, preferably greater than 15 g / 10 minutes, more preferably greater than 20 g / 10 minutes, as determined according to ISO 1133 at 290°C and 2.16 kilograms, preferably wherein the polyethylene comprises a low density polyethylene, a high density polyethylene, or a combination thereof.

11. The composition of any of claims 1 to 10, wherein the composition further comprises 0.01 to 2 weight percent, based on the total weight of the composition, of an additive composition.

12. The composition of claim 1, comprising:60 to 70 weight percent of the poly (methyl methacrylate);10 to 20 weight percent of the poly(carbonate-siloxane);10 to 20 weight percent of the acrylic impact modifier; and1 to 2.5 weight percent of the polyethylene; and0.5 to 4.5 weight percent of the siloxane-containing anti-scratch additive.

13. The composition of claim 12, wherein the poly(methyl methacrylate) is a poly(methyl methacrylate) homopolymer; the poly(carbonate-siloxane) has a weight average molecular weight of 25,000 to 45,000 g / mol; the poly(carbonate-siloxane) has a siloxane content of 35 to 65 weight percent based on the total weight of the poly(carbonate-siloxane); the acrylic impact modifier is a core-shell impact modifier having a multilayer structure; and the siloxane-containing anti-scratch additive is an organo-modified polysiloxane; and wherein a molded sample of the composition exhibits: a notched Izod impact strength of greater than 50 J / m, preferably greater than 60 J / m, at 23 °C, 5.5 Ibf, as measured in accordance with ASTM D256; and a hardness of greater than 350 N / mm2, preferably greater than 400 N / mm2, as measured in accordance with the Erichsen scratch hardness test at a force of 2 Newton (N); and a scratch line roughness Ra of less than 0.2, preferably less than 0.15, determined using Keyence Laser Scanning Confocal Microscopy.

14. A method of making the composition of any of claims 1 to 12, the method comprising melt-mixing the components of the composition, and, optionally, extruding the composition.

15. An article comprising the composition of any of claims 1 to 12, preferably wherein the article is: an automotive component or a consumer electronic component; or an automotive body panel, an automotive instrument panel, an automotive console, automotive trim, an automotive visor; or an electrical or lighting cover, an electrical or lighting housing, an electrical or lighting enclosure; or a personal electronic device or a home appliance.

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