Polycarbonate composition

Abstract

The present invention relates to a polycarbonate composition comprising the following components, relative to the total weight of the composition: A) 0-76% by weight of a copolycarbonate resin containing bis (4-hydroxyphenyl)-3, 3, 5-trimethylcyclohexane units and substituted or unsubstituted bisphenol units, B) 0-58% by weight of an aromatic linear polycarbonate resin, C) 15-52% by weight of a poly (1, 3, 5-trimethylcyclohexane unit, D) 0-50% by weight of a polycarbonate resin, and E) 0-50% by weight of a polycarbonate resin. The present invention relates to a composition comprising: A) 1-60 wt% of 1, 4-cyclohexanedicarboxylic acid 1, 4-cyclohexylidene dimethylene ester), and D) 1-60 wt% of a methyl methacrylate-n-butyl acrylate-butadiene-styrene copolymer, the composition according to the present invention having high light transmittance, low haze and low birefringence.

Description

Technical Field

[0001] The present invention relates to a polycarbonate composition and also to a molded article made from the polycarbonate composition. Background Art

[0002] Displays are already used in numerous locations within the car interior, requiring seamless integration into diverse materials and structures. From large, curved displays to fully functional smart surfaces and personalized lighting to reimagined flooring, materials are the driving force behind this mobility evolution. Display cover shapes will be three-dimensional, and product structures will be highly complex.

[0003] Compared to traditional glass materials, polycarbonate (PC) has advantages related to design freedom, component and function integration, and impact resistance. However, the high birefringence of polycarbonate is a major technical challenge for this application. The residual birefringence of polycarbonate after injection molding causes a rainbow-like color spectrum on the display cover. The rainbow-like color spectrum can be visible under polarized light. This color spectrum can be reduced by injection compression molding and annealing processes, but it cannot be completely removed at the corners of the display cover (where the internal stress is strong). Therefore, there is a great need in the market to develop a new polycarbonate blend material that has a lower birefringence while maintaining the advantages of polycarbonate mentioned above.

[0004] In anisotropic materials, the refractive index varies with the direction of the electric field vector of the light. The difference in refractive index between the principal axes is called birefringence. Birefringence depends on the inherent polymer structure and the orientation of the polymer chains. During the molding process of polymers, the molten resin flows and cools rapidly, the polymer chains orient, so that flow stresses and birefringence are not completely relaxed and remain in the molded part. This is often called flow-induced or froze-inbirefringence. Polarized light passing through a deformed polycarbonate article splits into two wave components, which travel at different speeds and are parallel to the direction of the principal stresses but perpendicular to each other. These two components of the light wave passing through the sample interfere with each other to produce a spectrum of colors. This is the origin of the rainbow-like pattern problem on display covers.

[0005] US20020111428A discloses transparent polycarbonate polyester compositions comprising a resin blend of polycarbonate and a cycloaliphatic polyester resin, and an impact-modified amorphous resin having a refractive index of about 1.51 to about 1.58 to improve ductility, chemical resistance, and melt flow properties. However, these compositions fail to achieve low birefringence for display applications.

[0006] US Pat. No. 6,465,102B discloses a molded article comprising a decorative film or substrate and an adjacent injection-molded polymer base comprising a substantially transparent cycloaliphatic polyester resin and a substantially transparent impact modifier having a refractive index of 1.51 to 1.58. The molded article exhibits high clarity with a light transmittance greater than 75% and improved chemical resistance. However, the molded article does not achieve the low birefringence required for display applications.

[0007] Therefore, there remains a need to develop molded articles having a good combination of high transmittance (greater than 85%), low haze, and low birefringence for display cover applications. SUMMARY OF THE INVENTION

[0009] Therefore, one object of the present application is to provide a polycarbonate composition from which molded articles have a good combination of high light transmittance, low haze, and low birefringence.

[0010] Another object of the present application is to provide molded articles having a good combination of high light transmittance, low haze, and low birefringence.

[0011] In a first aspect, the present invention provides a polycarbonate composition comprising the following components, relative to the total weight of the composition:

[0012] A) 0 to 76% by weight of copolycarbonate (CoPC) containing bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BPTMC) units and substituted or unsubstituted bisphenol units,

[0013] B) 0 to 58% by weight of an aromatic linear homopolycarbonate comprising substituted or unsubstituted bisphenol units,

[0014] C) 15-52 wt% of poly(1,4-cyclohexylenedimethylene 1,4-cyclohexanedicarboxylate) (PCCD), and

[0015] D) 1 to 60% by weight of methyl methacrylate-n-butyl acrylate-butadiene-styrene copolymer (MBABS),

[0016] The content relationship index (r) of the components AD having the following formula (A) is:

[0017]

[0018] In the range of 0-32,

[0019] In formula (A),

[0020] C A represents the content of component A in the composition,

[0021] C A+B represents the total content of components A and B in the composition, which is 22% to 76% by weight,

[0022] BPTMC% A represents the content of bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BPTMC) units in component A,

[0023] C C represents the content of component C in the composition,

[0024] C A+B+C represents the total content of components A, B and C in the composition,

[0025] C D represents the content of component D in the composition,

[0026] All contents are percentages by weight.

[0027] The inventors have surprisingly found that molded articles made from the compositions according to the invention have high light transmittance (greater than 85%), low haze at 2 mm (less than 5%) as measured according to ASTM method D1003, and low birefringence.

[0028] In a second aspect, the present invention provides a shaped article made from the polycarbonate composition according to the first aspect of the invention.

[0029] In a third aspect, the present invention provides a method for preparing the above-mentioned shaped article, which comprises injection molding, extrusion molding, blow molding or thermoforming the polycarbonate composition according to the present invention.

[0030] Other subjects and features, aspects and advantages of the present invention will appear more clearly on reading the following description and examples. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] The present invention will be described and explained in detail below with reference to the accompanying drawings, in which

[0033] Figure 1 The corresponding fractions for the different birefringence phenomena are shown. Detailed Description of the Invention

[0035] In the following text, and unless otherwise indicated, the limits of the numerical ranges are included in this range, particularly in the expressions "between and" and "from to."

[0036] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the invention belongs. When the definition of a term in this specification conflicts with the meaning commonly understood by those skilled in the art to which the invention belongs, the definition set forth herein shall apply.

[0037] Throughout this application, the term "comprising" should be interpreted to encompass all specifically mentioned elements as well as optional, additional, unspecified elements. As used herein, the use of the term "comprising" also discloses embodiments in which no elements other than the specifically mentioned elements are present (i.e., "consisting of").

[0038] Unless otherwise indicated, all numbers expressing quantities of ingredients and so forth used in the specification and claims are to be understood as modified by the term "about."

[0039] As used herein, "light transmittance" is interchangeable with light transmittance.

[0040] Component A

[0041] According to a first aspect, the polycarbonate composition according to the present invention comprises a copolycarbonate.

[0042] In this application, copolycarbonate refers to a polycarbonate comprising the following components:

[0043] i) Bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BPTMC) units of formula (1)

[0044]

[0045] wherein * indicates the position at which formula (1) is attached to the polymer chain, i.e., the BPTMC unit of formula (1) is derived from bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BPTMC) having formula (1a):

[0046]

[0047] ii) substituted or unsubstituted bisphenol units of formula (2):

[0048]

[0049] in

[0050] * indicates the position where formula (2) is attached to the polymer chain,

[0051] R 3 Each independently represents H, a linear or branched C1-C 10 Alkyl, preferably H, linear or branched C1-C4 alkyl, and

[0052] R4 Each independently is a straight chain or branched C1-C 10 Alkyl group, preferably a linear or branched C1-C4 alkyl group.

[0053] The unit of formula (2) may be derived from a diphenol of formula (2'):

[0054]

[0055] R 3 Each independently represents H, a straight or branched C1-C 10 alkyl,

[0056] R 4 Each independently represents a straight or branched C1-C 10 alkyl.

[0057] Preferably, the unit of formula (2) has the following formula (2a),

[0058]

[0059] Where * indicates the position where formula (2a) is attached to the polymer chain,

[0060] That is, the unit of formula (2) is derived from bisphenol A, that is, the diphenol of formula (2'a)

[0061]

[0062] Preferably, the copolycarbonate comprises units derived from bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BPTMC) and bisphenol A.

[0063] Preferably, the units of formula (1) in the copolycarbonate are derived from bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BPTMC), and the units of formula (2) in the copolycarbonate are derived from bisphenol A.

[0064] The diphenols of the formula (1) and (2′) are known and can be prepared by methods known from the literature (eg HJ Buysch et al., Ullmann's Encyclopedia of Industrial Chemistry, VCH, New York 1991, 5th edition, volume 19, page 348).

[0065] Preferably, based on the total molar number of units of formula (1) and formula (2), the molar content of the units of formula (1) in the copolycarbonate is 20-80 mol%, and the molar content of the units of formula (2) in the copolycarbonate is 80-20 mol%.

[0066] More preferably, based on the total molar number of units of formula (1) and formula (2), the molar content of the units of formula (1) in the copolycarbonate is 30-75 mol%, and the molar content of the units of formula (2) in the copolycarbonate is 70-25 mol%.

[0067] The copolycarbonates used in the compositions according to the invention are commercially available or can be produced by methods known in the art.

[0068] For example, the copolycarbonates used in the compositions according to the invention can be produced by an interfacial process. In particular, the diphenols of formula (1) and (2') and optionally a branching agent are dissolved in an alkaline aqueous solution and reacted with a carbonate source, such as phosgene, optionally dissolved in a solvent, in a two-phase mixture comprising an alkaline aqueous solution, an organic solvent and a catalyst, preferably an amine compound. This reaction procedure can also be carried out in a multi-step process.

[0069] Such a process for preparing copolycarbonates is known in principle as the two-phase interfacial process, for example from H. Schnell, Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9, Interscience Publishers, New York 1964, p. 33 ff., and Polymer Reviews, Vol. 10, "Condensation Polymers by Interfacial and Solution Methods", Paul W. Morgan, Interscience Publishers, New York 1965, Chapter VIII, p. 325, so that the basic conditions are familiar to those skilled in the art.

[0070] The concentration of diphenol in the alkaline aqueous solution is 2% to 25% by weight, preferably 2% to 20% by weight, more preferably 2% to 18% by weight, and even more preferably 3% to 15% by weight. The alkaline aqueous solution consists of water in which an alkali metal or alkaline earth metal hydroxide is dissolved. Sodium hydroxide and potassium hydroxide are preferred.

[0071] The concentration of the amine compound is 0.1 to 10 mol %, preferably 0.2 to 8 mol %, particularly preferably 0.3 to 6 mol %, and more particularly preferably 0.4 to 5 mol %, relative to the molar amount of the diphenol used.

[0072] The carbonate source is phosgene, diphosgene or triphosgene, preferably phosgene. When phosgene is used, the solvent can optionally be omitted and the phosgene can be passed directly into the reaction mixture.

[0073] Tertiary amines such as triethylamine or N-alkylpiperidines can be used as catalysts. Suitable catalysts are trialkylamines and 4-(dimethylamino)pyridine. Triethylamine, tripropylamine, triisopropylamine, tributylamine, triisobutylamine, N-methylpiperidine, N-ethylpiperidine and N-propylpiperidine are particularly suitable.

[0074] Suitable organic solvents include halogenated hydrocarbons such as dichloromethane, chlorobenzene, dichlorobenzene, trichlorobenzene or mixtures thereof, or aromatic hydrocarbons such as toluene or xylene. The reaction temperature can be between -5°C and 100°C, preferably between 0°C and 80°C, particularly preferably between 10°C and 70°C, and very particularly preferably between 10°C and 60°C. It is also possible to prepare the copolycarbonates by the melt transesterification process, in which diphenols are reacted with diaryl carbonates, typically diphenyl carbonate, in the presence of catalysts such as alkali metal salts, ammonium or phosphonium compounds in the melt.

[0075] The melt transesterification process is described, for example, in Encyclopedia of Polymer Science, Vol. 10 (1969), Chemistry and Physics of Polycarbonates, Polymer Reviews, H. Schnell, Vol. 9, John Wiley and Sons, Inc. (1964) and DE-C 1031512.

[0076] In the transesterification process, the aromatic dihydroxy compounds already described in the case of the phase boundary process are transesterified with carbonic acid diesters by means of suitable catalysts and optionally further additives in the melt.

[0077] The reaction of aromatic dihydroxy compounds and carbonic acid diesters to give copolycarbonates can be carried out batchwise or preferably continuously, for example in stirred vessels, thin-film evaporators, falling-film evaporators, stirred vessel cascades, extruders, kneaders, simple disk reactors and high-viscosity disk reactors.

[0078] Preferably, the copolycarbonate is selected from block copolycarbonates and random copolycarbonates. More preferably, the copolycarbonate is selected from random copolycarbonates.

[0079] Advantageously, the copolycarbonate has a weight average molecular weight (Mw) of 16,000 to 40,000 g / mol, preferably 17,000 to 32,000 g / mol, as determined by gel permeation chromatography (GPC) in dichloromethane at 25° C. with a UV-IR detector using polycarbonate standards.

[0080] As examples of commercial products of copolycarbonates suitable for the compositions according to the invention, mention may be made of the copolycarbonates sold under the name The product sold is a polycarbonate copolymer made by copolymerization of phosgene with bisphenol A (BPA) and 3,3,5-trimethyl-1,1-bis(4-hydroxyphenyl)cyclohexane (BPTMC).

[0081] Advantageously, the copolycarbonate is present in the composition of the invention in an amount ranging from 0% to 76% by weight, more preferably from 5% to 60% by weight and even more preferably from 7% to 50% by weight relative to the total weight of the composition.

[0082] Component B

[0083] According to a first aspect, the polycarbonate composition according to the present invention comprises an aromatic linear homopolycarbonate containing substituted or unsubstituted bisphenol units.

[0084] In the present application, homopolycarbonate refers to a polycarbonate comprising units of formula (2) as defined above.

[0085] The unit of formula (2) is derived from a diphenol of formula (2'):

[0086]

[0087] in

[0088] R 3 Each independently represents H, a straight or branched C1-C 10 Alkyl, preferably linear or branched C1-C6-alkyl, more preferably linear or branched C1-C4 alkyl, still more preferably H or methyl, and

[0089] R 4 Each independently represents a straight or branched C1-C 10 Alkyl group, preferably a linear or branched C1-C6 alkyl group, more preferably a linear or branched C1-C4 alkyl group, and even more preferably a methyl group.

[0090] Preferably, the units of formula (2) are derived from a diphenol of formula (2'a), ie bisphenol A.

[0091]

[0092] The homopolycarbonates used in the compositions according to the invention are commercially available or can be produced by methods known in the art.

[0093] For example, a homopolycarbonate can be produced by the preparation method described with reference to component A.

[0094] Advantageously, the homopolycarbonate has a weight average molecular weight (Mw) of 20,000 to 32,000 g / mol, preferably 20,000 to 30,000 g / mol, as determined by gel permeation chromatography (GPC) in dichloromethane at 25° C. with a UV-IR detector using polycarbonate standards.

[0095] As commercial products of homopolycarbonates suitable for use in the composition according to the invention, mention may be made of the polycarbonates sold by the company CovestroPolymer (China). FS2000, 2400, 2600 and 2800.

[0096] Advantageously, the homopolycarbonate is present in the polycarbonate composition of the invention in an amount ranging from 0% to 60% by weight, preferably from 14% to 60% by weight and more preferably from 14% to 58% by weight relative to the total weight of the composition.

[0097] Component C

[0098] According to a first aspect, the polycarbonate composition according to the present invention comprises poly(1,4-cyclohexylenedimethylene 1,4-cyclohexanedicarboxylate) (PCCD), sometimes also referred to as poly(1,4-cyclohexanedimethanol-1,4-dicarboxylate), which is a cycloaliphatic polyester and has repeating units of the formula:

[0099]

[0100] R is derived from 1,4-cyclohexanedimethanol

[0101] The cycloaliphatic polyester is the condensation product of a cycloaliphatic diacid or chemical equivalent and a cycloaliphatic diol or chemical equivalent.Preferred PCCDs have a cis / trans chemical formula.

[0102] The polyester polymerization reaction is typically carried out in the melt in the presence of a suitable catalyst such as tetra(2-ethylhexyl) titanate in a suitable amount (typically about 50 to 200 ppm titanium based on the final product).

[0103] The cyclic component helps to impart good rigidity to the polyester and enables the formation of transparent blends due to favorable interactions with the polycarbonate resin.

[0104] The PCCD used may be standard PCCD available from Eastman Chemical as NEOSTAR COPOLYESTER.

[0105] Preferably, the PCCD has a weight average molecular weight of 30,000 to 80,000, preferably 41,000 to 60,000 as measured by GPC on a Perkin-Elmer instrument using 3% isopropyl alcohol / chloroform eluent and a refractive index of about 1.506-1.508 as measured at the sodium-D-line (wavelength 589 nm) with an Abbe refractometer according to ISO 489.

[0106] The refractive index of a miscible resin blend is determined by the components and their respective amounts. Pure polycarbonate (PC) has a refractive index of 1.585, while PCCD has a refractive index of 1.506-1.508. Therefore, the refractive index of a mixture of two components can be controlled to be between the upper and lower limits of their respective refractive indices.

[0107] Advantageously, PCCD is present in the polycarbonate composition according to the invention in an amount ranging from 15% to 52% by weight, preferably from 18% to 52% by weight, relative to the total weight of the polycarbonate composition.

[0108] Component D

[0109] According to a first aspect, the polycarbonate composition according to the present invention comprises methyl methacrylate-n-butyl acrylate-butadiene-styrene (MBABS) copolymer, which is an amorphous impact modifier copolymer resin.

[0110] The MBABS copolymer comprises 1 to 15 wt% of a dispersed phase made of a rubber-like elastic material and 99 to 85 wt% of a continuous phase made of a polymer comprising 35 to 75 wt% of styrene units and 65 to 25 wt% of a combination of methyl methacrylate units and n-butyl acrylate units, wherein the weight ratio of methyl methacrylate units to n-butyl acrylate units is 6:1 to 7:1, and the elastic material is a styrene-butadiene block copolymer comprising 30 to 50 wt% of styrene monomer units and 70 to 50 wt% of butadiene monomer units.

[0111] Preferably, the weight ratio of styrene units to the total units of methyl methacrylate and n-butyl acrylate in the continuous phase is 42:58 to 59:41.

[0112] Preferably, the iodine content is determined by GPC on a Perkin-Elmer instrument using a 3% isopropanol / chloroform eluent.

[0113] The weight average molecular weight (Mw) of the polystyrene portion of the styrene-butadiene block copolymer is 45,000 to 75,000, and the ratio (Mw / Mn) of Mw to number average molecular weight (Mn) of the styrene-butadiene block copolymer is 1.20 to 1.80.

[0114] MBABS copolymers are produced by copolymerizing a monomer mixture comprising styrene monomer, methyl methacrylate, and n-butyl acrylate in the presence of a styrene-butadiene block copolymer.

[0115] Amorphous MBABS copolymers are produced by copolymerizing a monomer mixture comprising styrene, methyl methacrylate, and n-butyl acrylate in the presence of an elastomeric material which is a styrene-butadiene block copolymer.

[0116] By adding amorphous impact modifiers such as MBABS to PC / PCCD compositions, molded parts with high light transmittance, low haze values and even low birefringence are obtained.

[0117] Although MBABS copolymer is a transparent material with a transmittance of 90% and a haze of 2.5%, the addition of MBABS to a PC / PCCD blend can reduce the transparency of the entire blend. To achieve high transparency in the overall composition of the present invention, the contents of PC and PCCD, as well as the content of MBABS, need to be adjusted so that the refractive index of the PC / PCCD blend closely matches that of MBABS. Specifically, when their refractive indices are sufficiently close, the overall composition can achieve high transmittance and low haze.

[0118] The present inventors have found that when the content relationship index (r) of components AD in the composition of the present invention defined according to the following formula (A) is in the range of 0-32, molded parts made from the polycarbonate composition of the present invention are transparent and have desirable properties suitable for applications requiring high light transmittance, low haze and low birefringence:

[0119]

[0120] in,

[0121] C A represents the content of component A in the composition,

[0122] C A+B represents the total content of components A and B in the composition, which is 22% to 76% by weight,

[0123]

[0124] BPTMC% A represents the content of BPTMC units in component A in the composition,

[0125] C C represents the content of component C in the composition,

[0126] C A+B+C represents the total content of components A, B and C in the composition,

[0127] C D represents the content of component D in the composition,

[0128] All contents are percentages by weight.

[0129] Advantageously, MBABS is present in the polycarbonate composition of the present invention in an amount of 1 to 60 wt. %, preferably 3 to 50 wt. %, more preferably 3 to 40 wt. %, relative to the total weight of the polycarbonate composition.

[0130] Advantageously, the total amount of components AD is at most 98% by weight, preferably at most 98.5% by weight, more preferably at most 99% by weight, relative to the total weight of the polycarbonate composition according to the invention.

[0131] Other components

[0132] In addition to the above-mentioned components A to D, the polycarbonate composition according to the present invention may optionally contain one or more additives conventionally used in polycarbonate compositions. Such additives are, for example, ultraviolet stabilizers, infrared stabilizers, heat stabilizers, antistatic agents, colorants, lubricants, mold release agents (such as pentaerythritol tetrastearate), antioxidants, flow improvers, anti-drip agents (such as poly(tetrafluoroethylene)), etc.

[0133] Such additives are described, for example, in WO 99 / 55772, pages 15-25 and in “Plastics Additives”, R. Gachter and H. Müller, Hanser Publishers 1983.

[0134] One skilled in the art can select the type of additive so as not to adversely affect the desired properties of the polycarbonate composition according to the present invention.

[0135] Advantageously, the total amount of additives is at most 2% by weight, preferably at most 1.5% by weight, more preferably at most 1% by weight, relative to the total weight of the polycarbonate composition according to the invention.

[0136] Preparation of polycarbonate compositions

[0137] The polycarbonate composition according to the invention may be in the form of pellets, for example.

[0138] The polycarbonate compositions according to the present invention exhibit good processing behavior and can be prepared by various methods. For example, the materials contained in the composition of the present invention are fed into the throat of a twin-screw extruder via a hopper. Alternatively, at least one component can be incorporated into the composition by feeding it directly into the extruder at the throat and / or feeding it downstream via a side filler. Additives can also be compounded into a masterbatch with the desired polymer resin and fed into the extruder. The operating temperature of the extruder is generally higher than the temperature required to make the composition flow. The extrudate is immediately quenched in a water bath and pelletized. As needed, the pellets can be 1 / 4 inch long or less. Such pellets can be used for subsequent molding, shaping, or forming.

[0139] Melt blending methods are preferred due to the availability of melt blending equipment in commercial polymer processing facilities.

[0140] Illustrative examples of equipment used in such melt processing methods include co-rotating and counter-rotating extruders, single screw extruders, co-kneaders, and various other types of extrusion equipment.

[0141] The melt temperature during processing is preferably minimized to avoid excessive degradation of the polymer. It is generally desirable to maintain the melt temperature in the molten resin composition between 230°C and 320°C, although higher temperatures can be used as long as the residence time of the resin in the processing equipment is kept short.

[0142] In some cases, the molten composition is discharged from processing equipment, such as an extruder, via a small exit hole in the die. The resulting strands of molten resin are cooled by passing them through a water bath. The cooled strands can be cut into small pellets or other suitable shapes for packaging and further processing.

[0143] Molded products

[0144] The polycarbonate composition according to the invention can be used, for example, for producing various types of transparent shaped articles.

[0145] In a second aspect, the present invention also provides a shaped article made from the polycarbonate composition according to the first aspect of the present invention.

[0146] As examples of such shaped articles, there may be mentioned, for example, films; profiles; housing parts, sheets; pipes; lenses, display covers (automotive interior applications); electric and electronic parts.

[0147] Preparation of molded products

[0148] The polycarbonate composition according to the present invention can be processed into a transparent shaped article by various means, such as injection molding, extrusion molding, blow molding or thermoforming to form a shaped article.

[0149] In a third aspect, the present invention provides a method for preparing a shaped article made from the composition according to the first aspect of the present invention, which comprises injection molding, extrusion molding, blow molding or thermoforming the polycarbonate composition according to the present invention. Example

[0150] The present invention will be described in detail with reference to the following examples, which are provided for illustration only and are not intended to limit the scope of the present invention.

[0151] Materials used

[0152] Component A

[0153] CoPC-1: A copolycarbonate based on 70 mol% of 3,3,5-trimethyl-1,1-bis(4-hydroxyphenyl)cyclohexane (BPTMC) units and 30 mol% of bisphenol A units, based on the total amount of bisphenol units, having a 7 cm 3 The MVR of 10 min and the weight average molecular weight of about 30,000 g / mol as determined by gel permeation chromatography (GPC) in dichloromethane at 25° C. using polycarbonate standards are commercially available from Covestro Polymer (China) Co., Ltd.

[0154] CoPC-2: A copolycarbonate based on 47 mol % of 3,3,5-trimethyl-1,1-bis(4-hydroxyphenyl)cyclohexane (BPTMC) units and 53 mol % of bisphenol A units, based on the total amount of bisphenol units, having a viscosity of 16 cm as measured at 330° C. and 1.2 kg according to ISO 1133:2011. 3 10 min and a weight average molecular weight of about 27,000 g / mol as determined by gel permeation chromatography (GPC) in dichloromethane at 25° C. using polycarbonate standards, is commercially available from Covestro Polymer (China) Co., Ltd.

[0155] Component B

[0156] PC: available from Covestro Polymer (China) Co., Ltd., bisphenol A-based linear polycarbonate having a weight average molecular weight of 24,000 g / mol as determined by gel permeation chromatography (GPC) in dichloromethane at 25° C. using polycarbonate standards.

[0157] Component C

[0158] PCCD: A copolymer of 1,4-cyclohexanedimethanol (CHDM) and 1,4-dimethylcyclohexanedicarboxylate (DMCD) having an intrinsic viscosity of 0.92 dL / g as measured at a concentration of 0.5 g / 100 ml in 60 / 40 (wt / wt) phenol / tetrachloroethane at 25° C., available as NEOSTAR COPOLYESTER 24303 from Eastman Chemical Company.

[0159] Component D

[0160] ABS: A core-shell impact modifier available from INEOS Styrolution GmbH under the trade name P60, prepared by emulsion polymerization of a mixture of 58 wt % of 24 wt % acrylonitrile and 76 wt % styrene, based on ABS polymer, in the presence of 42 wt % of linear polybutadiene rubber, based on ABS polymer.

[0161] MBS: a methyl methacrylate-butadiene-styrene copolymer having a core-shell structure, available from Japan Kaneka Chemical Co. Ltd. as Kane Ace M732.

[0162] MBABS: contains 50 wt% of styrene units, 35 wt% of methyl methacrylate units, 5 wt% of n-butyl acrylate units and 10 wt% of butadiene units, based on the total weight of all units, and is available from Denka Singapore Private. Ltd under the trade name DENKA Transparent Polymer (TH-21).

[0163] Other components

[0164] H3PO3: phosphorous acid, a heat stabilizer, available from Sigma-Aldrich Chemie GmbH.

[0165] PETS: Pentaerythritol tetrastearate powder, a mold release agent, available as FACI L348 from Faci AsiaPacific Pte Ltd.

[0166] B900: 80% sold by BASF 168 and 20% A mixture of 1076, wherein 168 is tris(2,4-di-tert-butylphenyl) phosphite, 1076 is 2,6-di-tert-butyl-4-(octadecyloxy-carbonylethyl)phenol.

[0167] Test methods

[0168] The physical properties of the samples in the examples were tested as follows.

[0169] Vicat softening temperature

[0170] The Vicat softening temperature (T) was determined with a Coesfeld Eco 2920 instrument from Coesfeld Materialtest on test specimens with the dimensions of 80 mm×10 mm×4 mm according to ISO 306:2013 with a punch load of 50 N and a heating rate of 120° C. / h. Vicat ).

[0171] Transmittance and temperature

[0172] The light transmittance and haze were measured on 2 mm plaques using an instrument UitraScan Pro. from HunterLab (with a D65 illuminant illumination source) according to ASTM method D1003:2013.

[0173] Birefringence

[0174] The birefringence was qualitatively evaluated by observing the molded plaques having a thickness of 2 mm under a polarizing microscope model SV-2000 from the company Strainoptics.

[0175] Figure 1 Displays the score of the corresponding phenomenon.

[0176] A score of 1 indicates the strongest rainbow pattern, and a score of 5 indicates the weakest. A stronger rainbow pattern indicates a higher birefringence. Generally, a score of 3.0 is acceptable, and a score of 5 is optimal.

[0177] Comparative Examples (CE) 1-6 and Inventive Examples (IE) 1-7

[0178] The materials listed in Table 1 were compounded on a twin-screw extruder (ZSK-26) (from Coperion, Werner and Pfleiderer) at a rotation speed of 250 rpm, a throughput of 20 kg / h and a barrel temperature of 250-290° C. and pelletized.

[0179] The granules were processed on an injection molding machine (from Arburg) at a melt temperature of 270-290° C. and a mold temperature of 60-80° C. to give corresponding test specimens.

[0180] The resulting compositions were tested for physical properties including Vicat softening temperature, light transmittance, haze, and birefringence levels, and the results are summarized in Table 1.

[0181]

[0182] As can be seen from Table 1, the pure linear polycarbonate resin of Comparative Example 1 has high transmittance and low haze, but its birefringence fraction is low.

[0183] The composition of Comparative Example 2, which does not include MBABS, has high transmittance and low haze, but its birefringence fraction is low.

[0184] The compositions of Comparative Examples 3 and 4, which included ABS instead of MBABS, had low light transmittance and high haze.

[0185] The composition of Comparative Example 5 including MBS instead of MBABS had low light transmittance and high haze.

[0186] The composition of Comparative Example 6 having an r value exceeding 32 did not have high light transmittance and low haze.

[0187] The compositions of Examples 1 to 7 of the present invention have high light transmittance, low haze, and low birefringence.

[0188] Comparative Examples (CE) 7-11 and Inventive Examples (IE) 8-14

[0189] Similarly, the materials listed in Table 2 were compounded, the properties of the resulting compositions were tested, and the results are summarized in Table 2.

[0190] As can be seen from Table 2, the compositions of Comparative Examples 7 to 11 having r values exceeding 32 have high haze.

[0191] The compositions of Examples 8 to 14 of the present invention have high light transmittance, low haze, and low birefringence.

[0192]

[0193] Comparative Examples (CE) 12-13 and Inventive Examples (IE) 15-30

[0194] Similarly, the materials listed in Table 3 were compounded, the properties of the resulting compositions were tested, and the results are summarized in Table 3.

[0195] As can be seen from Table 3, the compositions of Comparative Examples 12-13 having r values exceeding 32 have high haze.

[0196] The compositions of Examples 15 to 30 of the present invention have high light transmittance, low haze, and low birefringence.

[0197]

Claims

1. A polycarbonate composition comprising the following components relative to the total weight of the composition: A) 0 to 76% by weight of a copolycarbonate containing bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane units and substituted or unsubstituted bisphenol units, B) 0 to 58% by weight of an aromatic linear homopolycarbonate comprising substituted or unsubstituted bisphenol units, C) 15-52 wt. % of poly(1,4-cyclohexylenedimethylene 1,4-cyclohexanedicarboxylate), and D) 1 to 60% by weight of a methyl methacrylate-n-butyl acrylate-butadiene-styrene copolymer, The content relationship index (r) of the components AD having the following formula (A) is: (A) In the range of 0-32, In formula (A), C A represents the content of component A in the composition, C A+B represents the total content of components A and B in the composition, which is 22% to 76% by weight, BPTMC% A represents the content of bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BPTMC) units in component A, C C represents the content of component C in the composition, C A+B+C represents the total content of components A, B and C in the composition, C D represents the content of component D in the composition, All contents are percentages by weight.

2. The composition of claim 1, wherein the copolycarbonate comprises i) Bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane unit of formula (1) where * indicates the position at which formula (1) is attached to the polymer chain, and ii) substituted or unsubstituted bisphenol units of formula (2): in * indicates the position where formula (2) is attached to the polymer chain, R 3 Each independently represents H, a linear or branched C1-C 10 Alkyl, preferably H, linear or branched C1-C4 alkyl, and R 4 Each independently is a straight chain or branched C1-C 10 Alkyl group, preferably a linear or branched C1-C4 alkyl group.

3. The composition of claim 2, wherein the units of formula (1) in the copolycarbonate are derived from bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and the units of formula (2) in the copolycarbonate are derived from bisphenol A.

4. The composition according to claim 2 or 3, wherein the molar content of the units of formula (1) in the copolycarbonate is 20-80 mol%, based on the total molar number of the units of formula (1) and formula (2), and the molar content of the units of formula (2) in the copolycarbonate is 80-20 mol%. Preferably, the molar content of the units of formula (1) in the copolycarbonate is 30-75 mol%, based on the total molar number of the units of formula (1) and formula (2), and the molar content of the units of formula (2) in the copolycarbonate is 70-25 mol%.

5. The composition according to any one of claims 1 to 4, wherein the copolycarbonate is present in an amount of 5% to 60% by weight, preferably 7% to 50% by weight, relative to the total weight of the composition.

6. The composition according to any one of claims 1 to 5, wherein the homopolycarbonate comprises units of formula (2) as defined in claim 2 or 3.

7. The composition according to any one of claims 1 to 6, wherein the homopolycarbonate is present in an amount of 14% to 60% by weight, preferably 14% to 58% by weight, relative to the total weight of the composition.

8. The composition of any one of claims 1 to 7, wherein the poly(1,4-cyclohexylenedimethylene 1,4-cyclohexanedicarboxylate) has a weight average molecular weight of 30,000 to 80,000, preferably 41,000 to 60,000 as measured by GPC on a Perkin-Elmer instrument using 3% isopropyl alcohol / chloroform eluent and a refractive index of 1.506 to 1.508 as measured at the sodium-D-line (wavelength 589 nm) with an Abbe refractometer according to ISO 489.

9. The composition according to any one of claims 1 to 8, wherein the methyl methacrylate-n-butyl acrylate-butadiene-styrene copolymer comprises 1 to 15 wt% of a dispersed phase made of a rubber-like elastic material and 99 to 85 wt% of a continuous phase made of a polymer comprising 35 to 75 wt% of styrene units and 65 to 25 wt% of a combination of methyl methacrylate units and n-butyl acrylate units, wherein the weight ratio of methyl methacrylate units to n-butyl acrylate units is 6:1 to 7:1, and the elastic material is a styrene-butadiene block copolymer comprising 30 to 50 wt% of styrene monomer units and 70 to 50 wt% of butadiene monomer units.

10. The composition according to any one of claims 1 to 9, wherein the methyl methacrylate-n-butyl acrylate-butadiene-styrene copolymer is present in an amount of 3 to 50 wt%, more preferably 3 to 40 wt%, relative to the total weight of the composition.

11. The composition according to any one of claims 1 to 10, wherein the total amount of components AD is at most 98% by weight, preferably at most 98.5% by weight, more preferably at most 99% by weight, relative to the total weight of the composition.

12. A shaped article made from the composition according to any one of claims 1 to 11.

13. A method for preparing the molded article according to claim 12, comprising injection molding, extrusion molding, blow molding or thermoforming the polycarbonate composition according to any one of claims 1 to 11.

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