Anti-scratch composition and article comprising same

Abstract

A composition comprising specific 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 compositions and articles comprising the compositions are also disclosed.

Description

Anti-scratch compositions and articles comprising them

[0001] Citations of relevant applications

[0002] This application claims priority and benefit to European Patent Application No. 23202147.7, filed on 6 October 2023, the entire contents of which are incorporated herein by reference. Background Technology

[0003] Poly(methyl methacrylate) (PMMA) is advantageous for scratch-resistant and transparent or high-gloss thermoplastic compositions. However, due to its low impact strength, PMMA is generally not well-suited for demanding applications such as automotive components or consumer electronics (e.g., housings). Polycarbonate (PC) offers excellent impact strength and transparency but tends to lack scratch resistance.

[0004] Efforts to improve scratch resistance include, for example, hard coating the composition. This approach may not be suitable for all applications. For example, hard coatings introduce expensive additional processing steps into the preparation process. The 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).

[0005] Therefore, there remains a need in the art for improved scratch-resistant compositions. Providing scratch-resistant compositions that also have improved impact strength would be a further advantage. Summary of the Invention

[0006] The composition comprises 40 to 79.4 wt% poly(methyl methacrylate); 10 to 25 wt% poly(carbonate-siloxane) having a siloxane content of 30 to 70 wt%, preferably 35 to 65 wt%, based on the total weight of the poly(carbonate-siloxane); 10 to 25 wt% acrylic impact modifier; 0.1 to less than 3 wt% polyethylene; and 0.5 to 5 wt% siloxane-containing anti-scratch additive; wherein the wt% of each component is based on the total weight of the composition, and wherein molded samples of the composition exhibit: a notched cantilever beam impact strength greater than 50 J / m, preferably greater than 60 J / m, measured according to ASTM D256 at 23°C and 5.5 lbf, and a scratch line roughness less than 0.2, preferably less than 0.15, determined using Keyence laser scanning confocal microscopy. Roughness (Ra, the roughness of the scratch line).

[0007] Methods for preparing the composition include melt-mixing the components of the composition, and optionally, extruding the composition.

[0008] Articles comprising the composition embody another aspect of this disclosure.

[0009] The above and other features are illustrated by the following detailed description. Attached Figure Description

[0010] The following figures are exemplary embodiments.

[0011] Figure 1 is a laser scanning confocal micrograph of the scraping in the composition according to different examples.

[0012] Figure 2 shows the stratified test results for the selected instances. Detailed Implementation

[0013] This document provides compositions exhibiting a combination of good scratch resistance and impact strength. The compositions comprise specific amounts of poly(methyl methacrylate), poly(carbonate-siloxane), an acrylic impact modifier, polyethylene, and a siloxane-containing anti-scratch additive. The inventors have unexpectedly determined that compositions comprising the specific components described herein possess a synergistic effect due to the use of low concentrations of polyethylene and the siloxane-containing anti-scratch additive. The resulting compositions avoid processing problems (e.g., delamination) and exhibit a desirable combination of physical properties and compatibility.

[0014] Therefore, one aspect of this disclosure is a composition comprising poly(methyl methacrylate), poly(carbonate-siloxane), acrylic impact modifier, polyethylene, and siloxane-containing anti-scratch additive.

[0015] Any suitable poly(methyl methacrylate) polymer or copolymer thereof can be used. In one aspect, the poly(methyl methacrylate) can be a homopolymer obtained by polymerization (e.g., free radical polymerization) of methyl methacrylate monomers. In another aspect, the poly(methyl methacrylate) can be a copolymer obtained by polymerization (e.g., free radical polymerization) of methyl methacrylate monomers with at least one additional monomer suitable for copolymerization with methyl methacrylate. Suitable comonomers can be readily determined by those skilled in the art. For example, comonomers may include, but are not limited to, C. 2-10Alkyl (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 group may be substituted or unsubstituted; cycloalkyl (meth)acrylates, such as 3-vinylcyclohexyl (meth)acrylate, or (methyl)... The copolymerizable monomer may include: borneol acrylate; hydroxyalkyl acrylates, such as 3-hydroxypropyl methacrylate, 3,4-dihydroxybutyl methacrylate, 2-hydroxyethyl methacrylate, or 2-hydroxypropyl methacrylate; 1,4-butanediol methacrylate; tetrahydrofurfuryl methacrylate; ethyleneoxyethoxyethyl methacrylate; ethyl sulfinyl methacrylate; 4-thiocyanobutyl methacrylate; ethyl sulfonyl methacrylate; methyl thiocyanate methacrylate; methyl sulfinyl methacrylate; bis((meth)acryloyloxyethyl) sulfide; or trimethylolpropane tri(meth)acrylate. In one aspect, the copolymerizable monomer may include an amide or nitrile derivative of (meth)acrylic acid, such as N-(3-dimethylaminopropyl)(meth)acrylamide or (meth)acrylonitrile. In one aspect, the copolymerizable monomer may include 1-olefins, such as 1-hexene, 1-heptene, or butene; branched olefins, such as vinylcyclohexane, 3,3-dimethyl-1-propylene, 3-methyl-1-diisobutylene, or 4-methyl-1-pentene; vinyl esters, such as vinyl acetate; styrene, o-methylstyrene, or o-ethylstyrene; and monomers having a C14-2-O-methyl ester. 1-4Styrene substituted with alkyl or halogen substituents, such as vinyltoluene, p-methylstyrene, monochlorostyrene, dichlorostyrene, tribromostyrene, or tetrabromostyrene; 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-1-vinylimidazole, N-vinyl... 2-vinylpyrrolidone, N-vinylpyrrolidone, 3-vinylpyrrolidone, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxacyclopentane, vinylfuran, vinylthiophene, vinylthiolane, vinylthiazole, hydrogenated vinylthiazole, vinyloxazole, or hydrogenated vinyloxazole; vinyl ethers; isopentenyl ethers; maleic acid derivatives, such as maleic anhydride, methylmaleic anhydride, maleimide, or methylmaleimide; or dienes, such as divinylbenzene. Any combination of the foregoing copolymerizable monomers may also be used.

[0016] In one aspect, based on the total weight of the poly(methyl methacrylate) polymer, the poly(methyl methacrylate) may have a methyl methacrylate content of at least 70 wt%, or at least 80 wt%, or at least 90 wt%, or at least 95 wt%. In another aspect, the poly(methyl methacrylate) comprises 100 wt% of repeating methyl methacrylate units (i.e., a methyl methacrylate homopolymer).

[0017] In one aspect, poly(methyl methacrylate) may include a combination of different poly(methyl methacrylate) homopolymers or copolymers (e.g., as blends), such as poly(methyl methacrylate) with different molecular weights or composed of different repeating units.

[0018] In one respect, the weight-average molecular weight of poly(methyl methacrylate) can be, for example, 10,000 to 1,000,000 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. The weight-average molecular weight can be determined by gel permeation chromatography relative to a poly(methyl methacrylate) standard.

[0019] In one respect, poly(methyl methacrylate) can have a density of 7 to 12 cubic centimeters per 10 minutes (cm³) as measured according to ISO 1133 at 240°C, 2.16 kg, and 300 seconds. 3 Melt volume flow rate ( / 10 minutes).

[0020] Poly(methyl methacrylate) is commercially available from sources such as ACRYLITE from Evonik. TM POQ66, or both from Arkema's PLEXIGLAS TM V920A or ALTUGLAS TM V825T.

[0021] In one respect, poly(methyl methacrylate) can be derived from post-consumer or post-industrial recycled materials, or can be produced from at least one monomer derived from bio-based or plastic waste raw materials.

[0022] Based on the total weight of the composition, poly(methyl methacrylate) may be present in the composition in an amount of 40 to 79.4 wt%. Within this range, poly(methyl methacrylate) may be present in an amount of 45 to 75 wt%, or 50 to 75 wt%, or 55 to 75 wt%, or 57 to 72 wt%, or 60 to 70 wt%, respectively, based on the total weight of the composition.

[0023] In addition to poly(methyl methacrylate), the composition further comprises poly(carbonate-siloxane). The poly(carbonate-siloxane) comprises polycarbonate blocks containing repeating units according to formula (1): (1) and polysiloxane blocks. In formula (1), R 1 At least 60% of the total number of groups contains an aromatic moiety, and the remainder is aliphatic, alicyclic, or aromatic. In one aspect, each R 1 It is C 6-30 Aromatic groups, that is, containing at least one aromatic moiety. R 1 It can be derived from HO-R 1 -OH, especially aromatic dihydroxy compounds of formula (2): HO–A 1 –Y 1 –A 2 –OH(2) where, A 1 and A 2 Each of them is a monocyclic divalent aromatic group, and Y 1 Is it a single bond or has A 1 With A 2 A bridging base consisting of one or more separate atoms. In one aspect, an atom will connect A... 1 With A 2 Separate. Preferably, each R 1 Bisphenols that can be derived from formula (3): (3) Wherein, R a and R b Each is independently a halogen, C 1-12 alkoxy, or C1-12 Alkyl groups, and p and q are each independent integers from 0 to 4. It should be understood that when p or q is less than 4, the valence of each carbon in the ring is filled with hydrogen. Also in equation (3), X a It is a bridging group that connects two hydroxyl-substituted aromatic groups, wherein the bridging group and the hydroxyl substituents of each C6 arylene are arranged ortho, meta, or para (preferably para) on the C6 arylene. In one aspect, the bridging group X a It is a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, or C 1-60 Organic bridging groups. Organic bridging groups can be cyclic or acyclic, aromatic or non-aromatic, and can further contain heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorus. C1 can be arranged... 1-60 The organic group causes each of the C6 arylene groups attached to it to be attached to a common alkylene carbon or to a C6 alkylene carbon. 1-60 Different carbons in an organic bridging group. In one respect, p and q are each 1, and R a and R b Each is C 1-3 Alkyl groups, preferably methyl groups, are arranged in a meta position on the hydroxyl groups of each arylene group.

[0024] The polysiloxane block comprises repeating diorganosiloxane units as shown in formula (4): (4) Where each R is independently C 1-13 Monovalent organic groups. For example, R can be C. 1-13 Alkyl, C 1-13 Alkoxy, C 2-13 alkenyl, C 2-13 alkenyloxy group, C 3-6 cycloalkyl, C 3-6 Cycloalkoxy, C 6-14 Aryl, C 6-10 aryloxy group, C 7-13 Arylalkylene, C 7-13 Arylalkyleneoxy, C 7-13 alkylarylene, or C 7-13 Alkylaryloxy groups. These groups can be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or combinations thereof. In one aspect, when a transparent poly(carbonate-siloxane) is desired, R is not substituted with a halogen. Combinations of the aforementioned R groups can be used in the same copolymer.

[0025] The value of E in equation (4) can vary widely depending on the type and relative amount of each component in the composition, the desired performance of the composition, and similar considerations. Typically, 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 one aspect, E has an average value of 10 to 80 or 10 to 40, and in another aspect, E has an average value of 40 to 80 or 40 to 70. When E has a lower value, for example less than 40, a relatively large amount of poly(carbonate-siloxane) can be expected to be used. Conversely, when E has a higher value, for example greater than 40, a relatively low amount of poly(carbonate-siloxane) can be used. A combination of a first poly(carbonate-siloxane) and a second poly(carbonate-siloxane) (or more poly(carbonate-siloxane)) 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.

[0026] In one respect, the polysiloxane block is of formula (5): (5) Wherein, E and R are as defined in equation (4); each R can be the same or different and as defined above; and Ar can be the same or different and is substituted or unsubstituted C. 6-30 Aryl groups, wherein the bond is directly attached to the aromatic moiety. The Ar group in formula (5) can be derived from C 6-30 Dihydroxyaryl compounds, such as dihydroxyaryl compounds of formula (3) or aromatic dihydroxy compounds of formula (6): (6) Wherein, each R h Independently, it is a halogen atom, C 1-10 Hydrocarbon groups (such as C) 1-10 Alkyl, halogen-substituted C 1-10 Alkyl, C 6-10 Aryl or halogen-substituted C 6-10 (aryl), and n is 0 to 4. Halogen is usually bromine. Specific dihydroxyaryl compounds are 1,1-bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)n-butane, 2,2-bis(4-hydroxy-1-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfide, and 1,1-bis(4-hydroxy-tert-butylphenyl)propane.

[0027] In another aspect, the polysiloxane block is of formula (7): (7) Wherein, R and E are as described above, and each R 2 Independently is divalent C 1-30Organic groups, wherein the polymerized polysiloxane unit is a reactive residue of its corresponding dihydroxy compound. In one particular aspect, the polysiloxane block is of formula (8): (8) Where R and E are as defined above. R in equation (8) 2 It is divalent C 2-8 Aliphatic groups. Each M in formula (8) may be the same or different, and may be halogen, cyano, nitro, C 1-8 Alkylthio, C 1-8 Alkyl, C 1-8 Alkoxy, C 2-8 alkenyl, C 2-8 alkenyloxy group, C 3-8 cycloalkyl, C 3-8 Cycloalkoxy, C 6-10 Aryl, C 6-10 aryloxy group, C 7-12 Aryl alkyl, C 7-12 Arylalkoxy, C 7-12 alkylaryl, or C 7-12 Alkyl aryloxy groups, wherein each n is independently 0, 1, 2, 3, or 4.

[0028] In one respect, M is bromine or chlorine, alkyl (such as methyl, ethyl, or propyl), alkoxy (such as methoxy, ethoxy, or propoxy), or aryl (such as phenyl, chlorophenyl, or tolyl); R 2 It is dimethylene, trimethylene, or tetramethylene; and R is C. 1-8 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 yet another aspect, R is methyl, M is methoxy, n is 1, and R... 2 It is divalent C 1-3 Aliphatic groups. Specific polysiloxane blocks are as follows: (9a) (9b) (9c), or combinations 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.

[0029] The blocks of formula (9) can be derived from the corresponding dihydroxy polysiloxanes, which can then be prepared by platinum-catalyzed addition between a siloxane hydride and an aliphatic unsaturated monohydric phenol (such as eugenol, 2-alkylphenol, 4-allyl-2-methylphenol, 4-allyl-2-phenylphenol, 4-allyl-2-bromophenol, 4-allyl-2-tert-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). Then, for example, poly(carbonate-siloxane) can be prepared by the synthetic process of Preparation Example 2, as described in Hoover's European Patent Application Publication No. 0 524 731 A1, page 5.

[0030] The transparent poly(carbonate-siloxane) comprises carbonate units (1) derived from bisphenol A and repeating siloxane units (9a), (9b), (9c) or combinations thereof (preferably 9a), wherein E has an average value of 4 to 50, preferably 5 to 15, more preferably 6 to 15, and even more preferably 7 to 10. This transparent copolymer can be prepared using one or both of the tubular reactor methods described in U.S. Patent Application No. 2004 / 0039145A1, or synthesized using the method described in U.S. Patent No. 6,723,864.

[0031] Based on the total weight of the poly(carbonate-siloxane), the poly(carbonate-siloxane) has a siloxane content of 30 to 70 wt%. Within this range, the poly(carbonate-siloxane) may have a siloxane content greater than 30 to 70 wt%, or 35 to 70 wt%, or 35 to 65 wt%. As used herein, the “siloxane content” of the poly(carbonate-siloxane) refers to the content of siloxane units based on the total weight of the poly(carbonate-siloxane).

[0032] In one respect, poly(carbonate-siloxane) can be derived from post-consumer or post-industrial recycled materials, or can be produced from at least one monomer derived from bio-based or plastic waste raw materials.

[0033] In one 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 one respect, 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 cross-linked styrene-divinylbenzene column at a sample concentration of 1 mg / mL, calibrated using polystyrene standards and calculated for polycarbonate.

[0034] Poly(carbonate-siloxane) can have a melt volumetric flow rate of 1 to 50 cubic centimeters per 10 minutes (cc / 10 minutes), preferably 2 to 30 cc / 10 minutes, as measured at 300°C / 1.2 kg. The desired overall flow properties can be achieved using combinations of poly(carbonate-siloxane) with different flow properties.

[0035] Based on the total weight of the composition, the poly(carbonate-siloxane) may be present in the composition in an amount that effectively provides 1 to 25 wt%, or 3 to 22 wt%, or 3 to 15 wt%, or 3 to 10 wt%, or 5 to 10 wt% of the total siloxane content.

[0036] In one aspect, the composition may have a total siloxane content of 6 to 10 wt%, and the weight-average molecular weight of the poly(carbonate-siloxane) may be greater than 21,000 g / mol. In another aspect, the composition may have a total siloxane content of 6 to 10 wt%, and the weight-average molecular weight of the polycarbonate-siloxane copolymer may be greater than 25,000 and less than 45,000 g / mol. In yet another aspect, the composition may have a total siloxane content of 6 to 10 wt%, and the weight-average molecular weight of the poly(carbonate-siloxane) may be greater than 30,000 and less than 40,000 g / mol.

[0037] Based on the total weight of the composition, poly(carbonate-siloxane) may be present in the composition in an amount of 10 to 25 wt%. Within this range, poly(carbonate-siloxane) may be present in an amount of 10 to 20 wt%, or 10 to 18 wt%, or 12 to 18 wt%, respectively, based on the total weight of the composition.

[0038] In one aspect, the composition comprises less than or equal to 5 wt%, or less than or equal to 1 wt%, or less than or equal to 0.1 wt% of an auxiliary poly(carbonate-siloxane), which comprises greater than 70 to 98 wt%, more preferably 75 to 97 wt% of carbonate units and less than 30 wt%, or 2 to less than 30 wt%, or 3 to 25 wt% of siloxane units. In one aspect, the composition may not contain the auxiliary poly(carbonate-siloxane) copolymer. In other words, in one aspect, based on the total weight of the poly(carbonate-siloxane), the composition may be minimized (e.g., comprising less than 5 wt%, or less than 1 wt%, or less than 0.1 wt%) or may not contain poly(carbonate-siloxane) having a siloxane content of less than 30 wt%.

[0039] In addition to poly(methyl methacrylate) and poly(carbonate-siloxane), the composition further comprises an acrylic impact modifier. The acrylic impact modifier may be in the form of a homopolymer or copolymer, including random, block, radial block, graft, and core-shell copolymers. Combinations of acrylic impact modifiers may be used.

[0040] In one aspect, an exemplary acrylic impact modifier may comprise an impact modifier containing an acrylic copolymer, which may include an 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 combinations thereof.

[0041] In one aspect, the impact modifier may be a multilayer impact modifier comprising a core and one or more shells. As described above, the core may be an elastomer and the shell may be rigid. In one aspect, the multilayer impact modifier may comprise butyl acrylate as a rubber component. In one aspect, the multilayer impact modifier may comprise methyl methacrylate polymer as a rigid component. In one aspect, the multilayer impact modifier may have a core-shell-shell structure, wherein the core (C) is surrounded by a first shell (S1), which in turn is surrounded by a second shell (S2). The core and the first shell (e.g., the inner shell) may be elastomers and the second shell (e.g., the outer shell) may be rigid. In one aspect, the weight ratio of C : (S1+S2) may be from 10 : 90 to 40 : 60. The core and the first shell may comprise an elastomer (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 may comprise a rigid polymer overlayer grafted onto the elastomeric phase. In one aspect, the core may comprise a first butyl acrylate polymer. In another aspect, the first shell may comprise a second butyl acrylate polymer. In one aspect, based on the total weight of the second shell, the second shell may comprise at least 50 wt% of a methyl methacrylate polymer. In one aspect, the multilayer impact modifier may have a particle size of 100 to 1000 nanometers (nm), for example, 150 to 500 nm, or 175 to 250 nm. In one aspect, the number-average particle size of the multilayer impact modifier may be 30 to 400 nm. The particle size can be determined by commonly known methods, such as light scattering methods.

[0042] In one aspect, the core of the multilayer impact modifier may comprise a core polymer, which, based on the total weight of the core, comprises: 40 to 99.9 wt%, or 55 to 90 wt%, alkyl methacrylate repeating units, alkyl acrylate repeating units, or styrene repeating units; 0 to 59.9 wt%, copolymerizable monomers other than alkyl methacrylate, alkyl acrylate, or styrene repeating units; and 0.1 to 5 wt%, multifunctional monomers. In another aspect, the core polymer may be a butyl acrylate polymer.

[0043] In one aspect, the first shell of the multilayer impact modifier may comprise a first shell polymer, wherein, based on the total weight of the first shell, the first shell polymer comprises: 50 to 99.9 wt%, preferably 70 to 99 wt% of (C 2-8Alkyl acrylate; 0 to 49.9 wt%, preferably 0 to 29 wt%, of a non-alkyl acrylate copolyvinyl monomer; and 0.1 to 10 wt%, preferably 0.1 to 5 wt%, of a multifunctional monomer. Polymerization of the monomer used for the first shell in the presence of the core polymer can result in the core polymer being predominantly distributed in the central portion of the impact modifier. In one aspect, the first shell polymer can be a butyl acrylate polymer.

[0044] In one aspect, the second shell of the multilayer impact modifier can be a grafted component. In another aspect, the second shell can comprise compounds derived from styrene compounds, (meth)acrylonitrile, (meth)acrylic acid, (C... 1-6 Homopolymers or copolymers of alkyl(meth)acrylates, or combinations thereof. In one aspect, based on the total weight of the outer shell, the second shell may comprise: 50 to 100 wt%, preferably 80 to 100 wt%, of repeating methyl methacrylate units; and 0 to 50 wt%, preferably 0 to 20 wt%, of copolyvinyl monomers other than methyl methacrylate. In one aspect, the outer shell polymer may be a methyl methacrylate polymer.

[0045] In one aspect, the refractive index of the multilayer impact modifier may be 1.45 to 1.55, or 1.47 to 1.51, or about 1.49, or selected from, equal to, or between any two of the following: 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 another aspect, the ratio of the refractive indices of poly(methyl methacrylate) and the multilayer impact modifier may be from 1.05:1 to 1:1.05.

[0046] In one aspect, the rubber content of the impact modifier can be from 30 to 90 wt%. The impact modifier can be described, for example, in U.S. Publication No. 2013 / 0184375. In another aspect, the impact modifier can be a powder product having a multilayer structure, containing butyl acrylate as a rubber component, such as KANE ACE available from Kaneka. TM M-210.

[0047] Based on the total weight of the composition, the acrylic impact modifier may be included in the composition in an amount of 10 to 25 wt%. Within this range, each impact modifier may be present in an amount of 12 to 25 wt%, or 10 to 20 wt%, or 12 to 18 wt%, or 13 to 17 wt%, based on the total weight of the composition.

[0048] In addition to poly(methyl methacrylate), poly(carbonate-siloxane), and acrylic impact modifiers, the composition further comprises polyethylene. The polyethylene may be low-density polyethylene (LDPE), high-density polyethylene (HDPE), or a combination thereof. In one aspect, polyethylene having a medium to high melt volume flow rate is preferred. For example, the polyethylene may preferably have a melt volume flow rate greater than 6 g / 10 min, preferably greater than 15 g / 10 min, and more preferably greater than 20 g / 10 min, as determined according to ISO 1133 at 290°C and 2.16 kg.

[0049] In one aspect, the composition may contain low-density polyethylene (LDPE). LDPE is branched polyethylene. LDPE typically has reduced crystallinity and a lower density. For example, the density of LDPE can be less than 0.940 g / cm³, as determined according to ASTM D792. 3 Or 0.91 to 0.93 g / cm³ 3 LDPE can be prepared under high temperature and high pressure, resulting in a complex branched molecular structure. The amount and density of branching can be controlled by the polymerization conditions.

[0050] In one aspect, the composition may contain high-density polyethylene (HDPE). HDPE has virtually no branches in its polyethylene structure. HDPE typically exhibits increased crystallinity and a higher density (e.g., compared to LDPE). For example, the density of HDPE can be greater than or equal to 0.940 g / cm³. 3 Or 0.94 to 0.97 g / cm³ 3 For example, as determined according to ASTM D792.

[0051] Based on the total weight of the composition, polyethylene may be present in the composition in an amount from 0.1 to less than 3 wt%. Within this range, each of the first anti-scratch additives may be present in an amount from 0.5 to 2.5 wt%, or 0.5 to 2.25 wt%, or 0.75 to 2.25 wt%, or 1 to 2.5 wt%, or 1 to 2 wt%, based on the total weight of the composition.

[0052] The composition further comprises a siloxane-containing anti-scratch additive. The siloxane-containing anti-scratch additive may be an organically modified polysiloxane, for example, according to the following formula:

[0053] Where R 3 It is C independently each time it appears. 1-11 Alkyl, preferably C 1-4 Alkyl, more preferably methyl; R 4 It is R independently each time it appears. 3Group or polyester moiety; R 5 It is R independently each time it appears. 3 Group, polyester moiety, or C 12-36 Hydrocarbon 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. Furthermore, when m and p are 0, R 4 Not R 3 And when R 4 It is R 3 When, at least one of m and p is not 0. When R 5 It is R 3 When, then R 4 Not R 3 When R 4 It is R 3 When, then at least one R 5 Not R 3 In one respect, p=0.

[0054] If R 4 Or R 5 If it is a polyester moiety, then these polyester moieties contain 3 to 30, 8 to 25, or 15 to 25 ester repeating units. The polyester moieties may have an alcohol moiety derived from a primary unsaturated alcohol as the starting alcohol. The polyester moieties preferably have a structure -R q -(R r ) z H, where R q It is -(CH2) x -O- and R r It is -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.

[0055] The polyester moiety can be derived from the same or different starting molecules. In one aspect, the polyester moiety is derived from the same starting molecule. Preferably, the polyester moiety includes those obtained by, for example, ring-opening polyesterification of lactones. In one aspect, the polyester moiety is obtained via caprolactone or valproic acid, particularly... Those obtained by polyesterification of β-caprolactone, 3,5,5-trimethylcaprolactone, or 8-valerolactone. In one aspect, the polyester portion can be derived from... -Caprolactone.

[0056] In one respect, R 4 and / or R 5 It is the polyester portion, wherein the polyester portion contains derivatives from -Repeating units of caprolactone (e.g., 3 to 30 repeating units). In one aspect, each R 4 It is the same polyester component.

[0057] In one respect, besides R which includes a polyester portion 4 In addition, at least one R is preferred. 5 It is also the polyester component. When R 4 and R 5 When each contains a polyester portion, preferably, the polyester portion can be the same (i.e., having the same number of repeating units derived from the same starting molecule).

[0058] In one respect, if all parts R 4 It is R 3 , where R 3 The preferred form is methyl, R 5 C is preferred. 12-36 Hydrocarbon portion, preferably C 20-30 Hydrocarbon portion. In this respect, n+m+p+2 is preferably greater than or equal to 30, more preferably 40 to 50, wherein p is preferably 0, and m is preferably 30 to 48.

[0059] In one respect, if part of R 4 and / or R 5 If one or more of the components are polyester portions, then n+m+p+2 is preferably 10 to 45, more preferably 20 to 30, and particularly preferably 20 to less than 30. If R 5 If the portion is polyester, then p is preferably 0, and the value of m is 1 to 10, preferably 2 to 5.

[0060] Anti-scratch compounds containing siloxanes can be obtained by known methods via the reaction of the corresponding hydrogenated siloxane with an unsaturated hydrocarbon or unsaturated alcohol and subsequent (poly)esterification, or via the direct reaction of an unsaturated polyester with a hydrogenated siloxane. The reaction can be carried out via hydrogenation silylation or via dehydrogenation hydrogenation silylation as described in European Patent Application Publication No. 1 640 418. The preparation of polysiloxanes having a polyester moiety can be found, for example, in European Patent Application Publication No. 0 208 734.

[0061] Suitable examples of siloxane-containing compounds may include TEGOMER. TM H-Si 6441 P, TEGOMER TM H-Si6444 P and TEGOMER TM M-Si 2650, each can be purchased from Evonik.

[0062] In one aspect, the siloxane-containing additive can be an ultra-high molecular weight (UHMW) polysiloxane contained in the polymer matrix. As used herein, "ultra-high molecular weight" refers to a polysiloxane having a number average molecular weight greater than 40,000 g / mol, or greater than or equal to 100,000 g / mol, or greater than or equal to 200,000 g / mol. The polymer matrix can comprise a thermoplastic polymer, such as low-density polyethylene, polycarbonate, styrene-acrylonitrile copolymer, or polycarbonate / acrylonitrile-butadiene-styrene blend.

[0063] Exemplary UHMW polysiloxane additives may include those marketed under the trade name MULTIBASE TM Those purchased from DuPont.

[0064] Based on the total weight of the composition, the siloxane-containing anti-scratch additive is present in the composition in an amount of 0.5 to 5 wt%. Within this range, each of the second anti-scratch additives may be present in an amount of 0.5 to 4.5 wt%, or 0.5 to 4 wt%, or 0.75 to 4.5 wt%, or 0.75 to 4 wt%, or 1 to 4.5 wt%, or 1 to 4 wt%, based on the total weight of the composition.

[0065] The composition may further optionally include an additive composition. The additive composition may contain a variety of additives typically incorporated into this type of polymer composition, provided that the selected additives do not significantly adversely affect the desired properties of the composition, particularly scratch resistance and impact strength. Such additives may be mixed at appropriate times during the mixing of the components used to form 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 titanium dioxide, carbon black, and organic dyes), surface effect additives, radiation stabilizers, flame retardants, hydrostabilizers, epoxy resins, and anti-dripping agents. Combinations of additives may be used, such as one or more combinations of processing aids, heat stabilizers, UV stabilizers, and colorants.

[0066] Typically, additives are used in amounts that are generally known to be effective. For example, the total amount of additives (other than any impact modifiers, fillers, or reinforcing agents) may be 0.01 to 2 wt%, or 0.1 to 2 wt%, or 0.2 to 2 wt%, or 0.2 to 1 wt%, each based on the total weight of the composition.

[0067] The compositions of the present invention may optionally exclude other components not specifically described herein. For example, the compositions may exclude thermoplastic polymers other than poly(methyl methacrylate), poly(carbonate-siloxane), impact modifiers, and polyethylene. The compositions may optionally exclude impact modifiers other than acrylic impact modifiers. The compositions may optionally exclude polyolefins other than polyethylene. The compositions may optionally exclude anti-scratch additives other than polyethylene and siloxane-containing anti-scratch additives.

[0068] It should be understood that the total amount of the combined components is 100 wt%.

[0069] When a specific combination of poly(methyl methacrylate), poly(carbonate-siloxane), acrylic impact modifier, polyethylene, and siloxane-containing anti-scratch additives is present in the composition (each in a specific amount), the composition can exhibit good scratch resistance and impact strength.

[0070] Molded specimens of compositions containing specific amounts of the components described herein can exhibit improved scratch resistance and impact strength, either or both, preferably both. It is not desirable to be bound by theory, but it is believed that a surprising combination of scratch resistance and impact strength can be achieved through careful selection of the composition's components, including the weight percentage of siloxane units in the poly(carbonate-siloxane), the polyethylene load, and the load of the siloxane-containing anti-scratch additive. Molded specimens of the compositions exhibit a cantilever beam notched impact strength greater than 50 J / m, preferably greater than 60 J / m, measured according to ASTM D256 at 23°C and 5.5 lbf, and a scratch line roughness Ra of less than 0.2, preferably less than 0.15, determined using Keyence laser scanning confocal microscopy.

[0071] In one respect, molded specimens of the composition can exhibit good impact strength. For example, molded specimens of the composition can exhibit a cantilever beam notched impact strength greater than 50 J / m, preferably greater than 60 J / m, as measured according to ASTM D256 at 23°C and 5.5 lbf.

[0072] Molded samples of the composition also exhibit good scratch resistance. For example, molded samples of the composition can show a scratch resistance greater than 350 N / mm² under a force of 2 Newtons (N) according to the Erichsen scratch hardness test. 2 ), preferably greater than 400 N / mm 2 The hardness.

[0073] The molded samples of the composition can also exhibit a scratch line roughness Ra of less than 0.2, preferably less than 0.15, as measured using a Keyence laser scanning confocal microscope.

[0074] In one respect, the molded samples of the composition exhibited a cantilever beam notched impact strength greater than 50 J / m and a strength greater than 350 N / mm². 2 The hardness and the roughness Ra of the scratch line are less than 0.2.

[0075] In one particular aspect, the composition may comprise 60 to 70 wt% poly(methyl methacrylate); 10 to 20 wt% poly(carbonate-siloxane); 10 to 20 wt% acrylic impact modifier; and 1 to 2.5 wt% polyethylene; and 0.5 to 4.5 wt% siloxane-containing anti-scratch additive. The poly(methyl methacrylate) may be a poly(methyl methacrylate) homopolymer. The poly(carbonate-siloxane) may have a weight-average molecular weight of 25,000 to 45,000 g / mol. Based on the total weight of the poly(carbonate-siloxane), the poly(carbonate-siloxane) may have a siloxane content of 35 to 65 wt%. The acrylic impact modifier may be a core-shell impact modifier with a multilayer structure. The siloxane-containing anti-scratch additive may be an organically modified polysiloxane. Molded samples of the composition exhibit the following: a notched cantilever beam impact strength greater than 50 J / m, preferably greater than 60 J / m, measured according to ASTM D256 at 23°C and 5.5 lbf; and a scratch hardness greater than 350 N / mm², measured according to the Erichsen scratch hardness test, under a force of 2 Newtons (N). 2 Preferably greater than 400 N / mm 2 The hardness; and the scratch line roughness Ra of less than 0.2, preferably less than 0.15, as measured using a Keyence laser scanning confocal microscope.

[0076] The composition can be prepared by various methods known in the art. For example, poly(methyl methacrylate) and poly(carbonate-siloxane), along with other components, can be blended, optionally with any filler, first in a high-speed mixer or by manual mixing. The blend is then fed through a hopper into the throat of a twin-screw extruder. Alternatively, at least one component can be incorporated into the composition by feeding at least one component directly into the extruder through the throat and / or downstream via a side filler, or by preparing a masterbatch with the desired polymer and feeding it into the extruder. The extruder is typically operated at a temperature above that required to cause flow in the composition. The extrudate can be immediately quenched in a water bath and granulated. The granules thus prepared can be quarter-inch long or smaller, as needed. Such granules can be used for subsequent molding, shaping, or forming.

[0077] Also provided are molded, formed, cast, or molded articles containing the composition. The composition can be molded into useful molded articles by various methods such as injection molding, extrusion, rotational molding, blow molding, and thermoforming. Articles can be molded articles, thermoformed articles, extruded films, extruded sheets, honeycomb structures, one or more layers of multilayer articles, substrates for coating articles, or substrates for metallizing articles.

[0078] Articles containing this composition can be used in a variety of consumer products. In one aspect, the article can be an automotive component. In another aspect, the article can be a consumer electronics component, such as a housing for a consumer electronic device.

[0079] Articles may include, but are not limited to, external automotive components (e.g., grilles, mirror housings, pillars, spoilers, logos, roof racks, borders, trim, fenders), internal automotive components (e.g., decorative parts, electronic housings, dashboard components, navigation systems, housing frames), storage boxes, personal device components, household appliance components, furniture, appliance housings (e.g., robotic vacuum cleaners, drones), and consumer electronic devices (e.g., device housings or components for laptops, phones, tablets, batteries, wireless charging, AR / VR goggles).

[0080] In one aspect, articles can be automotive bumpers, automotive exterior components, automotive rearview mirror housings, automotive wheel covers, automotive dashboards or trim, automotive glove boxes, automotive door hardware or other interior trim, automotive exterior lights, automotive components in the engine compartment, agricultural tractor or equipment components, windows or components thereof, construction equipment vehicle or equipment parts, marine or personal watercraft parts, all-terrain vehicles or all-terrain vehicle parts, piping equipment, valves or pumps, air conditioning heating or cooling components, furnace or heat pump parts, computer housings, computer housings or commercial machine housings or parts, monitor housings or parts, computer routers, desktop printers, large office / industrial printers, electronic components, projector parts, electronic display parts, copier parts, scanner parts, electronic printer toner cartridges, handheld electronic device housings, handheld device housings, hair dryers, irons, coffee makers, toasters, washing machines or washing machines. Clothing machine parts, microwave ovens, ovens, power tools, electrical components, electrical housings, lighting components, components for lighting equipment, dental instruments, medical instruments, medical or dental lighting components, aircraft parts, train or track parts, seating components, sidewalls, ceiling components, cookware, medical device trays, animal cages, fibers, laser-welded medical devices, optical fibers, lenses (automatic and non-automatic), mobile phone parts, greenhouse components, solar panel components, fire helmets, safety shields, safety glasses, air pump parts, humidifier housings, thermostat housings, air conditioner drain pans, outdoor cabinets, telecommunications housings or infrastructure, Simple Network Inspection System (SNIDS) equipment, network interface equipment, smoke detectors, components or equipment in gas collection chambers, medical scanners, X-ray equipment, components for medical applications or devices, electrical boxes or housings, and electrical connectors, building or agricultural equipment, and turbine blades.

[0081] In one aspect, the articles can be components for the interior of an aircraft or train, access panels, access doors, airflow regulators, vents, ventilation grilles, handrails, luggage compartment doors, balcony components, cabinet walls, ceiling panels, door handles, doorknobs, pipe housings, housings for electronic devices, equipment housings, equipment panels, floor panels, dining carts, plates, kitchen work surfaces, handles, television housings, light panels, magazine racks, telephone housings, partitions, trolley parts, seat backs, seat assemblies, railing assemblies, seat housings, brackets, sidewalls, speaker housings, storage compartments, storage housings, toilet seats, folding tables, trays, decorative panels, window trims, window rails, balcony components, balconies, ceiling panels, life jacket covers, storage box covers, window dust covers, electrochromic device layers, television lenses, electronic displays, instruments or instrument panels, lampshades, light diffusers, lamp tubes, light tubes, reflectors, partitions, railings, refrigerator doors, shower doors, sinks, trolley containers, trolley side panels or windows.

[0082] This disclosure is further illustrated by the following embodiments, which are not limiting.

[0083] Example

[0084] The materials used in the following examples are described in Table 1.

[0085] Table 1

[0086] The compositions of the following examples were prepared by blending the components together and extruding them on a 37 mm twin-screw extruder. The compositions were then injection molded at temperatures ranging from 210 to 240°C, but those skilled in the art will recognize that the method is not limited to these temperatures. The extrusion and molding conditions are shown in Tables 2 and 3, respectively.

[0087] Table 2

[0088] Table 3

[0089] Physical measurements were performed using the following test methods. Before the melt volumetric rate (MVR) test, the sample was pre-dried at 75°C for 6 hours. For all other tests, the sample was pre-conditioned at 23°C and 50% relative humidity for 48 hours.

[0090] According to ASTM D256 or ASTM D4812, the notched impact strength and unnotched impact strength of a cantilever beam are determined on an 80 x 10 x 4 mm bar (test bar) at a temperature of 23°C under a load of 5.5 lbf.

[0091] According to ISO 1133, the melt volumetric rate (MVR) is determined at 240°C, under a load of 2.16 kg, with a residence time of 300 seconds.

[0092] According to ISO 527, tensile properties are measured at 50 mm / min on a standard ISO tensile bar at a temperature of 23°C.

[0093] Hardness was determined using the Erichsen scratch test at 2 N.

[0094] The scratch morphology, including scratch line roughness, was characterized using Keyence laser scanning confocal microscopy.

[0095] A scratch whitening test was performed on the molded plate. Three scratches were generated on the plate at 1.5 N, 2 N, and 4 N. The scratch whitening marks on the plate surface were visually inspected. Scratch whitening was defined as a white line or color change visible (through the eye) at all angles. A score of 0 indicates that the scratch was visible at all loads (1.5 N, 2 N, and 4 N). A score of 1 indicates that the scratch was slightly visible at 1.5 N, but visible at 2 N and 4 N. A score of 2 indicates that the scratch was almost invisible at 1.5 N and 2 N, but visible at 4 N. A score of 3 indicates that the scratch was almost invisible at 1.5 N, slightly visible at 2 N, but visible at 4 N. A score of 4 indicates that the scratch was invisible at 1.5 N, almost invisible at 2 N, but visible at 4 N.

[0096] The composition and results are shown in Table 4. In Table 4, the amounts of each component are provided in wt% based on the total weight of the composition.

[0097] Table 4

[0098] 1 Additives include mixtures containing stabilizers, release agents, and colorants.

[0099] Table 4 (continued)

[0100] 1 Additives include mixtures containing stabilizers, release agents, and colorants.

[0101] The mechanical properties of the molded components of the compositions described in Table 4 were tested. The results are summarized in Table 5.

[0102] Table 5

[0103] Table 5 (continued)

[0104] It would be advantageous to maintain the impact performance of the compositions of Examples E1-E18 within 10% of that of the comparative composition CE1. As shown in Table 5, the compositions of Examples E1-E18 achieved the desired impact performance.

[0105] The scratch performance of the composition was also evaluated. Three annular scratches were produced on a MAI disc (Ø=100 mm, thickness=3 mm) at 1.5 N, 2 N, and 4 N using an Erichsen scratcher equipped with a tapered tip of 18 μm diameter. Whitening of the scratch on the disc surface was visually inspected. Whitening was defined as a white line or color change visible at all angles (through the eye) and rated on a scale of 0-4 based on the above criteria. Microscopic analysis of the scratches was also performed to determine scratch dimensions (e.g., scratch width, scratch depth, pileup height, and scratch roughness). Scratches that were smooth and invisible to low-visibility to the naked eye appeared as smooth scratches in the microscopic visualization tool. Visible and white scratches tended to have a rougher profile. Linear roughness measurements (Ra) across the scratch measurements were correlated with scratch visibility: scratches with higher Ra values ​​scattered more light and were therefore more visible than smooth scratches with lower Ra values.

[0106] Typically, it is desirable to provide compositions exhibiting the following scratching properties: a whiteness rating greater than or equal to 3, preferably greater than or equal to 4; a linear roughness Ra less than 0.2, preferably less than 0.15; a scratch width less than 120 micrometers; a bulge height less than 10 micrometers, preferably less than 5 micrometers; a residual depth less than 10 micrometers, preferably less than 5 micrometers; a total groove height less than 20 micrometers, preferably less than 5 micrometers; and a value greater than 350 N / m. 2 Preferably greater than 400 N / m 2 Erichsen hardness.

[0107] The scratch performance is summarized in Table 6.

[0108] Table 6

[0109] Table 6 (continued)

[0110] A key scratch performance indicator is linear scratch roughness (Ra), especially when it relates to scratch visibility (i.e., scratch whitening). Formulations with the lowest scratch roughness (i.e., close to the reference CE1 formulation) exhibit good scratch whitening performance. Other parameters such as scratch width, depth, and ridge height indicate the material's resistance to scratching. As shown in Table 6, the whitening grade indicates the level of scratch visible to the naked eye under a force of 2 N, with grades ranging from 0 to 4. As mentioned above, grade 0 indicates very white and visible scratches, while a scratch whitening grade of 4 indicates almost invisible scratches. As seen in Table 6, the whitening grade correlates with an objective analysis of linear roughness.

[0111] Further, as shown in Table 6, the compositions of Examples E1-E10 exhibited better scratch visibility (line roughness) and better scratch resistance compared to CE1, as indicated by the scratch dimensions. Formulations E1, E5, and E6 showed performance comparable to reference CE1. The composition according to Example E12 showed better scratch performance compared to the reference CE1 formulation. Microscopic images of scratch evaluations on molded parts of the different compositions are also shown in Figure 1.

[0112] The blackness and gloss of various compositions were also evaluated. Gloss was determined according to ISO 2813. Blackness was determined by colorimetric measurement according to ASTM E308. The results for the selected compositions are shown in Table 7.

[0113] Table 7

[0114] It is desirable to provide compositions with high blackness (e.g., greater than 230) and high gloss (e.g., gloss greater than 70 at 20°), particularly for automotive applications. As shown in Table 7, in addition to the desired scratch and mechanical properties described above, the various compositions according to the invention also exhibit this combination of properties.

[0115] Delamination of various compositions was also tested. Delamination can be evaluated using the tape test according to ASTM D3359. Compositions exhibiting no delamination (i.e., 0% peeling from the surface in the tape test) are designated as Grade 5B. Compositions exhibiting less than 5% peeling are designated as Grade 4B. Compositions exhibiting 5 to 15% peeling are designated as Grade 3B. Compositions exhibiting 15 to 35% peeling are designated as Grade 2B. Compositions exhibiting 35 to 65% peeling are designated as Grade 1B. Compositions exhibiting more than 65% peeling are designated as Grade 0B.

[0116] The composition according to CE1 exhibited delamination in the tape test. In contrast, the compositions according to this disclosure generally achieved a grade of 4B or 5B, with less than 5% delamination observed. Exemplary tape test results for the selected compositions are shown in Figure 2. Specifically, as shown in Figure 2, the composition according to CE1 achieved a delamination grade of 2B. In contrast, the compositions according to E1 and E12 each achieved a delamination grade of 5B.

[0117] Therefore, as shown in the embodiments of the present invention, the inventors have advantageously discovered that a specific combination of an anti-scratch additive comprising polyethylene and a second anti-scratch additive can provide an anti-scratch composition that simultaneously retains the desired physical and mechanical properties. The compositions according to this disclosure ideally comprise a low amount (i.e., less than 3 wt%) of polyethylene, which avoids compatibility problems leading to delamination, and further comprise a low amount of the second anti-scratch additive to improve scratch performance. Thus, the inventors have discovered a synergistic effect between using a low concentration of polyethylene to avoid processing problems such as delamination and using the second anti-scratch additive to provide the desired combination of physical properties and compatibility / processability.

[0118] Therefore, this disclosure provides a significant improvement in scratch-resistant compositions.

[0119] The present invention further covers the following aspects.

[0120] Aspect 1: A composition comprising: 40 to 79.4 wt% poly(methyl methacrylate); 10 to 25 wt% poly(carbonate-siloxane) having a siloxane content of 30 to 70 wt%, preferably 35 to 65 wt%, based on the total weight of the poly(carbonate-siloxane); 10 to 25 wt% acrylic impact modifier; 0.1 to less than 3 wt% polyethylene; and 0.5 to 5 wt% siloxane-containing anti-scratch additive; wherein the weight percentages of each component are based on the total weight of the composition, and wherein molded samples of the composition exhibit a notched cantilever beam impact strength greater than 50 J / m, preferably greater than 60 J / m, measured according to ASTM D256 at 23°C and 5.5 lbf, and a scratch line roughness Ra of less than 0.2, preferably less than 0.15, determined using Keyence laser scanning confocal microscopy.

[0121] Aspect 2: The composition according to Aspect 1, wherein a molded sample of the composition exhibits a scratch hardness greater than 350 N / mm² under a force of 2 Newtons (N), as measured by the Erichsen scratch hardness test. 2 Preferably greater than 400 N / mm 2 The hardness.

[0122] Aspect 3: The composition according to aspect 1 or 2, wherein the poly(methyl methacrylate) is a poly(methyl methacrylate) homopolymer.

[0123] Aspect 4: The composition according to any one of Aspects 1 to 3, wherein the poly(carbonate-siloxane) comprises a bisphenol A carbonate repeating unit and a poly(dimethylsiloxane) repeating unit.

[0124] Aspect 5: The composition according to any one 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 cross-linked styrene-divinylbenzene column at a sample concentration of 1 mg / mL, and as calibrated using a polystyrene standard and calculated for polycarbonate.

[0125] Aspect 6: The composition according to any one of Aspects 1 to 5, wherein, based on the total weight of the poly(carbonate-siloxane), the composition does not contain poly(carbonate-siloxane) having a siloxane content of less than 30 wt%, or less than 20 wt%, or less than 10 wt%.

[0126] Aspect 7: The composition according to any one of Aspects 1 to 6, wherein the acrylic impact modifier is a core-shell impact modifier having a multilayer structure.

[0127] Aspect 8: The composition according to any one of Aspects 1 to 7, wherein the siloxane-containing additive comprises an organically modified polysiloxane, preferably wherein the organically modified polysiloxane is: a polyester-modified polysiloxane; or C 12-36 Hydrocarbon-modified polysiloxane.

[0128] Aspect 9: The composition according to any one 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, styrene-acrylonitrile copolymer, or polycarbonate / acrylonitrile-butadiene-styrene blend, preferably wherein the ultra-high molecular weight polysiloxane has a number average molecular weight greater than 40,000 g / mol, or greater than or equal to 100,000 g / mol, or greater than or equal to 200,000 g / mol.

[0129] Aspect 10: The composition according to any one of Aspects 1 to 9, wherein the polyethylene has a melt volume flow rate of greater than 6 g / 10 min, preferably greater than 15 g / 10 min, more preferably greater than 20 g / 10 min, as measured according to ISO 1133 at 290°C and 2.16 kg, and preferably wherein the polyethylene comprises low-density polyethylene, high-density polyethylene, or a combination thereof.

[0130] Aspect 11: The composition according to any one of aspects 1 to 10, wherein, based on the total weight of the composition, the composition further comprises 0.01 to 2 wt% of an additive composition.

[0131] Aspect 12: The composition according to aspect 1 comprises: 60 to 70 wt% poly(methyl methacrylate); 10 to 20 wt% poly(carbonate-siloxane); 10 to 20 wt% acrylic impact modifier; 1 to 2.5 wt% polyethylene; and 0.5 to 4.5 wt% siloxane-containing anti-scratch additive.

[0132] Aspect 13: The composition according to 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 g / mol to 45,000 g / mol; the poly(carbonate-siloxane) has a siloxane content of 35 to 65 wt% based on the total weight of the poly(carbonate-siloxane); the acrylic impact modifier is a core-shell impact modifier with a multilayer structure; and the siloxane-containing scratch-resistant additive is an organically modified polysiloxane; and wherein molded samples of the composition exhibit: a cantilever beam notched impact strength greater than 50 J / m, preferably greater than 60 J / m, measured according to ASTM D256 at 23°C and 5.5 lbf; and a scratch hardness greater than 350 N / mm, measured according to the Erichsen scratch hardness test, under a force of 2 Newtons (N). 2 Preferably greater than 400 N / mm 2 The hardness; and the scratch line roughness Ra of less than 0.2, preferably less than 0.15, as measured using a Keyence laser scanning confocal microscope.

[0133] Aspect 14: A method for preparing a composition according to any one of aspects 1 to 12, the method comprising melt-mixing the components of the composition and optionally extruding the composition.

[0134] Aspect 15: An article comprising a composition according to any one of Aspects 1 to 12, preferably wherein the article is: an automotive component or consumer electronics component; or an automotive body panel, automotive dashboard, automotive console, automotive trim, automotive sun visor; or an electrical or lighting cover, electrical or lighting housing, electrical or lighting enclosure; or a personal electronic device or household appliance.

[0135] Alternatively, compositions, methods, and articles may include, consist of, or consist substantially of any suitable materials, steps, or components disclosed herein. Compositions, methods, and articles may additionally, or alternatively, be configured to be free of, or substantially free of, any materials (or substances), steps, or components unnecessary for achieving the function or purpose of the composition, method, and article.

[0136] All scopes disclosed herein include endpoints, and endpoints may be combined independently of each other. "Composition" includes blends, mixtures, alloys, reaction products, etc. The terms "first," "second," etc., do not indicate any order, quantity, or importance, but are used to distinguish one element from another. Unless otherwise stated herein or clearly contradicted by the context, the terms "a," "an," and "the" do not indicate a limitation of quantity, but are interpreted to cover both singular and plural. Unless otherwise expressly stated, "or" means "and / or." Throughout the specification, reference to "an aspect" means that a particular element described in connection with that aspect is included in at least one aspect described herein and may or may not be present in other aspects. The term "compositions thereof," as used herein, includes one or more of the listed elements and is open to the presence of one or more unspecified similar elements. Furthermore, it should be understood that the described elements may be combined in any suitable manner in each aspect.

[0137] Unless otherwise specified herein, all test standards are the most recent standards effective from 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.

[0138] Unless otherwise defined, the technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if any terminology in this application contradicts or conflicts with a terminology in a cited reference, the terminology from this application shall take precedence over the conflicting terminology from the cited reference.

[0139] Compounds are described using standard nomenclature. For example, any position not substituted by any indicator group should be understood as having its valence filled by a bond or hydrogen atom as indicated. A dash ("-") not between two letters or symbols is used to indicate the connection point of a substituent. For example, -CHO is connected through the carbonyl group.

[0140] As used herein, the term "alkyl group," whether used alone or as a prefix, suffix, or prefix of another term, refers to a residue containing only carbon and hydrogen. The residue can be aliphatic or aromatic, linear, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain combinations of aliphatic, aromatic, linear, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. However, when an alkyl group residue is described as substituted, it may optionally contain heteroatoms other than the carbon and hydrogen members of the substituent residue. Thus, when specifically described as substituted, an alkyl group residue may also contain one or more carbonyl, amino, hydroxyl, etc., or it may contain heteroatoms within the backbone of the alkyl group residue. The term "alkyl" refers to a branched or linear, saturated aliphatic alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, and n-hexyl and sec-hexyl. "Alkenyl" refers to a straight-chain or branched monovalent hydrocarbon group having at least one carbon-carbon double bond (e.g., vinyl (-HC=CH2)). "Alkoxy" refers to an alkyl group linked via oxygen (i.e., alkyl-O-), such as methoxy, ethoxy, and sec-butoxy. "Alkylene" refers to a straight-chain or branched, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH2-) or propylidene (-(CH2)3-)). "Cycloalkylene" refers to a divalent cyclic alkylene group, -C n H 2n-x The prefix "cycloalkenyl" refers to a monovalent group having one or more rings and one or more carbon-carbon double bonds within the rings, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" refers to an aromatic hydrocarbon group containing a specified number of carbon atoms, such as phenyl, cycloheptatrienone, indenyl, or naphthyl. "Arylidene" refers to a divalent aryl group. "Alkylarylidene" refers to an arylidene substituted with an alkyl group. "Arylalkylene" refers to an alkylene substituted with an aryl group (e.g., benzyl). The prefix "halogenated" refers to a group or compound comprising one or more of fluorine, chlorine, bromine, or iodine substituents. Combinations of different halogen atoms (e.g., bromine and fluorine) or only chlorine atoms may be present. The prefix "heterogeneous" refers to a compound or group comprising at least one ring member containing heteroatoms (e.g., 1, 2, or 3 heteroatoms), wherein each heteroatom is independently N, O, S, Si, or P. "Substituted" means that a compound or group is substituted by at least one (e.g., 1, 2, 3, or 4) substituents, each of which can be C16 or C26 independently. 1-9 Alkoxy, C 1-9 Halogenated alkoxy groups, nitro groups (-NO2), cyano groups (-CN), C 1-6 alkylsulfonyl (-S(=O)2-alkyl), C 6-12 Arylsulfonyl (-S(=O)2-aryl), mercapto (-SH), thiocyano (-SCN), p-toluenesulfonyl (CH3C6H4SO2-), C3-12 cycloalkyl, C 2-12 alkenyl, C 5-12 Cycloalkenyl, C 6-12 Aryl, C 7-13 Arylalkylene, C 4-12 Heterocyclic alkyl groups, and C 3-12 A heteroaryl group can replace hydrogen, provided that the valence of the substituted atom does not exceed the conventional valence of the substituted atom. The number of carbon atoms indicated in the group does not include any substituents. For example, -CH2CH2CN is a C2 alkyl group substituted with a nitrile.

[0141] Although specific embodiments have been described, alternatives, modifications, variations, improvements, and essentially equivalents may arise in the applicant or others skilled in the art that are not currently foreseeable or may not be foreseeable. Therefore, the appended claims, as well as any appended claims that may be modified thereto, are intended to cover all such alternatives, modifications, variations, improvements, and essentially equivalents.

Claims

1. A composition comprising: 40 to 79.4 wt% of poly(methyl methacrylate); 10 to 25 wt% of poly(carbonate-siloxane), said poly(carbonate-siloxane) having a siloxane content of 30 to 70 wt%, preferably 35 to 65 wt%, based on the total weight of said poly(carbonate-siloxane); 10 to 25 wt% of an acrylic impact modifier; 0.1 to less than 3 wt% of polyethylene; and 0.5 to 5 wt% of a siloxane-containing anti-scratch additive; wherein, The weight percentages of each component are based on the total weight of the composition, wherein molded samples of the composition exhibit: a cantilever beam notched impact strength greater than 50 J / m, preferably greater than 60 J / m, measured according to ASTM D256 at 23°C and 5.5 lbf, and a scratch line roughness Ra less than 0.2, preferably less than 0.15, determined using a Keyence laser scanning confocal microscope.

2. The composition according to claim 1, wherein, Molded samples of the composition exhibited a hardness greater than 350 N / mm² under a force of 2 Newtons (N), as measured by the Erichsen scratch hardness test. 2 Preferably greater than 400 N / mm 2 The hardness.

3. The composition according to claim 1 or 2, wherein, The poly(methyl methacrylate) is a poly(methyl methacrylate) homopolymer.

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

5. The composition according to any one 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, which is determined by gel permeation chromatography using a cross-linked styrene-divinylbenzene column at a sample concentration of 1 mg / mL, and calibrated using polystyrene standards and calculated for polycarbonate.

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

7. The composition according to any one of claims 1 to 6, wherein, The acrylic impact modifier is a core-shell impact modifier with a multi-layered structure.

8. The composition according to any one of claims 1 to 7, wherein, The siloxane-containing additives include organically modified polysiloxanes, preferably wherein, The organic-modified polysiloxane is: polyester-modified polysiloxane; or C 12-36 Hydrocarbon-modified polysiloxane.

9. The composition according to any one 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, styrene-acrylonitrile copolymer, or polycarbonate / acrylonitrile-butadiene-styrene blend, preferably wherein the ultra-high molecular weight polysiloxane has a number average molecular weight greater than 40,000 g / mol, or greater than or equal to 100,000 g / mol, or greater than or equal to 200,000 g / mol.

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

11. The composition according to any one of claims 1 to 10, wherein, Based on the total weight of the composition, the composition further comprises 0.01 to 2 wt% of an additive composition.

12. The composition of claim 1, comprising: 60 to 70 wt% of the poly(methyl methacrylate); 10 to 20 wt% of the poly(carbonate-siloxane); 10 to 20 wt% of the acrylic impact modifier; and 1 to 2.5 wt% of the polyethylene; and 0.5 to 4.5 wt% of the siloxane-containing anti-scratch additive.

13. The composition according to 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; based on the total weight of the poly(carbonate-siloxane), the poly(carbonate-siloxane) has a siloxane content of 35 to 65 wt%; the acrylic impact modifier is a core-shell impact modifier with a multilayer structure; and the siloxane-containing scratch-resistant additive is an organically modified polysiloxane; and wherein, Molded samples of the composition exhibited: a cantilever beam notched impact strength greater than 50 J / m, preferably greater than 60 J / m, measured at 23°C and 5.5 lbf according to ASTM D256; and a scratch hardness greater than 350 N / mm² under a force of 2 Newtons (N), measured according to the Erichsen scratch hardness test. 2 Preferably greater than 400 N / mm 2 The hardness; and the scratch line roughness Ra of less than 0.2, preferably less than 0.15, as measured using a Keyence laser scanning confocal microscope.

14. A method for preparing the composition according to any one 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 one of claims 1 to 12, preferably wherein the article is: an automotive component or a consumer electronics component; or an automotive body panel, an automotive dashboard, an automotive console, an automotive trim, an automotive sun visor; or an electrical or lighting cover, an electrical or lighting housing, an electrical or lighting enclosure; or a personal electronic device or a household appliance.

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