Polycarbonate compositions, methods for making the same, and articles comprising the same

Abstract

A polycarbonate composition includes specific amounts of a bisphenol A homo-polycarbonate, a polycarbonate including repeating units derived from a substituted or unsubstituted cyclohexylidene-bridged bisphenol, and a polyester-carbonate. The composition can exhibit desirable properties, including a combination of low haze and good scratch resistance. Methods for making the compositions and articles comprising the compositions are also disclosed.

Description

[0001] Citations of Related Applications

[0002] This application claims priority to and the benefit of European patent application No. 22202291.5 filed on October 18, 2022, the contents of which are incorporated herein by reference in their entirety. Technical Field

[0003] The present disclosure relates to polycarbonate compositions having improved optical properties and scratch resistance, methods of making, and articles prepared from the polycarbonate compositions. Background Art

[0004] Polycarbonate (PC) has excellent impact strength and clarity, but often lacks scratch resistance. Efforts to improve scratch resistance include, for example, hard coating the composition or including anti-scratch additives in the composition. These approaches may not be desirable in all applications. For example, in the case of hard coating, expensive additional processing steps are introduced into the manufacturing process.

[0005] Therefore, there remains a need in the art for scratch resistant compositions that also have good mechanical properties (including impact strength and tensile properties) and weatherability. Particularly desirable are compositions that have good optical clarity. Summary of the invention

[0006] The polycarbonate composition comprises: 10 to 60 weight percent of bisphenol A homopolycarbonate, based on the total weight of the composition; a polycarbonate comprising repeating units derived from substituted or unsubstituted cyclohexylidene-bridged bisphenols in an amount effective to provide a substituted or unsubstituted cyclohexylidene-bridged bisphenol content of 25 weight percent or less, based on the total weight of the composition; and a polyester-carbonate comprising ester units derived from isophthalic acid, terephthalic acid, and resorcinol; wherein the composition has a cyclohexylidene-bridged bisphenol:(isophthalic acid, terephthalic acid, and resorcinol ester units) weight ratio of less than 2.5.

[0007] A method of preparing a polycarbonate composition comprises melt mixing the components of the composition, and optionally extruding the composition.

[0008] An article comprises a polycarbonate composition.

[0009] The above described and other features are exemplified by the following figures and detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] The following figures represent exemplary embodiments.

[0011] Figure 1 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane carbonate (DMBPC) content versus turbidity of the compositions of Examples. DETAILED DESCRIPTION

[0012] Thus, provided herein are compositions having a combination of good scratch resistance, mechanical properties, and weatherability. In additional advantageous features, the compositions can exhibit low haze, which can facilitate the formulation of compositions having specific colors. The compositions comprise specific amounts of bisphenol A homopolycarbonate, polycarbonates comprising repeating units derived from substituted or unsubstituted cyclohexylidene-bridged bisphenols, and polyester-carbonates.

[0013] Therefore, a polycarbonate composition represents an aspect of the present disclosure. The composition comprises bisphenol A homopolycarbonate. The bisphenol A homopolycarbonate has a repeating structural carbonate unit of formula (1).

[0014]

[0015] Bisphenol A polycarbonate homopolymers can be prepared from bisphenol A ((2,2-bis(4-hydroxyphenyl)propane or BPA) by methods such as interfacial polymerization and melt polymerization, which are known and described, for example, in WO 2013 / 175448 A1 and WO 2014 / 072923 A1. End-capping agents may be included during polymerization to provide end groups, such as monocyclic phenols such as phenol, p-cyanophenol, and C 1-22 Alkyl-substituted phenols such as p-cumylphenol, resorcinol monobenzoate, and p-tert-butylphenol, monoethers of diphenols such as p-methoxyphenol, monoesters of diphenols such as resorcinol monobenzoate, functionalized chlorides of aliphatic monocarboxylic acids such as acryloyl chloride and methacryloyl chloride, and monochloroformates such as phenyl chloroformate, alkyl-substituted phenyl chloroformate, p-cumylphenyl chloroformate, and toluene chloroformate. Phenol and p-cumylphenol are specifically mentioned. Combinations of different end-capping agents can be used. Branched polycarbonate blocks can be prepared by adding a branching agent during the polymerization process, such as trimellitic acid, trimellitic anhydride, trimellitic acid chloride, tri-p-hydroxyphenylethane, isatin-bisphenol, trisphenol TC (1,3,5-tris((p-hydroxyphenyl)isopropyl)benzene), trisphenol PA (4(4(1,1-bis(p-hydroxyphenyl)-ethyl)α,α-dimethylbenzyl)phenol), 4-chloroformylphthalic anhydride, trimesic acid, and benzophenonetetracarboxylic acid. The branching agent can be added at a level of 0.05 to 4.0 weight percent (wt%), for example, 0.05 to 2.0 wt%. Combinations including linear polycarbonates and branched polycarbonates can be used.

[0016] The bisphenol A polycarbonate homopolymer may be a linear bisphenol A polycarbonate homopolymer, optionally end-capped with phenol or p-cumylphenol, and having a weight average molecular weight of 10,000 to 100,000 grams per mole (g / mol), or 10,000 to 75,000 g / mol, or 18,000 to 40,000 g / mol, or 20,000 to 40,000 g / mol, or 20,000 to 38,000 g / mol, as measured by gel permeation chromatography (GPC) using a cross-linked styrene-divinylbenzene column and calibrated relative to a bisphenol A polycarbonate reference. The GPC sample is prepared at a concentration of 1 milligram per milliliter (mg / mL) and eluted at a flow rate of 1.5 ml / min.

[0017] In one aspect, more than one bisphenol A polycarbonate homopolymer may be present. For example, the bisphenol A polycarbonate homopolymer may include a first bisphenol A polycarbonate homopolymer having a first weight average molecular weight and a second bisphenol A polycarbonate homopolymer having a second weight average molecular weight, wherein the first weight average molecular weight and the second weight average molecular weight are different. When present, the weight ratio of the first bisphenol A polycarbonate homopolymer to the second bisphenol A polycarbonate homopolymer may be 10:1 to 1:10, or 5:1 to 1:5, or 3:1 to 1:3, or 2:1 to 1:2.

[0018] Based on the gross weight of the composition, the bisphenol A homopolycarbonate can be present in the composition in an amount of 10 to 60 weight percent. Within this range, the bisphenol A homopolycarbonate can be present in an amount of, for example, 10 to 55 weight percent, or 14 to 60 weight percent, or 14 to 55 weight percent, or 15 to 60 weight percent, or 15 to 55 weight percent, or 10 to 50 weight percent, or 12 to 50 weight percent, or 14 to 50 weight percent, or 10 to 45 weight percent, or 12 to 45 weight percent, or 14 to 45 weight percent, each based on the gross weight of the composition.

[0019] In addition to bisphenol A homopolycarbonate, the composition comprises a polycarbonate comprising repeating units derived from substituted or unsubstituted cyclohexylidene bridged bisphenols. The repeating units derived from substituted or unsubstituted cyclohexylidene bridged bisphenols may be according to formula (2):

[0020]

[0021] Among them, R a and R b Each is independently C 1-12 Alkyl; R g It is C 1-12 alkyl; p and q are each independently 0 to 4; and t is 0 to 10. In one aspect, each Ra and R b In one aspect, at least one of R a and R b Each is independently C 1-4 Alkyl, R g It is C 1-4 alkyl, p and q are each 0 or 1, and t is 0 to 5. In one aspect, R a , R b and R g Each is methyl, p and q are each 0 or 1, and t is 0 or 3, preferably 0. In yet another aspect, p and q are each 0, each R g is methyl, and t is 3, such that the cyclohexylidene bridging group is 3,3-dimethyl-5-methylcyclohexylidene. In another aspect, p and q are each 1, R a and R b Each is a methyl group, and t is 0, such that the cyclohexylidene bridging group is an unsubstituted cyclohexylidene group. For example, a cyclohexylidene bridged polycarbonate may comprise repeating units according to formula (3):

[0022]

[0023] As used herein, "polycarbonate" includes homopolymers (e.g., wherein all repeating units are according to formula (2) or (3)), copolymers comprising repeating units derived from different bisphenols, and copolymers comprising carbonate units according to formula (2) or (3) and other types of polymer units such as ester units or siloxane units.

[0024] In one aspect, the cyclohexylidene-bridged polycarbonate can be a copolycarbonate further comprising repeating units derived from a bisphenol different from the cyclohexylidene-bridged bisphenol. For example, the copolycarbonate can comprise additional repeating units according to formula (4):

[0025]

[0026] Among them, each R 1 Contains at least one C 6-30 Aromatic groups. For example, each R 1 It may be derived from a dihydroxy compound such as an aromatic dihydroxy compound of formula (5) or a bisphenol of formula (6).

[0027]

[0028] In formula (5), each R h are independently halogen atoms, such as bromine, C 1-10 Hydrocarbon such as C 1-10 Alkyl, halogen substituted C1-10 Alkyl, C 6-10 Aryl or halogen substituted C 6-10 aryl, and n is 0 to 4. In formula (6), R a and R b are independently halogen, C 1-12 Alkoxy, or C 1-12 alkyl, and p and q are each independently an integer from 0 to 4, such that when p or q is less than 4, the valence of each carbon of the ring is filled by hydrogen. In one aspect, p and q are each 0, or p and q are each 1, and R a and R b Each is C 1-3 An alkyl group, preferably a methyl group, is disposed meta to the hydroxyl group on each arylene group. a It is a bridging group connecting two hydroxy-substituted aromatic groups, where each C 6 The bridging group and the hydroxyl substituent of the arylene group are at C 6 Arylene groups are arranged ortho, meta or para (preferably para) to each other, for example, a single bond, -O-, -S-, -S(O)-, -S(O) 2 -, -C(O)-, or C 1-18 An organic group, which may be cyclic or acyclic, aromatic or non-aromatic, and may further contain heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorus. For example, X a Can be substituted or unsubstituted C 3-18 Cycloalkylidene; Formula -C(R c )(R d )-C 1-25 Alkylene, where R c and R d are independently hydrogen, C 1-12 Alkyl, C 1-12 Cycloalkyl, C 7-12 Aralkyl, C 1-12 Heteroalkyl, or cyclic C 7-12 Heteroaralkyl; or -C(=R e )-, wherein R e It is a two-price C 1-12 Hydrocarbon.

[0029] Examples of the bisphenol compound include 4,4'-dihydroxybiphenyl, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)-1-naphthylmethane, 1,2-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 1,1-bis(hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)isobutylene, 1,1-bis(4-hydroxyphenyl)cyclodecane, dioxane, trans-2,3-bis(4-hydroxyphenyl)-2-butene, 2,2-bis(4-hydroxyphenyl)adamantane, α,α'-bis(4-hydroxyphenyl)toluene, bis(4-hydroxyphenyl)acetonitrile, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3-ethyl-4-hydroxyphenyl)propane, 2,2-bis(3-n-propyl-4-hydroxyphenyl)propane, 2,2-bis(3-isopropyl-4-hydroxyphenyl)propane, 2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2 -bis(3-allyl-4-hydroxyphenyl)propane, 2,2-bis(3-methoxy-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 1,1-dichloro-2,2-bis(4-hydroxyphenyl)ethylene, 1,1-dibromo-2,2-bis(4-hydroxyphenyl)ethylene, 1,1-dichloro-2,2-bis(5-phenoxy-4-hydroxyphenyl)ethylene, 4,4'-dihydroxybenzophenone, 3,3-bis(4-hydroxyphenyl)-2-butanone, 1,6-bis(4-hydroxyphenyl)-1,6-hexanedione, ethylene glycol bis(4-hydroxyphenyl) ether, bis(4-hydroxyphenyl) ether, bis(4-hydroxyphenyl) sulfide, (4-hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl) sulfone, 9,9-bis(4-hydroxyphenyl) fluorene, 2,7-dihydroxypyrene, 6,6'-dihydroxy-3,3,3',3'-tetramethylspiro(bis)indane ("spirobiindane bisphenol"), 3,3-bis(4-hydroxyphenyl)phthalimide, 2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene, 2,7-dihydroxyphenoxathin, 2,7-dihydroxy-9,10-dimethylphenazine, 3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, and 2,7-dihydroxycarbazole;Resorcinol, substituted resorcinol compounds such as 5-methylresorcinol, 5-ethylresorcinol, 5-propylresorcinol, 5-butylresorcinol, 5-tert-butylresorcinol, 5-phenylresorcinol, 5-cumylresorcinol, 2,4,5,6-tetrafluororesorcinol, 2,4,5,6-tetrabromoresorcinol, etc.; catechol; hydroquinone; substituted hydroquinones such as 2-methylhydroquinone, 2-ethylhydroquinone, 2-propylhydroquinone, 2-butylhydroquinone, 2-tert-butylhydroquinone, 2-phenylhydroquinone, 2-cumylhydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,5,6-tetra-tert-butylhydroquinone, 2,3,5,6-tetrafluorohydroquinone, 2,3,5,6-tetrabromohydroquinone, etc.;

[0030] Specific dihydroxy compounds include resorcinol, 2,2-bis(4-hydroxyphenyl)propane ("bisphenol A" or "BPA"), 3,3-bis(4-hydroxyphenyl)phthalimide, 2-phenyl-3,3'-bis(4-hydroxyphenyl)phthalimide (also known as N-phenylphenolphthalein bisphenol, "PPPBP", or 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one), and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (isophorone bisphenol).

[0031] In one aspect, the polycarbonate comprising repeating units derived from a substituted or unsubstituted cyclohexylidene-bridged bisphenol comprises a first carbonate repeating unit having the structure:

[0032] as well as

[0033] A second carbonate repeating unit having the structure:

[0034]

[0035] Among them, in the above formula, R a , R b and R g Each is independently C 1-12 Alkyl group, R c and R d are independently hydrogen, C 1-12 Alkyl, cyclic C 1-12 Alkyl, C 7-12 Aralkyl, C 1-12 Heteroalkyl, or cyclic C 7-12 heteroarylalkyl; p and q are each independently 0 to 4, and t is 0 to 10.

[0036] In one aspect, the cyclohexylidene-bridged polycarbonate is a copolycarbonate further comprising repeating units derived from bisphenol A. For example, the first polycarbonate can comprise repeating units of formula (2) and formula (4a):

[0037]

[0038] In one aspect, the polycarbonate comprising repeating units derived from substituted or unsubstituted cyclohexylidene-bridged bisphenols can have the following structure:

[0039]

[0040] Wherein, the molar ratio of x to y is 25:75 to 75:25.

[0041] The cyclohexylidene-bridged polycarbonate comprises repeating units derived from substituted or unsubstituted cyclohexylidene-bridged bisphenols in an amount effective to provide a substituted or unsubstituted cyclohexylidene-bridged bisphenol content of 25 weight percent or less, or 22 weight percent or less, or greater than 0 to 25 weight percent, or greater than 0 to 22 weight percent, or 1 to 25 weight percent, or 1 to 22 weight percent, or 5 to 25 weight percent, or 5 to 22 weight percent, each based on the total weight of the composition.

[0042] In one aspect, the polycarbonate comprising repeating units derived from substituted or unsubstituted cyclohexylidene-bridged bisphenol can have a substituted or unsubstituted cyclohexylidene-bridged bisphenol content of 40 to 60 weight percent, or 45 to 55 weight percent, or 47 to 53 weight percent, each based on the total weight of the polycarbonate comprising repeating units derived from substituted or unsubstituted cyclohexylidene-bridged bisphenol.

[0043] The polycarbonate comprising repeating units derived from substituted or unsubstituted cyclohexylidene bridged bisphenols can be present in the composition, for example, in an amount of 5 to 45 weight percent, based on the total weight of the composition, provided that the polycarbonate comprising repeating units derived from substituted or unsubstituted cyclohexylidene bridged bisphenols is present in an amount sufficient to provide a substituted or unsubstituted cyclohexylidene bridged bisphenol content of 25 weight percent or less. Within this range, the polycarbonate comprising repeating units derived from substituted or unsubstituted cyclohexylidene bridged bisphenols can be present in an amount of 7 to 43 weight percent, or 10 to 40 weight percent, each based on the total weight of the composition.

[0044] The composition further comprises a polyester-carbonate. The polyester-carbonate comprises repeating units derived from isophthalic acid, terephthalic acid and resorcinol. For example, the polycarbonate-ester may comprise repeating units according to formula (7):

[0045]

[0046] wherein J is a divalent group derived from an aromatic dihydroxy compound of formula (5) (e.g., resorcinol) or a bisphenol of formula (6) (e.g., bisphenol A); and T is a divalent group derived from a dicarboxylic acid including terephthalic acid and isophthalic acid. Specific dicarboxylic acids include a combination of isophthalic acid and terephthalic acid, wherein the weight ratio of isophthalic acid to terephthalic acid is 91:9 to 2:98.

[0047] The molar ratio of ester units to carbonate units in the polyester-carbonates may vary widely, for example 1:99 to 99:1, preferably 10:90 to 90:10, more preferably 25:75 to 75:25, or 2:98 to 15:85, depending on the desired properties of the final composition.

[0048] In one aspect, the polyester-carbonate is of the formula:

[0049]

[0050] Among them, R 1 Derived from an aromatic dihydroxy compound of the formula:

[0051]

[0052] Among them, R a and R b are independently halogen, C 1-12 Alkoxy, or C 1-12 alkyl, p and q are each independently an integer from 0 to 4, and X a is a single bond, -O-, -S-, -S(O)-, -S(O) 2 -, -C(O)-, or C 1-60 an organic group; and R h is independently a halogen atom, C 1-10 Alkyl groups, halogen-substituted C 1-10 Alkyl group, C 6-10 Aryl group, or halogen substituted C 6-10 An aryl group, and n is 0 to 4.

[0053] In one aspect, the polyester-carbonate comprises aromatic ester units and monoarylate ester units derived from the reaction of a combination of isophthalic acid and terephthalic acid (or reactive derivatives thereof) with resorcinol (or reactive derivatives thereof) to provide resorcinol isophthalate / resorcinol terephthalate ("ITR" ester units). The ITR ester units may be present in the polyester-carbonate in an amount greater than or equal to 95 mol%, preferably greater than or equal to 99 mol%, and even more preferably greater than or equal to 99.5 mol%, based on the total moles of ester units in the polycarbonate. Preferred polyester-carbonates comprise bisphenol A carbonate units, and ITR ester units derived from terephthalic acid, isophthalic acid, and resorcinol, i.e., poly(bisphenol A carbonate-co-isophthalic acid / terephthalic acid-resorcinol ester) of formula (8):

[0054]

[0055] Wherein, the molar ratio of x:z is from 98:2 to 2:98, or from 90:10 to 10:90. In one aspect, the molar ratio of x:z is from 50:50 to 99:1, or from 1:99 to 50:50. Based on the total moles of ester units in the copolymer, the ITR ester units may be present in the poly(bisphenol A carbonate-co-isophthalic acid-terephthalic acid-resorcinol ester) in an amount greater than or equal to 95 mol%, preferably greater than or equal to 99 mol%, and more preferably greater than or equal to 99.5 mol%. Based on the total moles of units in the copolymer, other carbonate units, other ester units, or combinations thereof may be present in a total amount of 1 to 20 mol%, such as monoaryl carbonate units of formula (9) and bisphenol ester units of formula (10):

[0056]

[0057] Among them, in the above formula, R h Each is independently C 1-10 Hydrocarbyl, n is 0-4, R a and R b Each is independently C 1-12 alkyl, p and q are each independently an integer of 0 to 4, and X a is a single bond, -O-, -S-, -S(O)-, -S(O) 2 -, -C(O)-, or -C(R c )(R d )-C 1-13 Alkylene, where R c and R d are independently hydrogen or C 1-12 Alkyl, or -C(=R e)-, wherein R e It is a two-price C 1-12 The bisphenol ester unit may be a bisphenol A phthalate unit of formula (10a):

[0058]

[0059] In one aspect, the poly(bisphenol A carbonate-co-isophthalic acid / terephthalic acid-resorcinol ester) comprises 1-90 mol% of bisphenol A carbonate units, 10-99 mol% of isophthalic acid-terephthalic acid-resorcinol ester units, and alternatively 1-60 mol% of resorcinol carbonate units, isophthalic acid-terephthalic acid-bisphenol A phthalate units, or combinations thereof. In another aspect, the poly(bisphenol A carbonate-co-isophthalic acid / terephthalic acid-resorcinol ester) comprises 10-20 mol% of bisphenol A carbonate units, 20-98 mol% of isophthalic acid-terephthalic acid-resorcinol ester units, and alternatively 1-60 mol% of resorcinol carbonate units, isophthalic acid-terephthalic acid-bisphenol A phthalate units, or combinations thereof. In one aspect, the ester units derived from isophthalic acid, terephthalic acid, and resorcinol are present in the polyester-carbonate in an amount of 10 to 30 weight percent, based on the total weight of the polyester-carbonate.

[0060] The polyester-carbonate may have an Mw of 2,000-100,000 g / mol, preferably 3,000-75,000 g / mol, more preferably 4,000-50,000 g / mol, more preferably 5,000-35,000 g / mol, and still more preferably 25,000-35,000 g / mol. Molecular weight determinations were performed using gel permeation chromatography (GPC) using a crosslinked styrene-divinylbenzene column at a sample concentration of 1 mg / ml and calibrated with bisphenol A homopolycarbonate standards. The sample was eluted with dichloromethane at a flow rate of 1.0 ml / min.

[0061] The polyester-carbonate can be present in the composition in an amount to provide a weight ratio of cyclohexylidene bridged bisphenol:(isophthalic acid, terephthalic acid, and resorcinol ester units) of less than 2.5, or less than 2.25. The ratio of cyclohexylidene bridged bisphenol:(isophthalic acid, terephthalic acid, and resorcinol ester units) is greater than 0, and can be, for example, 0.1 to less than 2.5, or 0.1 to less than 2.25, or 0.3 to less than 2.5, or 0.3 to less than 2.25, or 0.5 to less than 2.5, or 0.5 to less than 2.25. For example, the polyester-carbonate can be present in the composition in an amount of 35 to 55 weight percent, based on the total weight of the composition, provided that the weight ratio of cyclohexylidene bridged bisphenol:(isophthalic acid, terephthalic acid, and resorcinol ester units) is within the above limits. Within this range, the polyester-carbonate can be present in an amount of 37 to 53 weight percent, or 40 to 50 weight percent, or 42 to 48 weight percent, each based on the total weight of the composition.

[0062] In one aspect, the polycarbonate composition can comprise 15 to 55 weight percent bisphenol A homopolycarbonate; 35 to 55 weight percent polyester-carbonate; and 5 to 45 weight percent polycarbonate comprising repeating units derived from substituted or unsubstituted cyclohexylidene bridged bisphenols. The composition can have a cyclohexylidene bridged bisphenol content of 22 weight percent or less. The weight ratio of cyclohexylidene bridged bisphenol: (isophthalic acid, terephthalic acid, and resorcinol ester units) can be less than 2.25.

[0063] Thermoplastic composition can further include additive composition optionally.Additive composition can include one or more additives selected to realize the desired properties, condition is that additive is also selected to not significantly adversely affect the desired properties of thermoplastic composition.During the mixing of the components for forming the composition, additive composition or separate additive can be mixed at the appropriate time.Additive can be soluble or insoluble in polycarbonate.Additive composition can include flow modifier, filler (for example, granular polytetrafluoroethylene (PTFE), glass, carbon, mineral or metal), reinforcing agent (for example, glass fiber), antioxidant, heat stabilizer, light stabilizer, ultraviolet (UV) light stabilizer, UV absorbing additive, plasticizer, lubricant, release agent (such as mold release agent), antistatic agent, antifogging agent, biocide, colorant (for example, dye or pigment), surface effect additive, radiation stabilizer, flame retardant, anti-dripping agent (for example, PTFE encapsulated styrene-acrylonitrile copolymer (TSAN)) or their combination.For example, the combination of heat stabilizer, release agent and ultraviolet light stabilizer can be used. The additives may be used in amounts generally known to be effective. For example, the total amount of the additive composition (excluding any impact modifier, filler, or reinforcing agent) may be 0.1 to 10 weight percent, based on the total weight of the composition.

[0064] In one aspect, the composition may include a heat stabilizer additive. The heat stabilizer additive includes an organic phosphite (e.g., triphenyl phosphite, tri-(2,6-dimethylphenyl) phosphite, tri-(mixed mono- and di-nonylphenyl) phosphite, etc.), a phosphonate (e.g., dimethylphenylphosphonate, etc.), a phosphate (e.g., trimethyl phosphate, etc.), or a combination thereof. The heat stabilizer may be an IRGAPHOS TM 168 Available tris(2,4-di-tert-butylphenyl)phosphate. Heat stabilizers are generally used in amounts of 0.01 to 5 wt %, based on the total weight of the composition.

[0065] There is considerable overlap among plasticizers, lubricants, and mold release agents, including, for example, phthalates (e.g., octyl-4,5-epoxy-hexahydrophthalate), tris-(octyloxycarbonylethyl)isocyanurate, di- or polyfunctional aromatic phosphates (e.g., resorcinol tetraphenyl diphosphate (RDP), bis(diphenyl)phosphate of hydroquinone, and bis(diphenyl)phosphate of bisphenol A); poly-α-olefins; epoxidized soybean oil; silicones, including silicone oils (e.g., poly(dimethyldiphenylsiloxane); fatty acid esters (e.g., C 1-32Alkyl stearyl esters such as methyl stearate and stearyl stearate, and esters of stearic acid such as pentaerythritol tetrastearate, glyceryl tristearate (GTS), etc.), waxes (e.g., beeswax, montan wax, paraffin, etc.), or combinations thereof. These are generally used in an amount of 0.01 to 5 wt % based on the total weight of the composition.

[0066] Light stabilizers or ultraviolet (UV) absorbing additives, also known as UV stabilizers, may also be used. Light stabilizer additives include benzotriazoles such as 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-benzotriazole, and 2-hydroxy-4-n-octyloxybenzophenone, or the like, or combinations thereof.

[0067] UV absorbing additives include hydroxybenzophenones; hydroxybenzotriazoles; hydroxybenzotriazines; cyanoacrylates; oxalanilides; benzoxazinones; aryl salicylates; monoesters of diphenols, such as resorcinol monobenzoate; 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol (CYASORB TM 5411); 2-Hydroxy-4-octyloxybenzophenone (CYASORB TM 531); 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-(octyloxy)-phenol (CYASORB TM 1164); 2,2'-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one)(CYASORB TM UV-3638); poly[(6-morpholinyl-s-triazine-2,4-diyl)[2,2,6,6-tetramethyl-4-piperidinyl)imino]-hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imino], 2-hydroxy-4-octyloxybenzophenone (UVINUL TM 3008), 6-tert-butyl-2-(5-chloro-2H-benzotriazol-2-yl)-4-methylphenyl (UVINUL TM 3026), 2,4-di-tert-butyl-6-(5-chloro-2H-benzotriazol-2-yl)-phenol (UVINUL TM 3027), 2-(2H-benzotriazole-2-yl)-4,6-di-tert-amylphenol (UVINUL TM 3028), 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol (UVINUL TM3029), 1,3-bis[(2'cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis-{[(2'-cyano-3',3'-diphenylacryloyl)oxy]methyl}-propane (UVINUL TM 3030), 2-(2H-benzotriazole-2-yl)-4-methylphenol (UVINUL TM 3033), 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (UVINUL TM 3034), ethyl-2-cyano-3,3-diphenylacrylate (UVINUL TM 3035), (2-ethylhexyl)-2-cyano-3,3-diphenylacrylate (UVINUL TM 3039), N,N'-bisformyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine (UVINUL4050H), bis-(2,2,6,6-tetramethyl-4-piperidinyl)-sebacate (UVINUL TM 4077H), bis-(1,2,2,6,6-pentamethyl-4-piperidinyl)-sebacate + methyl-(1,2,2,6,6-pentamethyl-4-piperidinyl)-sebacate (UVINUL TM 4092H), 1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane (UVINUL TM 3030); 2,2'-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one); 1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane; TINUVIN TM 234; nano-sized inorganic materials such as titanium oxide, cerium oxide and zinc oxide, each having a particle size less than or equal to 100 nanometers; or others, or a combination thereof. The UV absorber can be used in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the polycarbonate and the impact modifier. UV absorbers that may be particularly suitable for the polycarbonate compositions disclosed herein include 2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol (e.g., CYASORB TM 5411, commercially available from Cytec Industries, Inc., Woodland Park, New Jersey) and 2,2'-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one) (e.g., CYASORB TMUV-3638, commercially available from Cytec Industries, Inc., Woodland Park, New Jersey), or a combination thereof. The UV stabilizer may be present in an amount of 0.01 to 1 wt %, preferably 0.1 to 0.5 wt %, and more preferably 0.15 to 0.4 wt %, based on the total weight of the polycarbonate composition.

[0068] Possible fillers or reinforcing agents include, for example, mica, clay, feldspar, quartz, quartzite, perlite, diatomite, diatomaceous earth, aluminosilicate (mullite), synthetic calcium silicate, fused silica, fumed silica, sand, boron-nitride powder, boron-silicate powder, calcium sulfate, calcium carbonate (such as chalk, limestone, marble, and synthetic precipitated calcium carbonate), talc (including fibrous, modular, needle-shaped, and layered talc), wollastonite, hollow or solid glass spheres, silicate spheres, coal cells, aluminosilicates or (Armosphere), kaolin, silicon carbide whiskers, aluminum oxide, boron carbide, iron, nickel or copper, continuous and chopped carbon fibers or glass fibers, molybdenum sulfide, zinc sulfide, barium titanate, barium ferrite, barium sulfate, barite, TiO 2 , aluminum oxide, magnesium oxide, granular or fibrous aluminum, bronze, zinc, copper or nickel, glass flakes, flaky silicon carbide, flaky aluminum diboride, flaky aluminum, steel flakes, natural fillers such as wood flour, fibrous cellulose, cotton, sisal, jute, starch, lignin, peanut shells or rice husks, reinforcing organic fiber fillers such as poly (ether ketone), polyimide, polybenzoxazole, poly (phenylene sulfide), polyester, polyethylene, aromatic polyamide, aromatic polyimide, polyetherimide, polytetrafluoroethylene and poly (vinyl alcohol), and combinations thereof. Fillers and reinforcing agents can be coated with a metal material layer to promote conductivity, or surface treated with silane to improve adhesion and dispersion with a polymer matrix. Fillers are used in an amount of 1 to 200 parts by weight based on 100 parts by weight of the total composition. In one aspect, fillers are not present in the composition.

[0069] Colorants such as pigments or dye additives may also be present. Useful pigments may include, for example, inorganic pigments such as metal oxides and mixed metal oxides such as zinc oxide, titanium dioxide, iron oxides, etc.; sulfides such as zinc sulfide, etc.; aluminates; sodium sulfo-silicates sulfates, chromates, etc.; carbon black; zinc ferrite; ultramarine; organic pigments such as azo, diazo, quinacridone, perylene, naphthalenetetracarboxylic acid, flavanone, isoindolinone, tetrachloroisoindolone, anthraquinone, anthrone, dioxazine, phthalocyanine, and azo lakes; Pigment Red 101, Pigment Red 122, Pigment Red 149, Pigment Red 177, Pigment Red 179, Pigment Red 202, Pigment Violet 29, Pigment Blue 15, Pigment Blue 60, Pigment Green 7, Pigment Yellow 119, Pigment Yellow 147, Pigment Yellow 150, Pigment Brown 24, Pigment Blue 29, or combinations thereof.

[0070] The dyes are typically organic materials and include coumarin dyes such as coumarin 460 (blue), coumarin 6 (green), Nile red, etc.; lanthanide complexes; hydrocarbon and substituted hydrocarbon dyes; polycyclic aromatic hydrocarbon dyes; scintillating dyes such as oxazole or oxadiazole dyes; aryl or heteroaryl substituted poly(C 2-8)Olefin dyes; carbocyanine dyes; indanthrene dyes; phthalocyanine dyes; oxazine dyes; quinolone dyes; naphthalenetetracarboxylic acid dyes; porphyrin dyes; bis(styryl)biphenyl dyes; acridine dyes; anthraquinone dyes; cyanine dyes; methine dyes; arylmethane dyes; azo dyes; indigo dyes, thioindigo dyes, diazo dyes; nitro dyes; quinoneimine dyes; aminoketone dyes; tetrazolium dyes; thiazole dyes; perylene dyes, peronone dyes; bis-benzoxazolylthiophene (BBOT); triarylmethane dyes ; xanthene dyes; thioxanthene dyes; naphthalimide dyes; lactone dyes; pyrazolone dyes; fluorophores such as anti-Stokes shift dyes, which absorb in the near infrared and emit in the visible wavelength, or others; luminescent dyes, such as 7-amino-4-methylcoumarin; 3-(2'-benzothiazolyl)-7-diethylaminocoumarin; 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole; 2,5-bis-(4-biphenylyl)-oxazole; 2,2'-dimethyl-p-tetra biphenyl; 2,2-dimethyl-p-terphenyl; 3,5,3",5""-tetra-tert-butyl-p-pentaphenyl; 2,5-diphenylfuran; 2,5-diphenyloxazole; 4,4'-diphenylstilbene; 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran; 1,1'-diethyl-2,2'-carbocyanine iodide; 3,3'-diethyl-4,4',5,5'-dibenzothiatricarbocyanine iodide; 7-dimethylamino-1-methyl 2-(4-(4-dimethylaminophenyl)-1,3-butadienyl)-3-ethylbenzothiazolium perchlorate; 3-diethylamino-7-diethyliminophenoxazine perchlorate; 2-(1-naphthyl)-5-phenyloxazole; 2,2'-p-phenylene-bis(5-phenyloxazole); rhodamine 700; rhodamine 800; pyrene, chrysene, rubrene, coronene, etc.; or combinations thereof.

[0071] In one aspect, the polycarbonate composition can include a colorant composition that can include, for example, those known under their color index numbers: solvent green 3, solvent green 28, solvent red 52, solvent red 111, solvent red 135, solvent red 169, solvent red 179, solvent red 207, disperse red 22, vat red 41, solvent orange 60, solvent orange 63, solvent violet 13, solvent violet 14, solvent violet 50, amino ketone black, solvent black 7, nigrosine dye, disperse blue 73, solvent blue 97, solvent blue 101, solvent blue 104, solvent blue 138, disperse yellow 160, solvent yellow 84, solvent yellow 93, solvent yellow 98, solvent yellow 163, solvent yellow 160:1, and mixtures comprising at least one of the foregoing colorants. Preferred colorants can include solvent red 207, disperse orange 47, solvent green 3, and mixtures comprising at least one of the foregoing colorants.

[0072] Colorants can be used in amounts and combinations sufficient to darken and opacify the molded article, and more specifically to provide the brightness values ​​described below. The specific amount of the colorant used can depend, among other factors, on its solubility and extinction coefficient in the polycarbonate composition, and whether it is used in combination with one or more additional colorants. Suitable amounts and combinations can be easily determined by one of ordinary skill in the art guided by the present disclosure. The amount of a typical colorant can be, for example, 0.1 to 1 weight percent based on the total weight of the composition, for example, 0.5 to 1 weight percent based on the total weight of the composition.

[0073] In one aspect, the colorant composition, when present, can provide the polycarbonate composition with a black color, such as piano black or jet black.

[0074] In one aspect, the composition can include a flame retardant. Useful flame retardants can include organic compounds that include phosphorus, bromine, or chlorine. For regulatory reasons, non-brominated and non-chlorinated phosphorus-containing flame retardants, such as organic phosphates and organic compounds containing phosphorus-nitrogen bonds, may be preferred in certain applications.

[0075] Flame retardant aromatic phosphates include triphenyl phosphate, tricresyl phosphate, isopropylated triphenyl phosphate, phenyl bis(dodecyl) phosphate, phenyl bis(neopentyl) phosphate, phenyl bis(3,5,5'-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, bis(2-ethylhexyl) p-tolyl phosphate, tricresyl phosphate, bis(2-ethylhexyl) phenyl phosphate, tri(nonylphenyl) phosphate, bis(dodecyl) p-tolyl phosphate, dibutylphenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl di(2,5,5'-trimethylhexyl) phosphate, and 2-ethylhexyl diphenyl phosphate. Difunctional or polyfunctional aromatic phosphorus-containing compounds are also useful, such as resorcinol tetraphenyl diphosphate (RDP), bis(diphenyl) phosphate of hydroquinone, and bis(diphenyl) phosphate of bisphenol A, and their oligomeric and polymeric counterparts, respectively.

[0076] Flame retardant compounds containing phosphorus-nitrogen bonds include phosphazenes, phosphazene chlorides, phosphorus ester amides, phosphoric acid amides, phosphonic acid amides, phosphinic acid amides, and tri(aziridinyl)phosphine oxides. These flame retardant additives are commercially available. In one aspect, the organophosphorus flame retardant containing a phosphorus-nitrogen bond is a phosphazene or cyclophosphazene of the formula:

[0077]

[0078] wherein w1 is 3 to 10,000; w2 is 3 to 25, or 3 to 7; and each R w Independently C 1-12 Alkyl, alkenyl, alkoxy, aryl, aryloxy, or polyoxyalkylene groups. In the above groups, at least one hydrogen atom in these groups may be substituted by a group having N, S, O, or F atoms, or an amino group. For example, each R w It may be a substituted or unsubstituted phenoxy, amino, or polyoxyalkylene group. w There may further be a cross-linking group to another phosphazene group. Exemplary cross-linking groups include bisphenol groups, such as bisphenol A groups. Examples include phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, decaphenoxycyclopentaphosphazene, and the like. In one aspect, the phosphazene has a structure represented by the following formula:

[0079]

[0080] Commercially available phenoxyphosphazenes having the above structure are LY202 manufactured and sold by Lanyin Chemical Co., Ltd., FP-110 manufactured and sold by Fushimi Pharmaceutical Co., Ltd., and SPB-100 manufactured and sold by Otsuka Chemical Co., Ltd.

[0081] Halogenated materials can also be used as flame retardants, such as the following representative bisphenols: 2,2-bis-(3,5-dichlorophenyl)-propane; bis-(2-chlorophenyl)-methane; bis-(2,6-dibromophenyl)-methane; 1,1-bis-(4-iodophenyl)-ethane; 1,2-bis-(2,6-dichlorophenyl)-ethane; 1,1-bis-(2-chloro-4-iodophenyl)-ethane; 1,1-bis-(2-chloro-4-methylphenyl)-ethane; 1,1-bis-(3,5-dichlorophenyl)-ethane; 2,2-bis-(3-phenyl-4-bromophenyl)-ethane; 2,6-bis-(4,6-dichloronaphthyl)-propane; and 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane; 2,2-bis-(3-bromo-4-hydroxyphenyl)-propane. Other halogenated materials include 1,3-dichlorobenzene, 1,4-dibromobenzene, 1,3-dichloro-4-hydroxybenzene, and biphenyls such as 2,2'-dichlorobiphenyl, polybrominated 1,4-diphenoxybenzene, 2,4'-dibromobiphenyl, and 2,4'-dichlorobiphenyl and decabromodiphenyl ether, and oligomeric and polymeric halogenated aromatic compounds such as copolycarbonates of bisphenol A and tetrabromobisphenol A with carbonate precursors (e.g., phosgene). Metal synergists such as antimony oxides can also be used with flame retardants.

[0082] Alternatively, the thermoplastic composition can be substantially free of chlorine and bromine. "Substantially free of chlorine and bromine" is defined as having a bromine or chlorine content of less than or equal to 100 parts per million (ppm), less than or equal to 75 ppm, or less than or equal to 50 ppm by weight, based on the total weight of the composition.

[0083] Inorganic flame retardants such as C 1-16 Salts of alkyl sulfonates, such as potassium perfluorobutanesulfonate (Rimar salt), potassium perfluorooctanesulfonate, tetraethylammonium perfluorohexanesulfonate, and potassium diphenylsulfonesulfonate; salts such as Na 2 CO 3 , K 2 CO 3 MgCO 3 、CaCO 3 and BaCO 3 , or fluoride anion complexes such as Li 3 AlF 6 ,BaSiF 6 KBF4 , K 3 AlF 6 , KAlF 4 , K 2 SiF 6 Or Na 3 AlF 6 .

[0084] When present, the flame retardant can be included in the composition in an amount of 0.01 to 10 weight percent. Within this range, the flame retardant can be present in an amount of 0.1 to 10 weight percent, or 1 to 10 weight percent, or 1 to 8 weight percent, or 2 to 6 weight percent, or 3 to 5 weight percent, each based on the gross weight of the composition.

[0085] The polycarbonate composition may optionally exclude other components not specifically described herein. For example, the polycarbonate composition may exclude thermoplastic polymers other than bisphenol A homopolycarbonate, polycarbonate comprising repeating units of bisphenol derived from substituted or unsubstituted cyclohexylidene bridged bisphenols and polyester-carbonate. For example, the composition may minimize or exclude polyesters (for example, polyesters may be present in an amount of 1 weight percent or less, preferably, wherein polyesters are excluded from the composition). The composition may optionally exclude polycarbonates other than bisphenol A homopolycarbonate, polycarbonate comprising repeating units of bisphenol derived from substituted or unsubstituted cyclohexylidene bridged bisphenols and polyester-carbonate, such as polycarbonate-siloxane copolymers. The polycarbonate composition may optionally exclude impact modifiers, such as silicone-based impact modifiers, methyl methacrylate-butadiene-styrene copolymers, acrylonitrile-butadiene, styrene copolymers, etc., or combinations thereof. The composition can exclude halogenated flame retardants, such as brominated flame retardants, including brominated polycarbonates (e.g., polycarbonates containing brominated carbonates include units derived from 2,2',6,6'-tetrabromo-4,4'-isopropylidene diphenol (TBBPA) and carbonate units derived from at least one dihydroxy aromatic compound that is not TBBPA), brominated epoxy resins, etc., or combinations thereof. The composition can optionally exclude phosphorus-containing flame retardants.

[0086] The composition can advantageously exhibit one or more desired properties. For example, it has been found that by combining specific amounts of bisphenol A homopolymer, polycarbonate comprising repeating units derived from substituted or unsubstituted cyclohexylidene bridged bisphenols, and polyester-carbonate, improved scratch resistance can be unexpectedly obtained. The composition can further exhibit good optical properties.

[0087] In one aspect, a molded sample of the composition can exhibit a haze of less than 2.5, or less than 2, or less than 1.5 as measured according to ASTM-D1003-00 using a 2.5 mm thick plaque.

[0088] In one aspect, a molded sample of the composition can exhibit a visible scratch appearance of less than 20 Newtons (N) or less than 18 N. Scratch resistance can be determined according to ASTM D7027-13 / ISO 19252:08 according to the procedure further described in the working examples.

[0089] The polycarbonate composition can further exhibit good color. For example, the polycarbonate composition can have an L* value of 20 to 35, or 25 to 35, or 25 to 30; an a* value of 0.1 to 0.3, or 0.1 to 0.2, or 0.15 to 0.2; and a b* value of -1.5 to -0.5, or -1.1 to -0.5, or -1.1 to -0.74, measured according to ASTM E 308-08 by the CIE Lab method using a 10 degree observation angle, a D65 light source, excluding specular components, and measured in reflection mode, and using a sample with a thickness of 3.2 millimeters.

[0090] The composition may also exhibit a desired combination of mechanical properties. For example, a molded sample of the composition may exhibit a notched Izod impact strength greater than 40 J / m measured at a temperature of 23° C. under a load of 5 lbf according to ASTM D256. A molded sample of the composition may exhibit a tensile strength at break greater than 60 MPa and a tensile elongation at break greater than 100% measured at a rate of 50 mm / min using a Type I rod according to ASTM D638.

[0091] The polycarbonate composition of the present disclosure can be prepared according to various methods. For example, bisphenol A homopolymer, polycarbonate containing repeating units of bisphenols derived from substituted or unsubstituted cyclohexylidene bridges, and polyester-carbonate and other optional components can be first blended with any filler in a high-speed mixer or by manual mixing. The blend is then fed to the throat of a twin-screw extruder through a hopper. Alternatively, it can be fed directly to the extruder through a side filler and / or downstream through a side filler, or at least one of the components is incorporated into the composition by mixing it into a masterbatch with the desired polymer and feeding it to the extruder. The extruder is usually operated at a temperature higher than that necessary to cause the composition to flow. The extrudate can be immediately quenched and granulated in a water bath. As required, the pellets prepared in this way can be a quarter inch long or less. Such pellets can be used for subsequent molding, shaping or forming.

[0092] Also provided are shaped, formed, cast or molded articles comprising the composition. The composition can be molded into a shaped article 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 multilayer article, a substrate for a coated article, or a substrate for a metallized article.

[0093] Articles comprising the composition can be used in a variety of consumer products. In one aspect, the article can be an automotive component. In one aspect, the article can be a consumer electronic component, for example, a housing for a consumer electronic device.

[0094] Specific articles may include, but are not limited to, exterior automotive parts (e.g., grilles, mirror housings, pillars, spoilers, emblems, roof rails, bezels, trim, fenders), interior automotive parts (e.g., trim parts, electronic housings, dashboard parts, navigation systems, housing frames), storage bins, personal device parts, household appliance parts, furniture, appliance housings (e.g., robotic vacuum cleaners, drones), and consumer electronic devices (e.g., device housings or parts for laptops, phones, tablets, batteries, wireless charging, AR / VR goggles).

[0095] In one aspect, the article can be an automobile bumper, an automobile exterior component, an automobile reflector housing, an automobile wheel cover, an automobile dashboard or trim, an automobile glove box, an automobile door hardware or other interior trim, an automobile exterior lamp, an automobile component in the engine compartment, an agricultural tractor or device component, a window or component thereof, a construction equipment vehicle or device part, a marine or personal watercraft part, an all-terrain vehicle or an all-terrain vehicle part, a plumbing fixture, a valve or pump, an air conditioning heating or cooling component, a furnace or heat pump part, a computer housing, a computer housing or business machine housing or part, a monitor housing or part, a computer router, a desktop printer, a large office / industrial printer, an electronic component, a projector component, an electronic display component, a copier component, a scanner component, an electronic printer toner cartridge, a handheld electronic device housing, a handheld device housing, a hair dryer, an iron, a coffee maker, a toaster, a washing machine or a laundry machine parts, microwave ovens, ovens, power tools, electrical components, electrical housings, lighting parts, parts for lighting fixtures, dental instruments, medical instruments, parts for medical or dental lighting, aircraft parts, train or track parts, seat assemblies, sidewalls, ceiling parts, cookware, medical instrument trays, animal cages, fibers, laser welded medical devices, optical fibers, lenses (automatic and non-automatic), cell phone parts, greenhouse parts, sunroom parts, fire helmets, safety shields, safety glasses, air pump parts, humidifier housings, thermostatic control housings, air conditioner drain pans, outdoor cabinets, telecommunications housings or infrastructure, simple network detection system (SNIDS) equipment, network interface devices, smoke detectors, parts or devices in plenum spaces, medical scanners, X-ray equipment, parts for medical applications or devices, electrical boxes or housings, and electrical connectors, construction or agricultural equipment, and turbine blades.

[0096] In one aspect, the article can be a component of an aircraft interior or train interior, an access panel, an access door, an air damper, an air filler, an air grille, a handrail, a luggage storage door, a balcony component, a cabinet wall, a ceiling panel, a door pull, a door handle, a duct housing, a housing for an electronic device, an equipment housing, an equipment panel, a floor panel, a food cart, a food tray, a kitchen surface, a handle, a television housing, a light panel, a magazine rack, a phone housing, a partition, a trolley part, a seat back, a seat component, a fence component , seat shells, brackets, side walls, speaker housings, storage compartments, storage housings, toilet seats, tray tables, trays, trim panels, window trim, window slides, balcony components, balers, ceiling panels, covers for life jackets, covers for storage boxes, dust covers for windows, layers for electrochromic devices, lenses for television sets, electronic displays, gauges or instrument panels, light covers, light diffusers, light tubes, light pipes, reflectors, partitions, railings, refrigerator doors, shower doors, sink bowls, cart containers, cart side panels or windows.

[0097] The present disclosure is further illustrated by the following examples, which are non-limiting.

[0098] Example

[0099] The materials used in the following examples are shown in Table 1.

[0100] Table 1

[0101]

[0102]

[0103] The components of the composition were mixed and extruded. Moulded parts for physical testing were prepared by injection moulding. The test methods are described below in Table 2.

[0104] Table 2

[0105]

[0106] Examples 1-8

[0107] Table 3 shows the composition and properties of Examples 1 to 8. The amount of each component is shown in weight percent based on the total weight of the composition.

[0108] Table 3

[0109]

[0110]

[0111] *Indicates comparative example

[0112] The addition of DMBPC-BPA copolycarbonate provided slight improvements in yield modulus and tensile strength and elongation at yield as shown in Table 3. Although the Izod impact strength was observed to decrease with increasing amount of DMBPC-BPA copolycarbonate, the multiaxial impact strength remained at 100% ductility with similar total energy values.

[0113] Examples 5-8 of Table 3 show three compositions that were colored using the same colorant package to provide a "piano black" appearance. As can be seen from the L*a*b* color measurements shown in Table 3 and the gloss measurements from three angles, the aesthetics and appearance of the three compositions are substantially the same, which is consistent with visual assessment (e.g., by the naked eye).

[0114] The compositions according to Examples 6 and 7 exhibit a slight decrease in modulus and tensile properties relative to Comparative Example 5*. However, the compositions of both Examples 6 and 7 exhibit a large improvement in elongation at break and total energy for multiaxial impact at both room temperature and at 0°C compared to Comparative Example 5*. The notched Izod impact strength of Examples 6 and 7 is also significantly improved compared to Comparative Example 5*.

[0115] Scratch test measurements were performed according to ASTM D7027-13 / ISO 19252:08 using an SMS Scratch test apparatus equipped with a stylus having a 1 mm spherical scratch tip, and a scratch speed of 100 mm / min. The scratch test results are shown in Table 4. The results are reported in terms of visibility appearance, expressed in Newtons (N), which is the force at which the scratch begins to become visible.

[0116] Table 4

[0117] Example Scratch performance (N, average value) Standard Deviation 5* 20 1 7 17 2 6 13 1 8* 9 1

[0118] As shown in Table 4, the introduction of the DMBPC copolymer resulted in a significant improvement in scratch resistance compared to the BPC-PC homopolymer composition (shown in Example 8*), with an even greater improvement in scratch resistance when DMBPC and ITR copolycarbonate were included in the composition at the same DMBPC loading.

[0119] Additional formulations were prepared and tested as shown in Tables 5 and 6. The amount of each component is provided as weight percent, based on the total weight of the composition.

[0120] Table 5

[0121]

[0122] *Indicates comparative example

[0123] Table 6

[0124]

[0125]

[0126] * indicates comparative example; "NM" means not measured

[0127] As shown in Tables 5 and 6, an unexpected increase in turbidity was observed when the amount of DMBPC in the composition was above 25 wt%. Figure 1 , which shows the turbidity of the composition according to the DMBPC content. Therefore, a desired combination of properties can be provided by the composition of the present disclosure.

[0128] Additional formulations were prepared and tested as shown in Table 7. The amount of each component is provided as weight percent, based on the total weight of the composition.

[0129] Table 7

[0130]

[0131] *Indicates comparative example

[0132] As shown in Table 7, the amount and type of additives such as mold release agents and slip promoters can be varied.

[0133] Additional formulations were prepared and tested as shown in Table 8. The amount of each component is provided as weight percent, based on the total weight of the composition.

[0134] Table 8

[0135]

[0136] * indicates comparative example; 1 Turbidity and transmittance were measured using 2.5 mm flat color film.

[0137] As shown in Table 8, when the cyclohexylidene bridged bisphenol: (isophthalic acid, terephthalic acid and resorcinol ester units) weight ratio is outside the range defined in the present disclosure, the desired combination of properties is not obtained. Specifically, when the cyclohexylidene bridged bisphenol: (isophthalic acid, terephthalic acid and resorcinol ester units) weight ratio is 2.5 or greater, the composition cannot achieve the desired turbidity. Therefore, the inventors have unexpectedly discovered that specific combinations of specific amounts of components set forth in the present disclosure can unexpectedly provide the desired combination of properties. Therefore, the present disclosure provides significant improvements.

[0138] The present disclosure further encompasses the following aspects.

[0139] Aspect 1: A polycarbonate composition comprising: 10 to 60 weight percent of bisphenol A homopolycarbonate, based on the total weight of the composition; a polycarbonate comprising repeating units derived from substituted or unsubstituted cyclohexylidene-bridged bisphenols in an amount effective to provide a substituted or unsubstituted cyclohexylidene-bridged bisphenol content of 25 weight percent or less, based on the total weight of the composition; and a polyester-carbonate comprising ester units derived from isophthalic acid, terephthalic acid, and resorcinol; wherein the composition has a cyclohexylidene-bridged bisphenol:(isophthalic acid, terephthalic acid, and resorcinol ester units) weight ratio of less than 2.5.

[0140] Aspect 2: The polycarbonate composition of Aspect 1, wherein the composition has a cyclohexylidene-bridged bisphenol:(isophthalic acid, terephthalic acid, and resorcinol ester units) weight ratio of less than 2.25.

[0141] Aspect 3: The polycarbonate composition of Aspect 1 or 2, wherein the composition exhibits a haze of less than 2.5, or less than 2, or less than 1.5 as measured according to ASTM-D1003-00 using a 2.5 mm thick plaque.

[0142] Aspect 4: The polycarbonate composition of any of Aspects 1 to 3, wherein the polycarbonate comprising repeating units derived from a substituted or unsubstituted cyclohexylidene-bridged bisphenol is present in an amount of 5 to 45 weight percent based on the total weight of the composition.

[0143] Aspect 5: The polycarbonate composition of any one of Aspects 1 to 4, wherein the polycarbonate comprising repeating units derived from a substituted or unsubstituted cyclohexylidene-bridged bisphenol comprises a first carbonate repeating unit having the following structure:

[0144] as well as

[0145] A second carbonate repeating unit having the structure:

[0146]

[0147] Among them, in the above formula, R a , R b and R g Each is independently C 1-12 Alkyl group, R c and R d are independently hydrogen, C 1-12 Alkyl, cyclic C 1-12 Alkyl, C 7-12 Aralkyl, C 1-12 Heteroalkyl, or cyclic C 7-12 heteroarylalkyl; p and q are each independently 0 to 4, and t is 0 to 10.

[0148] Aspect 6: The polycarbonate composition of any one of Aspects 1 to 5, wherein the polycarbonate comprising repeating units derived from substituted or unsubstituted cyclohexylidene-bridged bisphenols has the following structure:

[0149]

[0150] Wherein, the molar ratio of x to y is 25:75 to 75:25.

[0151] Aspect 7: The polycarbonate composition of any one of Aspects 1 to 6, wherein the polycarbonate comprising repeating units derived from substituted or unsubstituted cyclohexylidene-bridged bisphenols has a substituted or unsubstituted cyclohexylidene-bridged bisphenol content of 40 to 60 weight percent based on the total weight of the polycarbonate comprising repeating units derived from substituted or unsubstituted cyclohexylidene-bridged bisphenols.

[0152] Aspect 8: The polycarbonate composition of any one of Aspects 1 to 7, wherein the polyester-carbonate has the formula:

[0153]

[0154] Among them, R 1 Derived from an aromatic dihydroxy compound of the formula:

[0155]

[0156] Among them, R a and R b are independently halogen, C 1-12 Alkoxy, or C 1-12 alkyl, p and q are each independently an integer from 0 to 4, and X a is a single bond, -O-, -S-, -S(O)-, -S(O) 2 -, -C(O)-, or C 1-60 an organic group; and R h is independently a halogen atom, C 1-10 Alkyl groups, halogen-substituted C 1-10 Alkyl group, C 6-10 Aryl group, or halogen substituted C 6-10 An aryl group, and n is 0 to 4.

[0157] Aspect 9: The polycarbonate composition of any of Aspects 1 to 8, wherein the ester units derived from isophthalic acid, terephthalic acid, and resorcinol are present in the polyester-carbonate in an amount of 10 to 30 weight percent based on the total weight of the polyester-carbonate.

[0158] Aspect 10: The polycarbonate composition of any one of Aspects 1 to 9, comprising, based on the total weight of the composition: 10 to 50 weight percent of bisphenol A homopolycarbonate; 35 to 55 weight percent of polyester-carbonate; and 5 to 45 weight percent of a polycarbonate comprising repeating units derived from substituted or unsubstituted cyclohexylidene-bridged bisphenols; wherein the composition has a cyclohexylidene-bridged bisphenol content of 22 weight percent or less; and wherein the cyclohexylidene-bridged bisphenol: (isophthalic acid, terephthalic acid and resorcinol ester units) weight ratio is less than 2.25.

[0159] Aspect 11: The polycarbonate composition of any one of Aspects 1 to 10, further comprising 0.1 to 10 weight percent of an additive composition based on the total weight of the polycarbonate composition.

[0160] Aspect 12: The polycarbonate composition of Aspect 11, wherein the additive composition comprises a flame retardant, a colorant composition, a stabilizer, a mold release agent, or a combination thereof.

[0161] Aspect 13: A method of preparing the polycarbonate composition of any of Aspects 1 to 12, the method comprising melt mixing the components of the composition, and optionally extruding the composition.

[0162] Aspect 14: An article comprising the polycarbonate composition of any one of Aspects 1 to 12.

[0163] The compositions, methods and articles may alternatively comprise, consist of or consist essentially of any suitable material, step or component disclosed herein. The compositions, methods and articles may additionally or alternatively be formulated so as to be free of or essentially free of any material (or species), step, or component that is otherwise not necessary for achieving the function or purpose of the compositions, methods and articles.

[0164] All ranges disclosed herein include endpoints, and endpoints can be combined independently of each other. "Combination" includes blends, mixtures, alloys, reaction products, etc. The terms "first", "second", etc. do not represent any order, quantity, or importance, but are used to distinguish one element from another. Unless otherwise specified herein or clearly contradictory to the context, the terms "one" and "a kind of" and "the" do not represent the limitation of quantity, but are interpreted as covering the singular and plural. Unless otherwise clearly stated, "or" refers to "and / or". Mentioning "an aspect" throughout the specification means that the specific elements described in conjunction with the aspect are included in at least one aspect described herein, and may or may not be present in other aspects. The term "their combination" as used in this article includes one or more listed elements, and is open, allowing one or more unnamed similar elements to exist. In addition, it should be understood that the described elements can be combined in any suitable manner in various aspects.

[0165] Unless specified to the contrary herein, all test standards are the most current standards 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 standards appear.

[0166] Unless otherwise defined, the technical and scientific terms used herein have the same meanings as those generally understood by those of ordinary 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 this application contradicts or conflicts with a term in a combined reference, the term from this application takes precedence over the conflicting term from the combined reference.

[0167] Compounds are described using standard nomenclature. For example, any position not substituted by any indicator group is understood to have its valency filled by a bond or hydrogen atom as indicated. A dash ("-") not between two letters or symbols is used to indicate the point of attachment of a substituent. For example, -CHO is connected through the carbon of a carbonyl group.

[0168] As used in this article, the term "alkyl", whether used alone or as a prefix, suffix or fragment of another term, refers to a residue containing only carbon and hydrogen. The residue can be aliphatic or aromatic, straight chain, cyclic, bicyclic, branched, saturated or unsaturated. It can also include a combination of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated and unsaturated hydrocarbon parts. However, when the alkyl residue is described as substituted, it can optionally include heteroatoms on and above the carbon and hydrogen members of the substituent residue. Therefore, when specifically described as substituted, the alkyl residue can also include one or more carbonyls, amino, hydroxyl, etc., or it can include heteroatoms in the main chain of the alkyl residue. The term "alkyl" refers to a branched or straight chain saturated aliphatic hydrocarbon group, for example, 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 or branched monovalent hydrocarbon radical having at least one carbon-carbon double bond (e.g., vinyl (-HC=CH 2 )). "Alkoxy" refers to an alkyl group attached via an oxygen (i.e., alkyl-O-), such as methoxy, ethoxy, and sec-butoxy. "Alkylene" refers to a straight or branched chain, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH 2 -) or propylene (-(CH 2 ) 3 -). "Cycloalkylene" refers to a divalent cyclic alkylene group, -C n H 2n-x, wherein x is the number of hydrogens replaced by cyclization. "Cycloalkenyl" refers to 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" refers to an aromatic hydrocarbon group containing a specified number of carbon atoms, such as phenyl, cycloheptatrienone, indanyl, or naphthyl. "Arylene" refers to a divalent aryl group. "Alkylarylene" refers to an arylene group substituted by an alkyl group. "Arylalkylene" refers to an alkylene group substituted by an aryl group (e.g., benzyl). The prefix "halo" refers to a group or compound including one or more of fluorine, chlorine, bromine, or iodine substituents. There may be a combination of different halogen atoms (e.g., bromine and fluorine) or only chlorine atoms. The prefix "hetero" refers to a compound or group including at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatoms), wherein the heteroatoms are 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, each of which is independently C 1-9 Alkoxy, C 1-9 Haloalkoxy, nitro (-NO 2 ), cyano (-CN), C 1-6 Alkylsulfonyl (-S(=O) 2 -alkyl), C 6-12 Arylsulfonyl (-S(=O) 2 -aryl), thiol (-SH), thiocyanate (-SCN), tosyl (CH 3 C 6 H 4 SO 2 -), C 3-12 Cycloalkyl, C 2-12 Alkenyl, C 5-12 Cycloalkenyl, C 6-12 Aryl, C 7-13 Arylalkylene, C 4-12 Heterocycloalkyl and C 3-12 Heteroaryl groups, provided that the normal valence of the substituted atoms is not exceeded. The number of carbon atoms indicated in the group does not include any substituents. For example, -CH 2 CH 2 CN is C substituted by nitrile 2 Alkyl group.

[0169] Although specific embodiments have been described, the applicant or other persons skilled in the art may conceive of alternatives, modifications, variations, improvements, and substantial equivalents that are not currently foreseeable or may not be foreseeable. Therefore, the appended claims as filed and as they may be amended are intended to cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. A polycarbonate composition comprising: 10 to 60 weight percent of bisphenol A homopolycarbonate, based on the total weight of the composition; a polycarbonate comprising repeating units derived from a substituted or unsubstituted cyclohexylidene-bridged bisphenol in an amount effective to provide a substituted or unsubstituted cyclohexylidene-bridged bisphenol content of 25 weight percent or less, based on the total weight of the composition; and polyester-carbonates comprising ester units derived from isophthalic acid, terephthalic acid and resorcinol; in, The composition has a cyclohexylidene-bridged bisphenol:(isophthalic acid, terephthalic acid, and resorcinol ester units) weight ratio of less than 2.

5.

2. The polycarbonate composition according to claim 1, wherein The composition has a cyclohexylidene-bridged bisphenol:(isophthalic acid, terephthalic acid, and resorcinol ester units) weight ratio of less than 2.

25.

3. The polycarbonate composition according to claim 1 or 2, wherein The composition exhibits a haze of less than 2.5, or less than 2, or less than 1.5 as measured according to ASTM-D1003-00 using a 2.5 mm thick plaque.

4. The polycarbonate composition according to any one of claims 1 to 3, wherein The polycarbonate comprising repeating units derived from a substituted or unsubstituted cyclohexylidene-bridged bisphenol is present in an amount of 5 to 45 weight percent, based on the total weight of the composition.

5. The polycarbonate composition according to any one of claims 1 to 4, wherein The polycarbonate comprising repeating units derived from substituted or unsubstituted cyclohexylidene-bridged bisphenols comprises: A first carbonate repeating unit having the structure: as well as A second carbonate repeating unit having the structure: Among them, in the above formula, R a , R b and R g Each independently is C 1-12 Alkyl groups, R c and R d are independently hydrogen, C 1-12 Alkyl, cyclic C 1-12 Alkyl, C 7-12 Aralkyl, C 1-12 Heteroalkyl, or cyclic C 7-12 heteroarylalkyl; p and q are each independently 0 to 4, and t is 0 to 10.

6. The polycarbonate composition according to any one of claims 1 to 5, wherein The polycarbonate comprising repeating units derived from substituted or unsubstituted cyclohexylidene-bridged bisphenols has the following structure: Wherein, the molar ratio of x to y is 25:75 to 75:

25.

7. The polycarbonate composition according to any one of claims 1 to 6, wherein The polycarbonate comprising repeating units derived from substituted or unsubstituted cyclohexylidene-bridged bisphenol has a substituted or unsubstituted cyclohexylidene-bridged bisphenol content of 40 to 60 weight percent, based on the total weight of the polycarbonate comprising repeating units derived from substituted or unsubstituted cyclohexylidene-bridged bisphenol.

8. The polycarbonate composition according to any one of claims 1 to 7, wherein The polyester-carbonate has the formula: in, R 1 Derived from an aromatic dihydroxy compound of the formula: Among them, R a and R b are independently halogen, C 1-12 Alkoxy, or C 1-12 alkyl, p and q are each independently an integer from 0 to 4, and X a is a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, or C 1-60 organic groups; and R h is independently a halogen atom, C 1-10 Alkyl groups, halogen-substituted C 1-10 Alkyl group, C 6-10 Aryl group, or halogen substituted C 6-10 An aryl group, and n is 0 to 4.

9. The polycarbonate composition according to any one of claims 1 to 8, wherein The ester units derived from isophthalic acid, terephthalic acid and resorcinol are present in the polyester-carbonate in an amount of 10 to 30 weight percent, based on the total weight of the polyester-carbonate.

10. The polycarbonate composition according to any one of claims 1 to 9, comprising, based on the total weight of the composition: 10 to 50 weight percent of the bisphenol A homopolycarbonate; 35 to 55 weight percent of said polyester-carbonate; and 5 to 45 weight percent of said polycarbonate comprising repeating units derived from substituted or unsubstituted cyclohexylidene-bridged bisphenols; in, The composition has a cyclohexylidene-bridged bisphenol content of 22 weight percent or less; and Wherein, the weight ratio of cyclohexylidene-bridged bisphenol: (isophthalic acid, terephthalic acid and resorcinol ester units) is less than 2.

25.

11. The polycarbonate composition of any one of claims 1 to 10, further comprising 0.1 to 10 weight percent of an additive composition, based on the total weight of the polycarbonate composition.

12. The polycarbonate composition according to claim 11, wherein The additive composition includes a flame retardant, a colorant composition, a stabilizer, a mold release agent, or a combination thereof.

13. A method of preparing the polycarbonate composition of any one of claims 1 to 12, the method comprising melt mixing the components of the composition, and optionally extruding the composition.

14. An article comprising the polycarbonate composition of any one of claims 1 to 12.

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