EP3455295A1 - Polyphenylsulfone compositions including a polycarbonate-polysiloxane copolymer - Google Patents
Polyphenylsulfone compositions including a polycarbonate-polysiloxane copolymerInfo
- Publication number
- EP3455295A1 EP3455295A1 EP17720157.1A EP17720157A EP3455295A1 EP 3455295 A1 EP3455295 A1 EP 3455295A1 EP 17720157 A EP17720157 A EP 17720157A EP 3455295 A1 EP3455295 A1 EP 3455295A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymer composition
- group
- polycarbonate
- mol
- sipc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/06—Polysulfones; Polyethersulfones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/14—Macromolecular materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
- C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Definitions
- the present invention relates to high performance blends of
- compositions are particularly useful for the manufacture of parts for electronic devices.
- aluminum parts and/or aluminum plastic composite parts present in mobile devices are submitted generally to anodization, i.e. to electro chemical processes whose aim is to build an oxide layer on the aluminum surface, notably through the use of aggressive chemicals.
- anodization i.e. to electro chemical processes whose aim is to build an oxide layer on the aluminum surface, notably through the use of aggressive chemicals.
- the polymeric materials must be highly resistant to aggressive acids.
- plastics materials used in mobile electronics parts are resistant to consumer chemicals and staining agents that often come into contact with them, in particular with the housings.
- Typical consumer chemicals and staining agents include : lotions (hand lotions, sunscreen lotions, etc.), makeup (such as lipstick, lip gloss, lip liner, lip plumper, lip balm, foundation, powder, blush), food (olive oil, coffee, red wine, mustard, ketchup and tomato sauce), dyes and pigments (such as those found in dyed textiles and leather used for the manufacture of portable electronic devices housings).
- the portable electronic devices housings maybe easily stained : anti-stain properties are hence desired for maintaining good aesthetic appearance of said devices, in particular when they are white or have bright or clear colors.
- Exposure to consumer chemicals can lead to premature failure and/or environmental stress cracking of the part if the chemical resistance of the plastic material is not sufficient.
- polymeric materials should possess excellent impact resistance for use in electronic devices; however, the addition of coloring agents such as titanium dioxide (Ti0 2 ) may in some instances result in decreased toughness.
- coloring agents such as titanium dioxide (Ti0 2 ) may in some instances result in decreased toughness.
- Exemplary embodiments are directed to a polymer composition
- a polymer composition comprising at least one poly(aryl ether sulfone) (PAES) polymer, where the at least one poly(aryl ether sulfone) (PAES) includes a polyphenylsulfone (PPSU), and at least one polycarbonate-polysiloxane copolymer (SiPC).
- the polymer composition may optionally include one or more poly(aryl ether sulfones) (PAES) polymers other than the polyphenylsulfone (PPSU).
- the polymer composition may also optionally include one or more polyaryletherketones (PAEK), preferably polyetheretherketone (PEEK).
- the polymer composition additionally includes titanium dioxide (Ti0 2 ).
- Ti0 2 titanium dioxide
- halogen includes fluorine, chlorine, bromine and iodine, unless indicated otherwise;
- aromatic denotes any mono- or polynuclear cyclic group (or moiety) having a number of ⁇ electrons equal to 4n+2, wherein n is 0 or any positive integer; an aromatic group (or moiety) can be an aryl and arylene groups (or moiety) moieties.
- hydrocarbyl as used herein means the monovalent moiety obtained upon removal of a hydrogen atom from a parent hydrocarbon.
- hydrocarbyl are alkyls of 1 to 25 carbon atoms, inclusive such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, undecyl, decyl, dodecyl, octadecyl, nonodecyl eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl and the isomeric forms thereof; aryls of 6 to 25 carbon atoms, inclusive, such as phenyl, tolyl, xylyl, napthyl, biphenyl, tetraphenyl and the like; aralkyls of 7 to 25 carbon atoms, inclusive, such as benzyl,
- halogen-substituted hydrocarbyl as used herein means the
- hydrocarbyl moiety as previously defined wherein one or more hydrogen atoms have been replaced with halogen.
- PAES Poly(aryl ether sulfone)
- PAES poly(aryl ether sulfone)
- each R is selected from a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary ammonium; (ii) each h, equal to or different from each other, is an integer ranging from 0 to 4; and
- T is selected from the group consisting of a bond, a sulfone
- Rj and Rk are selected from a hydrogen, a halogen, an alkyl, an alkenyl, an alkynyl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary ammonium.
- R j and R k are preferably methyl groups.
- At least 60 mol %, 70 mol %, 80 mol %, 90 mol %, 95 mol %, 99 mol %, and most preferably all of recurring units in the PAES are recurring units (RPAES).
- the at least one PAES of the polymer composition includes a
- polyphenylsulfone PPSU
- PPSU polyphenylsulfone
- At least 60 mol %, 70 mol %, 80 mol %, 90 mol %, 95 mol 99 mol %, and most preferably all of the recurring units in the PPSU are recurring units of formula (K'-A).
- PPSU can be prepared by known methods and is notably available as RADEL ® PPSU from Solvay Specialty Polymers USA, L.L.C.
- the polymer composition further includes at least one PAES other than the PPSU.
- the at least one PAES other than the PPSU is preferably a polyethersulfone (PES), a polysulfone (PSU), or a combination thereof.
- PES polyethersulfone
- At least 60 mol %, 70 mol %, 80 mol %, 90 mol %, 95 mol %, 99 mol %, and most preferably all of the recurring units in the PES are recurring units of formula (K'-B).
- PES can be prepared by known methods and is notably available as VERADEL ® PESU from Solvay Specialty Polymers USA, L.L.C.
- PSU polysulfone
- At least 60 mol %, 70 mol %, 80 mol %, 90 mol %, 95 mol %, 99 mol %, and most preferably all of the recurring units in the PSU are recurring units of formula (K'-C).
- PSU can be prepared by known methods and is available as UDEL ® PSU from Solvay Specialty Polymers USA, L.L.C.
- the at least one poly(aryl ether sulfone) (PAES) polymer other than the polyphenylsulfone (PPSU) represents at most about 25 wt. % of the total weight of polymers in the polymer composition.
- the polycarbonate-polysiloxane copolymer (“SiPC copolymer”) includes any copolymer comprising more than 50 mol % of the sum by weight of polycarbonate blocks and polysiloxane blocks.
- the SiPC copolymer comprises :
- X represents a bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, -S-, -SO-, -SO2-, -O- or -CO- (preferably X is a group -QR ⁇ R 2 )-, wherein Pv 1 and Pv 2 independently represent hydrogen or an alkyl group having
- R 1 and R 2 are methyl
- R 3 represents a halogen, an alkyl group having 1-20 carbon atoms, or an aryl group
- n is an integer ranging from 0 to 4, and
- R 4 and R 5 independently represent a hydrogen, a halogen, a hydrocarbyl or halogen-substituted hydrocarbyl (preferably R 4 is methyl and R 5 is methyl or phenyl), R 6 and R 7 independently represent an organic residue having an aromatic nucleus, m is an integer raging from about 5 to more than 100 (preferably from about 5 to about 1000, preferably about 5 to about 200). In exemplary embodiments, R 6 and R 7 independently represent a
- the moiety -O-R - in Formula M above is a group of formula :
- wherin Y is a hydrogen, a hydrocarbyl, or a halogen-substituted hydrocarbyl (preferably methoxy), and
- SiPC copolymer is the polycarbonate blocks and polysiloxane blocks.
- the polysiloxane block is preferably a polydimethylsiloxane block.
- the ratio of the weight of the polycarbonate block to the weight of the polysiloxane block ranges from 0.05 to 3.
- the SiPC copolymer preferably includes about 0.5 % to about 30 %, preferably about 1 % to about 30 %, preferably about 4 % to about 8 % by weight, of the polysiloxane block.
- the viscosity average molecular weight of the SiPC copolymer preferably ranges from 10,000 g/mol to 50,000 g/mol, preferably 12,000 g/mol
- the SiPC copolymer exhibits at least one of :
- melt volume-flow rate as measured by ISO 1133 (300°C, 1.20 kg) ranging from about 8 to about 16 cm 3 /10 min, preferably about 12 to about 13 cm 3 / 10 min;
- Polycarbonate-polysiloxane copolymers are available, for example, as TARFLON ® NEO from Idemitsu Kosan Co., Ltd, and as LEXAN ® EXL from Saudi Basic Industries Corporation (SABIC).
- the amount of the SiPC copolymer ranges from about 5 wt. % to about 45 wt. %, preferably from about 10 wt. % to about 40 wt. %, preferably from about 15 wt. % to about 35 wt. %, preferably from about 20 wt. % to about 35 wt. % based on total weight of the composition.
- the amount of the SiPC copolymer may range from about 10 wt. % to about 40 wt. %, based on to total weight of the SiPC copolymer and the PPSU polymer.
- PAEK optionally poly(aryl ether ketone)
- PAEK poly(aryl ether ketone)
- the recurring units (R PAEK ) are selected from the group consisting of units of formulae (J- A) to (J-D) below :
- each of R' is selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; and
- the respective phenylene moieties may independently have 1,2-, 1,4- or 1,3-linkages to the other moieties different from R' in the recurring unit (R PAEK ).
- said phenylene moieties have 1,3- or 1,4- linkages, more preferably they have a 1,4-linkage.
- j ' is preferably at each occurrence zero so that the phenylene moieties have no other substituents than those linking the main chain of the polymer.
- the PAEK is poly(ether ether ketone) (PEEK).
- PEEK poly(ether ether ketone)
- a "poly(ether ether ketone) (PEEK)" denotes any polymer of which more than 50 mol % of the recurring units (R PAEK ) are recurring units of formula J'-A :
- At least 60 mol %, 70 mol %, 80 mol %, 90 mol %, 95 mol %, 99 mol %, and most preferably all of recurring units (R PAEK ) are recurring units (J'-A).
- the PAEK is poly(ether ketone ketone) (PEKK).
- PEKK poly(ether ketone ketone)
- R PAEK recurring units of formula J'-B and formula J"-B :
- At least 60 mol %, 70 mol %, 80 mol %, 90 mol %, 95 mol %, 99 mol %, and most preferably all of recurring units (R PAEK ) are a combination of recurring units (J'-B) and (J"-B).
- the PAEK is poly(ether ketone) (PEK).
- PEK poly(ether ketone)
- a "poly(ether ketone) (PEK)" denotes any polymer of which more than 50 mol % of the recurring units (R PAEK ) are recurring units of formula (J'-C) :
- At least 60 mol %, 70 mol %, 80 mol %, 90 mol %, 95 mol %, 99 mol %, and most preferably all of recurring units (R PAEK ) are recurring units (J'-C).
- the PAEK is a PEEK-PEDEK copolymer.
- a "PEEK-PEDEK copolymer” denotes any polymer of which more than 50 mol % of the recurring units (R PAEK ) are both recurring units of
- the PEEK-PEDEK copolymer may include relative molar proportions of recurring units J'-A and J'-D (PEEK/PEDEK) ranging from 95/5 to 60/40.
- PEEK/PEDEK relative molar proportions of recurring units J'-A and J'-D
- the sum of recurring units J'-A and J'-D represents at least 60 mol %, 70 mol %, 80 mol %, 90 mol %, 95 mol %, 99 mol %, of recurring units in the PAEK.
- recurring units J'-A and J'-D represent all of the recurring units in the PAEK.
- the PAEK is PEEK.
- KET ASPIRE ® PEEK is
- the optional polyaryletherketone (PAEK) is advantageously present in an amount of at most about 30 wt. % based on combined weight of all the polymers in the composition.
- the polyaryletherketone (PAEK) is present in an amount ranging from 0 wt. % to about 25 wt. %, preferably about 5 wt. % to about 20 wt. % based on the total weight of the polymer composition.
- the polymer composition includes titanium dioxide (Ti0 2 ).
- the amount of titanium dioxide (Ti0 2 ) preferably ranges from 0 phr to about 25 phr, preferably from about 0.1 phr to about 25 phr, preferably from about 5 phr to about 20 phr, preferably from about 6 phr to about 15 phr.
- the amount of titanium dioxide (Ti0 2 ) may be at most about 25 phr, preferably at most about 20 phr, preferably at most about 20 phr, preferably at most about 15 phr, preferably at most about 10 phr, preferably at most about 8 phr, preferably at most about 6 phr.
- the polymer composition may further optionally comprise additional additives such as ultraviolet light stabilizers (e.g. Tinuvin ® 234 available from BASF), heat stabilizers, antioxidants, pigments, processing aids, lubricants, flame retardants, and/or conductivity additive such as carbon black or carbon nano fibrils.
- the polymer composition may also further comprise other polymers such as polyetherimide and/or polycarbonate.
- the polymer composition may further comprise flame retardants such as halogen-containing and halogen- free flame retardants.
- the polymer composition can be manufactured by melt-mixing a polyphenylsulfone (PPSU), a polycarbonate-polysiloxane copolymer (SiPC), and optional ingredients such as a poly(aryl ether sulfone) (PAES) other than the polyphenylsulfone (PPSU), a poly(aryl ether ketone) (PAEK), and titanium dioxide (Ti0 2 ) to provide a molten mixture, followed by extrusion and cooling of the molten mixture.
- PPSU polyphenylsulfone
- SiPC polycarbonate-polysiloxane copolymer
- optional ingredients such as a poly(aryl ether sulfone) (PAES) other than the polyphenylsulfone (PPSU), a poly(aryl ether ketone) (PAEK), and titanium dioxide (Ti0 2 ) to provide a molten mixture, followed by extrusion and cooling of the mol
- Exemplary embodiments also include a method of increasing the chemical resistance and/or impact strength of a composition comprising a
- polyphenylsulfone PPSU
- SiPC polycarbonate- polysiloxane copolymer
- compositions described herein are advantageously provided in the form of pellets, which may be used in injection molding or extrusion processes known in the art.
- the preparation of the polymer composition can be carried out by any known melt-mixing process that is suitable for preparing thermoplastic molding compositions. Such a process is typically carried out by heating the
- thermoplastic polymer above the melting temperature of the thermoplastic polymer thereby forming a melt of the thermoplastic polymer.
- the process for the preparation of the composition can be carried out in a melt-mixing apparatus, for which any melt-mixing apparatus known to the one skilled in the art of preparing polymer compositions by melt mixing can be used.
- Suitable melt- mixing apparatus are, for example, kneaders, Banbury mixers, single-screw extruders, and twin-screw extruders.
- the constituting components for forming the composition are fed to the melt-mixing apparatus and melt-mixed in that apparatus.
- the components may be fed simultaneously as a powder mixture or granule mixture, also known as dry-blend, or may be fed separately.
- the structural parts of the mobile electronic devices according to the present invention are made from the polymer composition using any suitable melt-processing method.
- they are made by injection molding or extrusion. Injection molding is a preferred method.
- the structural parts of the mobile electronic devices according to the present invention may be coated with metal by any known methods for accomplishing that, such as vacuum deposition (including various methods of heating the metal to be deposited), electroless plating, electroplating, chemical vapor deposition, metal sputtering, and electron beam deposition.
- vacuum deposition including various methods of heating the metal to be deposited
- electroless plating electroplating
- chemical vapor deposition metal sputtering
- electron beam deposition electron beam deposition
- the metal may adhere well to the structural parts without any special treatment, usually some well-known in the art method for improving adhesion will be used. This may range from simple abrasion of the synthetic resin surface to roughen it, addition of adhesion promotion agents, chemical etching, functionalization of the surface by exposure to plasma and/or radiation (for instance laser or UV radiation) or any combination of these.
- some of the metal coating methods comprise at least one step where the structural part is immersed in an acid bath.
- More than one metal or metal alloy may be plated onto the structural parts made of the polymer composition, for example one metal or alloy may be plated directly onto the synthetic resin surface because of its good adhesion, and another metal or alloy may be plated on top of that because it has a higher strength and/or stiffness.
- Useful metals and alloys to form the metal coating include copper, nickel, iron-nickel, cobalt, cobalt-nickel, and chromium, and combinations of these in different layers. Preferred metals and alloys are copper, nickel, and iron-nickel, and nickel is more preferred.
- the surface of the structural part may be fully or partly coated with metal. Preferably more than 50 percent of the surface area will be coated, more preferably all of the surface will be coated. In different areas of the structural part the thickness and/or the number of metal layers, and/or the composition of the metal layers may vary. The metal may be coated in patterns to efficiently improve one or more properties in certain sections of the structural part.
- An aspect of the present invention is directed to mobile electronic devices comprising at least one structural part made of a polymer composition described herein, and in particular to a laptop, a mobile phone, a GPS, a tablet, personal digital assistants, portable recording devices, portable reproducing devices and portable radio receives.
- manufacture of formed articles in particular parts of electronic devices, more particularly parts of portable or mobile electronic devices.
- mobile electronic device is intended to denote any electronic device that is designed to be conveniently transported and used in various locations while exchanging/providing access to data, e.g. through wireless connections or mobile network connection.
- mobile electronic devices include mobile phones, personal digital assistants, laptop computers, tablet computers, radios, cameras and camera accessories, watches, calculators, music players, global positioning system receivers, portable games, hard drives and other electronic storage devices, and the like.
- the at least one part of the mobile electronic device according to the present invention may be selected from a large list of articles such as fitting parts, snap fit parts, mutually moveable parts, functional elements, operating elements, tracking elements, adjustment elements, carrier elements, frame elements, switches, connectors and (internal and external) components of housing, which can be notably produced by injection molding, extrusion or other shaping technologies.
- polymer compositions described herein are very well suited for the production of housing components of mobile electronic device.
- the at least one part of the mobile electronic device according to the present invention is advantageously a component of a mobile electronic device housing.
- mobile electronic device housing is meant one or more of the back cover, front cover, antenna housing, frame and/or backbone of a mobile electronic device.
- the housing may be a single component-article or, more often, may comprise two or more components.
- backbone is meant a structural component onto which other components of the device, such as electronics, microprocessors, screens, keyboards and keypads, antennas, battery sockets, and the like are mounted.
- the backbone may be an interior component that is not visible or only partially visible from the exterior of the mobile electronic device.
- the housing may provide protection for internal components of the device from impact and contamination and/or damage from environmental agents (such as liquids, dust, and the like). Housing components such as covers may also provide substantial or primary structural support for and protection against impact of certain components having exposure to the exterior of the device such as screens and/or antennas. Housing components may also be designed for their aesthetic appearance and touch.
- the mobile electronic device housing is selected from the group consisting of a mobile phone housing, a tablet housing, a laptop computer housing and a tablet computer housing. Excellent results were obtained when the part of the mobile electronic device according to the present invention was a mobile phone housing.
- the shaped articles obtained from (or comprising) polymer compositions described herein may be manufactured by molding techniques.
- any standard molding technique can be used; standard techniques including shaping the polymer compositions in a molten/softened form can be advantageously applied, and include notably compression molding, extrusion, injection molding, transfer molding and the like.
- the injection molding technique is the most versatile and extensively used. According to this technique, a ram or screw-type plunger is used for forcing a portion of polymer
- compositions in their molten state into a mold cavity wherein the same solidified into a shape that has confirmed to the contour of the mold.
- suitable means e.g. an array of pins, sleeves, strippers, etc.
- the method for manufacturing a part of an electronic device includes a step of machining of a standard shaped article so as to obtain said part having different size and shape from said standard shaped article.
- said standard shaped articles include notably a plate, a rod, a slab and the like.
- Said standard shaped parts can be obtained by any processing technique, including notably extrusion or injection molding of the polymer composition.
- the parts of the electronic devices according to the present invention may be coated with metal by any known methods for accomplishing that, such as vacuum deposition (including various methods of heating the metal to be deposited), electroless plating, electroplating, chemical vapor deposition, metal sputtering, and electron beam deposition.
- the method may additionally comprise at least one additional step comprising coating at least one metal onto at least a part of the surface of the said part.
- the metal may adhere well to the parts without any special treatment, usually some well-known in the art methods for improving adhesion can be used. This may range from simple abrasion of the surface to roughen it, addition of adhesion promotion agents, chemical etching, functionalization of the surface by exposure to plasma and/or radiation (for instance laser or UV radiation) or any combination of these.
- some of the metal coating methods may include at least one step where the part is immersed in an acid bath. More than one metal or metal alloy may be plated onto the parts made of the polymer composition, for example one metal or alloy may be plated directly onto the surface because of its good adhesion, and another metal or alloy may be plated on top of that because it has a greater strength and/or stiffness.
- Useful metals and alloys to form the metal coating include copper, nickel, iron-nickel, cobalt, cobalt- nickel, and chromium, and combinations of these in different layers. Preferred metals and alloys are copper, nickel, and iron-nickel, and nickel is more preferred.
- the surface of the part may be fully or partly coated with metal. In different areas of the part the thickness and/or the number of metal layers, and/or the composition of the metal layers may vary. The metal may be coated in patterns to efficiently improve one or more properties in certain sections of the part.
- the polymer composition may exhibit improved impact performance.
- mobile electronic devices While it is often desirable that mobile electronic devices (and parts thereof) be small and lightweight, excellent structural strength is highly desirable so that device will not be damaged in normal handling and occasional sudden impact (e.g. drops).
- structural parts are generally built into mobile electronic devices that impart strength, rigidity, and/or impact resistance to the device, and possibly also provide mounting places for various internal
- the polymer composition may have a notched Izod impact strength of at least 300 Joules/meter ("J/m"), preferably at least 400 J/m, preferably at least about 450 J/m, preferably at least about 500 J/m, preferably at least about 550 J/m, preferably at least about 600 J/m, preferably at least about 650 J/m.
- J/m Joules/meter
- the polymer composition has a notched Izod impact strength ranging from about 400 J/m to about 800 J/m, preferably about 450 J/m to about 800 J/m, preferably about 500 J/m to about 800 J/m, preferably about 550 J/m to about 800 J/m, preferably about 600 J/m to about 800 J/m.
- Impact resistance can be measured using the notched Izod impact test according the ASTM D256 standard, as described further in the Examples.
- the polymer composition may also exhibit improved chemical and staining resistance.
- a plastic component of a mobile electronic device can be exposed to environment external to the mobile electronic device (e.g. a mobile phone or a tablet computer).
- the exposed portion of the plastic component may come into contact with the external environment including, but not limited to, human body parts interacting with mobile electronic device. Agents in the external
- the plastic component includes, but are not limited to, acidic agents and staining agents.
- Typical staining agents include, but are not limited to makeup,
- plastic component e.g., lipstick, lip gloss, lip liner, lip plumper, lip balm, foundation, powder, and blush
- artificial or natural colorants e.g., those found in soft drinks, coffee, red wine, mustard, ketchup and tomato sauce
- dyes and pigments e.g., those found in dyed textiles and leather, used for the manufacture of portable electronic devices housings.
- the exposed portion of the plastic component could be easily stained when contacted with a staining agent and, correspondingly, plastic components having anti-stain properties are desirable, especially in the case where the plastic component is colored in shades of white or is clear colored. Staining resistance can be measured by determining the change
- the polymer composition can have a ⁇ , using the mustard test described in the Examples below, of not more than about 3, preferably not more than about 2.5, preferably not more than about 2.0, preferably not more than about 1.5, preferably not more than about 1.0, preferably not more than about 0.7.
- the resistance of a device component to polar organic chemicals can be measured by its resistance to sunscreen lotion, which generally represents one of the harshest consumer chemicals a device component is expected to endure in its intended application setting.
- sunscreen lotion generally contains a spectrum of ultraviolet absorbing chemicals that can be highly aggressive to plastic.
- a representative sunscreen may include at least 1.8 vol % avobenzone (l-(4-methoxyphenyl)-3-(4-tert-butylphenyl)-l,3-propanedione), at least 7 vol. % homosalate (3,3,5-trimethylcyclohexyl salicylate) and at least 5 vol.
- An example of the aforementioned sunscreen is commercially available under the trade name Banana Boat ® Sport Performance ® (SPF 30) from Edgewell (St. Louis, MO).
- the chemical resistance of a polymer composition can be measured as critical strain, the lowest strain necessary to visually observe cracking or crazing in a molded sample of the polymer composition after the sample is exposed to aggressive chemicals under stress and aged in a controlled environment. In general, the higher the critical strain, the higher the chemical resistance of the polymer composition to polar organic agents. In some aspects, the polymer composition has a Sunscreen Test strain to fail % (i.e.
- critical strain of greater than or equal to 1.7 %, preferably greater than or equal to about 1.8 %, preferably greater than or equal to about 1.9 %, preferably greater than or equal to about 2.0 %.
- the Sunscreen Test and measurement of critical strain is described further in the Examples below.
- the polymer compositions also have desirable colorability and/or whiteness.
- the polymer composition has a CIE L* value ranging from about 88.0 to about 98.0, preferably from about 90.0 to about 98.0, preferably from about 91.0 to about 98.0, preferably from about 91.0 to about 96.0, preferably from about 91.0 to about 95.0.
- the polymer composition has a CIE L* value that is at least about 90.0, preferably at least about 91.0, preferably at least about 92.0.
- the polymer composition has a CIE a* value ranging from about -2.0 to about +2.0, preferably from about -1.0 to about +1.0, preferably from about -0.5 to about +0.5, preferably from about -0.5 to about 0, preferably from about -0.2 to about 0.
- the polymer composition has a CIE b* value ranging from about -2.0 to about +6.0, preferably from about 0 to about +6.0, preferably from about 0 to about +4.0, preferably from about +1.0 to about +4.0, preferably from about +2.0 to about +4.0.
- the polymer composition may also exhibit anodization resistance.
- Metal parts e.g. aluminum parts
- metal-plastic composite parts e.g., aluminum- plastic parts
- Anodization treatment can include electro-chemical processes where the aim is to build an oxide layer on the metal surface, generally through the use of aggressive chemicals.
- polymeric materials exhibiting excellent anodization resistance are desirable in application settings in which anodization is performed on mobile electronic parts already containing or assembled to polymeric elements.
- Anodization resistance can be measured as the respective differences in tensile strength, tensile modulus, and elongation at break of an as-molded sample of a polymer composition and a molded sample that has been exposed to 70 wt. % sulfuric acid at 23° C for 24 hours. The measurement of the anodization resistance is further described in the Examples.
- the polymer composition may exhibit a difference in tensile strength of not more than about 5 MPa, preferably not more than about 4 MPa, preferably not more than about 3 MPa, preferably not more than about 2 MPa, preferably not more than about 1 MPa.
- the polymer composition may exhibit a difference in tensile modulus of not more than about 0.10 GPa, preferably not more than about 0.09 GPa, 0.08 GPa, 0.07 GPa, 0.06 GPa, 0.05 GPa, 0.04 GPa, most preferably not more than about 0.03 GPa.
- the polymer composition may exhibit a difference in tensile elongation at break of not more than about 20 %, preferably not more than about 15 %, preferably not more than about 10 %.
- the polymer composition may exhibit a combination of a notched Izod impact not less than about 450 J/m, a Sunscreen Test critical strain greater than or equal to 2.0 %, a mustard staining Delta E less than or equal to about 2.2, and a CIE color L* ranging from about 90.0 to about 95.0.
- MFR Melt flow rate
- PC Polycarbonate (PC) - Grade : Makrolon ® 3108 available from Bayer Materials Science, Inc.
- PC-PDMS copolymer Polycarbonate-polydimethylsiloxane block copolymer
- Grade : Tarflon ® AG 1760 available from Idemitsu Chemical Co.
- PC-PDMS copolymer Polycarbonate-polydimethylsiloxane block copolymer
- Grade Tarflon ® RC1760 available from Idemitsu Chemical Co.
- Tinuvin ® 234 available from BASF.
- the polymer blends of the Examples and Comparative examples were prepared by first drying the polymer ingredients for at least 16 hours in desiccated ovens.
- the PPSU was dried at a temperature of 300°C, while the PC and SiPC were dried at a temperature of 175 °F.
- the ingredients of each example were tumble-blended for about 20 minutes.
- Each formulation was then melt compounded using a 26 mm diameter Coperion ® ZSK-26 co-rotating partially intermeshing twin screw extruder having an L/D ratio of 48: 1.
- the barrel sections 2 through 12 and the die were heated to set point temperatures as follows :
- the resins and additives were fed at barrel section 1 using a gravimetric feeder at throughput rates in the range 30-35 lb/hr.
- the extruder was operated at screw speeds of around 200 RPM. Vacuum was applied at barrel zone 10 with a vacuum level of 650-700 mm of mercury.
- a single-hole die was used for all the compounds and the molten polymer strand exiting the die was cooled in a water trough and then cut in a pelletizer to form pellets
- the example formulations were injection molded to produce 3.2 mm (0.125 in) thick ASTM tensile and flexural specimens for mechanical property testing.
- Type I tensile ASTM specimens and 5 in x 0.5 in x 0.125 in flexural specimens were injection molded using the following approximate temperature conditions on the barrel and mold :
- As-molded color of each formulation was measured to assess the whiteness of the formulation.
- the color was measured according to the CIE L-a-b coordinates standard where the L* coordinate represents the lightness (black to white) scale, the a* coordinate represents the green-red chromaticity and the b* scale represents the blue-yellow chromaticity.
- the whiteness of the material was considered acceptable if the L* value was greater than 90.0 and the combined absolute values of the chromaticity coordinates a* and b* were less than 4.0 units.
- Color stability against staining was evaluated by measuring the Delta E color difference according to CIE Lab protocols between an as-molded Type I ASTM tensile bar and a bar that was exposed to mustard for 72 hours in a controlled humidity and temperature chamber at a temperature of 65°C and 90 % relative humidity.
- a second chemical resistance test was an acid bath immersion test in which Type I ASTM tensile specimens were immersed in 70 wt. % sulfuric acid at 23°C, after which the specimens were removed, washed with water, then tested for tensile properties.
- the tensile properties before and after the acid exposure were evaluated as an indicator of the material's ability to withstand the anodizing steps commonly applied in the manufacture of mobile devices having a combination of metal and plastic components parts, where the plastic material is exposed to chemical conditions in anodizing baths - typically including various strong acidic environments.
- the sunscreen chemical resistance was found to be significantly enhanced for the blends including SiPC as compared with the blend where standard PC was used in the formulation at the same low level of 25 wt. % of the composition.
- the acid resistance of the formulations (which is a proxy for anodizing bath resistance) was very good in all cases with no significant changes in strength and modulus (stiffness) following the acid treatment, with only a slight reduction in elongation at break observed.
- the whiteness of the formulations was excellent in all cases with L* (lightness scale) values in the range 90-95 and where the combined absolute value of the chromaticity coordinates (a* + b*) was less than 4 units. While all formulations exhibited excellent lightness as evidenced by the high L* values, the lightness of Example 2 utilizing Tarflon ® RC1760 SiPC was slightly higher than that of the Comparative Example utilizing standard PC. This result was also surprising and unexpected because the use of SiPC was not expected to result in improved whiteness as compared to the Comparative Example including PC and the same amount of Ti0 2 .
- compositions including SiPC would have exhibited a greater degree of compatibility with PPSU relative to standard PC.
- the polydimethylsiloxane component of the SiPC block copolymer is grossly incompatible with PPSU. Therefore it was expected that the SiPC copolymer would be much more incompatible with PPSU than standard PC homopolymer. As such, the blends would also be expected to have inferior properties.
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Abstract
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US201662333435P | 2016-05-09 | 2016-05-09 | |
EP16187802 | 2016-09-08 | ||
PCT/EP2017/060509 WO2017194364A1 (en) | 2016-05-09 | 2017-05-03 | Polyphenylsulfone compositions including a polycarbonate-polysiloxane copolymer |
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US20070066741A1 (en) * | 2005-09-16 | 2007-03-22 | Donovan Michael S | High glass transition temperature thermoplastic articles |
US20090069489A1 (en) * | 2007-09-12 | 2009-03-12 | Peter Vollenberg | Polycarbonate-poly(ester-ether) copolymer composition, method of manufacture, and articles therefrom |
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