WO2019112847A1 - Aromatic polymer composition for use in a camera module - Google Patents
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- WO2019112847A1 WO2019112847A1 PCT/US2018/062760 US2018062760W WO2019112847A1 WO 2019112847 A1 WO2019112847 A1 WO 2019112847A1 US 2018062760 W US2018062760 W US 2018062760W WO 2019112847 A1 WO2019112847 A1 WO 2019112847A1
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
- C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
- C08L23/0884—Epoxide-containing esters
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- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
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- 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
- C08L83/04—Polysiloxanes
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
- G03B17/00—Details of cameras or camera bodies; Accessories therefor
- G03B17/02—Bodies
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
- G03B30/00—Camera modules comprising integrated lens units and imaging units, specially adapted for being embedded in other devices, e.g. mobile phones or vehicles
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/017—Antistatic agents
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- C08L2205/00—Polymer mixtures characterised by other features
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- C08L2205/00—Polymer mixtures characterised by other features
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- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/12—Polymer mixtures characterised by other features containing additives being liquid crystalline or anisotropic in the melt
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- C—CHEMISTRY; METALLURGY
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
Definitions
- Camera modules are often employed in mobile phones, laptop computers, digital cameras, digital video cameras, etc. Examples include, for instance, compact camera modules that include a carrier mounted to a base, digital camera shutter modules, components of digital cameras, cameras in games, medical cameras, surveillance cameras, etc. Such camera modules have become more complex and now tend to include multiple moving parts. In some cases, for example, two compact camera module assemblies can be mounted within a single module to improve picture quality (“dual camera” modules). In other cases, an array of compact camera modules can be employed. Regardless of the particular design, liquid crystalline polymers are often used during manufacturing due to their highly oriented crystal structure, which allows the polymers to be readily molded into very small and complex parts. Unfortunately, however, the highly oriented structure also makes liquid crystalline polymers susceptible to wear. Namely, one or more skin layers of the polymer tend to be peeled off from the part during use, which can lead to a poor appearance and/or performance.
- a polymer composition that comprises at least one aromatic polymer (e.g., thermotropic liquid crystalline polymer) and a tribological formulation in an amount from about 1 to about 20 parts by weight per 100 parts by weight of the aromatic polymer.
- the tribological formulation contains a fluorinated additive and a siloxane polymer having a weight average molecular weight of about 100,000 grams per mole or more.
- the weight ratio of the fluorinated additive to the siloxane polymer is from about 0.5 to about 12.
- a camera module that comprises a base on which is mounted a carrier assembly.
- the base, carrier assembly, or both comprise a molded part.
- the molded part contains a polymer composition that includes at least one
- thermotropic liquid crystalline polymer and a tribological formulation.
- the polymer composition exhibits a dynamic coefficient of friction of about 0.4 or less as determined in accordance with VDA 230-206:2007.
- Figs. 1 -2 are perspective and front views of a compact camera module (“CCM”) that may be formed in accordance with one embodiment of the present invention.
- CCM compact camera module
- the present invention is directed to a polymer composition that contains an aromatic polymer in combination with a tribological formulation.
- a polymer composition that contains an aromatic polymer in combination with a tribological formulation.
- the present inventor has discovered that the resulting polymer composition can achieve a low degree of surface friction that minimizes the extent to which a skin layer is peeled off during use of a part containing the composition (e.g., in a camera module).
- the polymer composition may exhibit a dynamic coefficient of friction of about 1.0 or less, in some
- the wear depth may be about 500 micrometers or less, in some embodiments about 200 micrometers or less, in some
- the composition of the present invention has been found to possess excellent mechanical properties.
- the composition may exhibit a Charpy unnotched impact strength greater than about 20 kJ/m 2 , in some embodiments from about 25 to about 100 kJ/m 2 , and in some embodiments, from about 30 to about 80 kJ/m 2 , measured at 23°C according to ISO Test No. 179-1 :2010 (technically equivalent to ASTM D256-10e1 ).
- the composition may also exhibit a Charpy notched impact strength greater than about 0.5 kJ/m 2 , in some embodiments from about 1 to about 20 kJ/m 2 , and in some embodiments, from about 5 to about 15 kJ/m 2 , measured at 23°C according to ISO Test No. 179-1 :2010 (technically equivalent to ASTM D256-10e1 ).
- the tensile and flexural mechanical properties are also good.
- the composition may exhibit a tensile strength of from about 20 to about 500 MPa, in some
- tensile break strain of about 1 % or more, in some embodiments from about 2% to about 15%, and in some embodiments, from about 3% to about 10%
- tensile modulus of from about 4,000 MPa to about 20,000 MPa, in some embodiments from about 5,000 MPa to about 18,000 MPa, and in some embodiments, from about 6,000 MPa to about 12,000 MPa.
- the tensile properties may be determined in accordance with ISO Test No. 527:2012 (technically equivalent to ASTM D638-14) at 23°C.
- the composition may also exhibit a flexural strength of from about 20 to about 500 MPa, in some
- the flexural properties may be determined in accordance with ISO Test No. 178:2010 (technically equivalent to ASTM D790-10) at 23°C.
- the molded part may also exhibit a deflection temperature under load (DTUL) of about 180°C or more, and in some embodiments, from about 190°C to about 280°C, as measured according to ASTM D648-07 (technically equivalent to ISO Test No. 75-2:2013) at a specified load of 1 .8 MPa.
- the Rockwell hardness of the part may also be about 25 or more, some embodiments about 30 or more, and in some embodiments, from about 35 to about 80, as determined in accordance with ASTM D785-08 (Scale M).
- the composition can also exhibit excellent antistatic behavior, particularly when an antistatic filler is included within the polymer composition as discussed above.
- antistatic behavior can be characterized by a relatively low surface and/or volume resistivity as determined in accordance with IEC 60093.
- the composition may exhibit a surface resistivity of about 1 x 10 15 ohms or less, in some embodiments about 1 x 10 14 ohms or less, in some embodiments from about 1 x 10 10 ohms to about 9 x 10 13 ohms, and in some embodiments, from about 1 x 10 11 to about 1 x 10 13 ohms.
- the molded part may also exhibit a volume resistivity of about 1 x 10 15 ohm-m or less, in some embodiments from about 1 x 10 9 ohm-m to about 9 x 10 14 ohm-m, and in some embodiments, from about 1 x 10 1 ° to about 5 x 10 14 ohm-m.
- a volume resistivity of about 1 x 10 15 ohm-m or less, in some embodiments from about 1 x 10 9 ohm-m to about 9 x 10 14 ohm-m, and in some embodiments, from about 1 x 10 1 ° to about 5 x 10 14 ohm-m.
- such antistatic behavior is by no means required.
- the composition may exhibit a relatively high surface resistivity, such as about 1 x 10 15 ohms or more, in some embodiments about 1 x 10 16 ohms or more, in some embodiments from about 1 x 10 17 ohms to about 9 x 10 30 ohms, and in some embodiments, from about 1 x 10 18 to about 1 x 10 26 ohms.
- a relatively high surface resistivity such as about 1 x 10 15 ohms or more, in some embodiments about 1 x 10 16 ohms or more, in some embodiments from about 1 x 10 17 ohms to about 9 x 10 30 ohms, and in some embodiments, from about 1 x 10 18 to about 1 x 10 26 ohms.
- Aromatic polymers typically constitute from about 20 wt.% to about
- the aromatic polymers are generally considered“high
- the aromatic polymer may have a glass transition temperature of about 100°C or more, in some embodiments about 120°C or more, in some embodiments from about 140°C to about 350°C, and in some embodiments, from about 150°C to about 320°C.
- the aromatic polymer may also have a melting temperature of about 200°C or more, in some embodiments from about 220°C to about 400°C, and in some embodiments, from about 240°C to about 380°C.
- the glass transition and melting temperatures may be determined as is well known in the art using differential scanning calorimetry ("DSC"), such as determined by ISO Test No. 11357-2:2013 (glass transition) and 11357-3:2011 (melting).
- the aromatic polymer can be substantially amorphous, semi- crystalline, or crystalline in nature.
- a suitable semi-crystalline aromatic polymer for instance, is an aromatic polyamide.
- Particularly suitable aromatic polyamides are those having a relatively high melting temperature, such as about 200°C or more, in some embodiments about 220°C or more, and in some embodiments, from about 240°C to about 320°C, as determined using differential scanning calorimetry according to ISO Test No. 11357.
- the glass transition temperature of aromatic polyamides is likewise generally from about 110°C to about 160°C.
- Aromatic polyamides typically contain repeating units held together by amide linkages (NH-CO) and are synthesized through the polycondensation of dicarboxylic acids (e.g., aromatic dicarboxylic acids), diamines (e.g., aliphatic diamines), etc.
- dicarboxylic acids e.g., aromatic dicarboxylic acids
- diamines e.g., aliphatic diamines
- the aromatic polyamide may contain aromatic repeating units derived from an aromatic dicarboxylic acid, such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7- naphthalenedicarboxylic acid, 1 ,4-naphthalenedicarboxylic acid, 1 ,4- phenylenedioxy-diacetic acid, 1 ,3-phenylenedioxy-diacetic acid, diphenic acid, 4,4'- oxydibenzoic acid, diphenylmethane-4, 4' -dicarboxylic acid, diphenylsulfone-4,4'- dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, etc., as well as combinations thereof.
- aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7- naphthalenedicarboxylic acid
- Terephthalic acid is particularly suitable.
- acid units may also be employed, such as aliphatic dicarboxylic acid units, polyfunctional carboxylic acid units, etc.
- the aromatic polyamide may also contain aliphatic repeating units derived from an aliphatic diamine, which typically has from 4 to 14 carbon atoms.
- diamines examples include linear aliphatic alkylenediamines, such as 1 ,4- tetramethylenediamine, 1 ,6-hexanediamine, 1 ,7-heptanediamine, 1 ,8- octanediamine, 1 ,9-nonanediamine, 1 ,10-decanediamine, 1 ,11 -undecanediamine,
- 1 ,12-dodecanediamine, etc. branched aliphatic alkylenediamines, such as 2- methyl-1 ,5-pentanediamine, 3-methyl-1 ,5 pentanediamine, 2, 2, 4-trimethyl-1 ,6- hexanediamine, 2,4,4-trimethyl-1 ,6-hexanediamine, 2,4-dimethyl-1 ,6- hexanediamine, 2-methyl-1 ,8-octanediamine, 5-methyl-1 ,9-nonanediamine, etc.; as well as combinations thereof.
- Repeating units derived from 1 ,9-nonanediamine and/or 2-methyl-1 ,8-octanediamine are particularly suitable.
- other diamine units may also be employed, such as alicyclic diamines, aromatic diamines, etc.
- Particularly suitable polyamides may include po!y(nonamethyiene terephthalamide) (RD9T), poly(nonamethylene terephthalamide/nonamethylene decanediamide) (PA9T/910), poly(nonamethylene terephthalamide/nonamethylene dodecanediamide) (PA9T/912), poly(nonamethylene terephthalamide/11 - aminoundecanamide) (PA9T/11 ), poly(nonamethylene terephthalamide/12- aminododecanamide) (PA9T/12), poly(decamethylene terephthalamide/11 - aminoundecanamide) (PA 10T/11 ), poly(decamethylene terephthalamide/12- aminododecanamide) (PA10T/12), poly(decamethylene terephthalamide/12- aminododecanamide) (PA10T/12), poly(decamethylene
- PA10T/46 poly(decamethylene terephthalamide/caprolactam) (PA10T/6), poly(decamethylene terephthalamide/hexamethylene hexanediamide) (PA1 OT/66), poly(dodecamethylene lerephthalamide/dodecamelhylene
- polyaryletherketone is semi-crystalline polymers with a relatively high melting temperature, such as from about 300°C to about 400°C, in some embodiments from about 310°C to about 390°C, and in some embodiments, from about 330°C to about 380°C.
- the glass transition temperature may likewise be from about 1 10°C to about 200°C.
- Particularly suitable polyaryletherketones are those that primarily include phenyl moieties in conjunction with ketone and/or ether moieties.
- Examples of such polymers include polyetheretherketone (“PEEK”), polyetherketone (“PEK”), polyetherketoneketone (“PEKK”), polyetherketoneetherketoneketone
- PEKEKK polyetheretherketoneketone
- PEEKK polyetheretherketoneketone
- substantially amorphous polymers may also be employed in the polymer composition that lack a distinct melting point
- Suitable amorphous polymers may include, for instance, polyphenylene oxide (“PPO”), aromatic polycarbonates, aromatic
- Aromatic polycarbonates typically have a glass transition temperature of from about 130°C to about 160°C and contain aromatic repeating units derived from one or more aromatic diols.
- aromatic diols are bisphenols, such as gem-bisphenols in which two phenols groups are attached to a single carbon atom of a bivalent connecting radical.
- bisphenols may include, for instance, such as 4,4'- isopropylidenediphenol (“bisphenol A”), 4,4'-ethylidenediphenol, 4,4'-(4-chloro-a- methylbenzylidene)diphenol, 4,4'cyclohexylidenediphenol, 4,4
- aromatic diol may be reacted with a phosgene.
- the phosgene may be a carbonyl chloride having the formula C(0)Cl2.
- An alternative route to the synthesis of an aromatic polycarbonate may involve the transesterification of the aromatic diol (e.g., bisphenol) with a diphenyl carbonate.
- crystalline polymers may also be employed in the polymer composition.
- Particularly suitable are liquid crystalline polymers, which have a high degree of crystallinity that enables them to effectively fill the small spaces of a mold.
- Liquid crystalline polymers are generally classified as“thermotropic” to the extent that they can possess a rod-like structure and exhibit a crystalline behavior in their molten state (e.g., thermotropic nematic state).
- the polymers have a relatively high melting temperature, such as from about 250°C to about 400°C, in some embodiments from about 280°C to about 390°C, and in some embodiments, from about 300°C to about 380°C.
- Such polymers may be formed from one or more types of repeating units as is known in the art.
- a liquid crystalline polymer may, for example, contain one or more aromatic ester repeating units, typically in an amount of from about 60 mol.% to about 99.9 mol.%, in some embodiments from about 70 mol.% to about 99.5 mol.%, and in some embodiments, from about 80 mol.% to about 99 mol.% of the polymer.
- the aromatic ester repeating units may be generally represented by the following Formula (I):
- ring B is a substituted or unsubstituted 6-membered aryl group (e.g., 1 ,4- phenylene or 1 ,3-phenylene), a substituted or unsubstituted 6-membered aryl group fused to a substituted or unsubstituted 5- or 6-membered aryl group (e.g., 2,6-naphthalene), or a substituted or unsubstituted 6-membered aryl group linked to a substituted or unsubstituted 5- or 6-membered aryl group (e.g., 4,4- biphenylene); and
- Yi and Y2 are independently 0, C(O), NH, C(0)HN, or NHC(O).
- Y1 and Y2 are C(O).
- aromatic ester repeating units may include, for instance, aromatic dicarboxylic repeating units (Y1 and Y2 in Formula I are C(O)), aromatic hydroxycarboxylic repeating units (Y1 is O and Y2 is C(O) in Formula I), as well as various
- Aromatic dicarboxylic repeating units may be employed that are derived from aromatic dicarboxylic acids, such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl ether-4, 4'-dicarboxylic acid, 1 ,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'- dicarboxybiphenyl, bis(4-carboxyphenyl)ether, bis(4-carboxyphenyl)butane, bis(4- carboxyphenyl)ethane, bis(3-carboxyphenyl)ether, bis(3-carboxyphenyl)ethane, etc., as well as alkyl, alkoxy, aryl and halogen substituents thereof, and
- aromatic dicarboxylic acids may include, for instance, terephthalic acid (“TA”), isophthalic acid (“IA”), and 2,6- naphthalenedicarboxylic acid (“NDA”).
- TA terephthalic acid
- IA isophthalic acid
- NDA 2,6- naphthalenedicarboxylic acid
- repeating units derived from aromatic dicarboxylic acids typically constitute from about 5 mol.% to about 60 mol.%, in some embodiments from about 10 mol.% to about 55 mol.%, and in some embodiments, from about 15 mol.% to about 50% of the polymer.
- Aromatic hydroxycarboxylic repeating units may also be employed that are derived from aromatic hydroxycarboxylic acids, such as, 4-hydroxybenzoic acid; 4-hydroxy-4'-biphenylcarboxylic acid; 2-hydroxy-6-naphthoic acid; 2-hydroxy- 5-naphthoic acid; 3-hydroxy-2-naphthoic acid; 2-hydroxy-3-naphthoic acid; 4'- hydroxyphenyl-4-benzoic acid; 3'-hydroxyphenyl-4-benzoic acid; 4'-hydroxyphenyl- 3-benzoic acid, etc., as well as alkyl, alkoxy, aryl and halogen substituents thereof, and combination thereof.
- Particularly suitable aromatic hydroxycarboxylic acids are 4-hydroxybenzoic acid (“HBA”) and 6-hydroxy-2-naphthoic acid (“HNA”).
- repeating units derived from hydroxycarboxylic acids typically constitute from about 10 mol.% to about 85 mol.%, in some embodiments from about 20 mol.% to about 80 mol.%, and in some embodiments, from about 25 mol.% to about 75% of the polymer.
- repeating units may also be employed in the polymer.
- repeating units may be employed that are derived from aromatic diols, such as hydroquinone, resorcinol, 2,6- dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1 ,6-dihydroxynaphthalene, 4,4'- dihydroxybiphenyl (or 4,4’-biphenol), 3,3'-dihydroxybiphenyl, 3,4'- dihydroxybiphenyl, 4,4'-dihydroxybiphenyl ether, bis(4-hydroxyphenyl)ethane, etc., as well as alkyl, alkoxy, aryl and halogen substituents thereof, and combinations thereof.
- aromatic diols may include, for instance,
- repeating units derived from aromatic diols typically constitute from about 1 mol.% to about 30 mol.%, in some embodiments from about 2 mol.% to about 25 mol.%, and in some embodiments, from about 5 mol.% to about 20% of the polymer.
- Repeating units may also be employed, such as those derived from aromatic amides (e.g., acetaminophen (“APAP”)) and/or aromatic amines (e.g., 4- aminophenol (“AP”), 3-aminophenol, 1 ,4-phenylenediamine, 1 ,3- phenylenediamine, etc.).
- aromatic amides e.g., APAP
- aromatic amines e.g., AP
- repeating units derived from aromatic amides (e.g., APAP) and/or aromatic amines (e.g., AP) typically constitute from about 0.1 mol.% to about 20 mol.%, in some embodiments from about 0.5 mol.% to about 15 mol.%, and in some embodiments, from about 1 mol.% to about 10% of the polymer.
- the polymer may contain one or more repeating units derived from non-aromatic monomers, such as aliphatic or cycloaliphatic hydroxycarboxylic acids, dicarboxylic acids, diols, amides, amines, etc.
- non-aromatic monomers such as aliphatic or cycloaliphatic hydroxycarboxylic acids, dicarboxylic acids, diols, amides, amines, etc.
- the polymer may be“wholly aromatic” in that it lacks repeating units derived from non-aromatic (e.g., aliphatic or cycloaliphatic) monomers.
- the liquid crystalline polymer may be a“low naphthenic” polymer to the extent that it contains a minimal content of repeating units derived from naphthenic hydroxycarboxylic acids and naphthenic dicarboxylic acids, such as naphthalene-2, 6-dicarboxylic acid (“NDA”), 6-hydroxy-
- HNA 2-naphthoic acid
- the total amount of repeating units derived from naphthenic hydroxycarboxylic and/or dicarboxylic acids is typically no more than 30 mol.%, in some embodiments no more than about 15 mol.%, in some embodiments no more than about 10 mol.%, in some embodiments no more than about 8 mol.%, and in some embodiments, from 0 mol.% to about 5 mol.% of the polymer (e.g., 0 mol.%).
- the resulting“low naphthenic” polymers are still capable of exhibiting good thermal and mechanical properties.
- the liquid crystalline polymer may be formed from repeating units derived from 4-hydroxybenzoic acid (“HBA”) and terephthalic acid (“TA”) and/or isophthalic acid (“ IA”), as well as various other optional constituents.
- the repeating units derived from 4-hydroxybenzoic acid (“HBA”) may constitute from about 10 mol.% to about 80 mol.%, in some embodiments from about 30 mol.% to about 75 mol.%, and in some embodiments, from about 45 mol.% to about 70% of the polymer.
- the repeating units derived from terephthalic acid (“TA”) and/or isophthalic acid (“IA”) may likewise constitute from about 5 mol.% to about 40 mol.%, in some embodiments from about 10 mol.% to about 35 mol.%, and in some embodiments, from about 15 mol.% to about 35% of the polymer.
- Repeating units may also be employed that are derived from 4,4’-biphenol (“BP”) and/or hydroquinone (“HQ”) in an amount from about 1 mol.% to about 30 mol.%, in some embodiments from about 2 mol.% to about 25 mol.%, and in some embodiments, from about 5 mol.% to about 20% of the polymer.
- repeating units may include those derived from 6- hydroxy-2-naphthoic acid (“HNA”), 2,6-naphthalenedicarboxylic acid (“NDA”), and/or acetaminophen (“APAP”).
- HNA 6- hydroxy-2-naphthoic acid
- NDA 2,6-naphthalenedicarboxylic acid
- APAP acetaminophen
- repeating units derived from HNA, NDA, and/or APAP may each constitute from about 1 mol.% to about 35 mol.%, in some embodiments from about 2 mol.% to about 30 mol.%, and in some embodiments, from about 3 mol.% to about 25 mol.% when employed.
- a tribological formulation is also employed in the polymer composition, typically in an amount of from about 1 to about 30 parts, in some embodiments from about 2 to about 15 parts, and in some embodiments, from about 4 to about 12 parts per 100 parts of aromatic polymer(s) employed in the polymer composition.
- the tribological formulation may constitute from about 1 wt.% to about 30 wt.%, in some embodiments from about 2 wt.% to about 25 wt.%, and in some embodiments, from about 4 wt.% to about 10 wt.% of the polymer composition.
- the tribological formulation generally contains a siloxane polymer that improves internal lubrication and that also helps to bolster the wear and friction properties of the composition encountering another surface.
- siloxane polymers typically constitute from about 0.1 to about 20 parts, in some
- siloxane polymers may generally be employed in the tribological formulation.
- the siloxane polymer may, for instance, encompass any polymer, co-polymer or oligomer that includes siloxane units in the backbone having the formula:
- R is independently hydrogen or substituted or unsubstituted hydrocarbon radicals
- r is 0, 1 , 2 or 3.
- radicals R include, for instance, alkyl, aryl, alkylaryl, alkenyl or alkynyl, or cycloalkyl groups, optionally substituted, and which may be interrupted by heteroatoms, i.e. , may contain heteroatom(s) in the carbon chains or rings.
- Suitable alkyl radicals may include, for instance, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl and tert-pentyl radicals, hexyl radicals (e.g., n-hexyl), heptyl radicals (e.g., n- heptyl), octyl radicals (e.g., n-octyl), isooctyl radicals (e.g., 2,2,4-trimethylpentyl radical), nonyl radicals (e.g., n-nonyl), decyl radicals (e.g., n-decyl), dodecyl radicals (e.g., n-dodecyl), octadecyl radical
- suitable cycloalkyl radicals may include cyclopentyl, cyclohexyl cycloheptyl radicals, methylcyclohexyl radicals, and so forth;
- suitable aryl radicals may include phenyl, biphenyl, naphthyl, anthryl, and phenanthryl radicals;
- suitable alkylaryl radicals may include o-, m- or p-tolyl radicals, xylyl radicals, ethylphenyl radicals, and so forth;
- suitable alkenyl or alkynyl radicals may include vinyl, 1- propenyl, 1-butenyl , 1-pentenyl, 5-hexenyl, butadienyl, hexadienyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, ethynyl, propargyl 1 -propynyl, and so forth.
- substituted hydrocarbon radicals are halogenated alkyl radicals (e.g.,
- the siloxane polymer includes alkyl radicals (e.g., methyl radicals) bonded to at least 70 mol % of the Si atoms and optionally vinyl and/or phenyl radicals bonded to from 0.001 to 30 mol % of the Si atoms.
- the siloxane polymer is also preferably composed predominantly of diorganosiloxane units.
- the end groups of the polyorganosiloxanes may be trialkylsiloxy groups, in particular the trimethylsiloxy radical or the dimethylvinylsiloxy radical. However, it is also possible for one or more of these alkyl groups to have been replaced by hydroxy groups or alkoxy groups, such as methoxy or ethoxy radicals.
- Particularly suitable examples of the siloxane polymer include, for instance, dimethylpolysiloxane,
- the siloxane polymer may also include a reactive functionality on at least a portion of the siloxane monomer units of the polymer, such as one or more of vinyl groups, hydroxyl groups, hydrides, isocyanate groups, epoxy groups, acid groups, halogen atoms, alkoxy groups (e.g., methoxy, ethoxy and propoxy), acyloxy groups (e.g., acetoxy and octanoyloxy), ketoximate groups (e.g., dimethylketoxime, methylketoxime and methylethylketoxime), amino groups(e.g., dimethylamino, diethylamino and butylamino), amido groups (e.g., N- methylacetamide and N-ethylacetamide), acid amido groups, amino-oxy groups, mercapto groups, alkenyloxy groups (e.g., vinyloxy, isopropenyloxy, and 1 -ethy
- the siloxane polymer typically has a relatively high molecular weight, which reduces the likelihood that it migrates or diffuses to the surface of the polymer composition and thus further minimizes the likelihood of phase separation.
- the siloxane polymer typically has a weight average molecular weight of about 100,000 grams per mole or more, in some embodiments about 200,000 grams per mole or more, and in some embodiments, from about 500,000 grams per mole to about 2,000,000 grams per mole.
- the siloxane polymer may also have a relative high kinematic viscosity, such as about 10,000 centistokes or more, in some embodiments about 30,000 centistokes or more, and in some embodiments, from about 50,000 to about 500,000 centistokes.
- silica particles may also be employed in combination with the siloxane polymer to help improve its ability to be dispersed within the composition.
- Such silica particles may, for instance, have a particle size of from about 5 nanometers to about 50 nanometers, a surface area of from about 50 square meters per gram (m 2 /g) to about 600 m 2 /g, and/or a density of from about 160 kilogram per cubic meter (kg/m 3 ) to about 190 kg/m 3 .
- the silica particles typically constitute from about 1 to about 100 parts, and in some some embodiments, from about 20 to about 60 parts by weight based on 100 parts by weight of the siloxane polymer.
- the silica particles can be combined with the siloxane polymer prior to addition of this mixture to the polymer composition.
- a mixture including an ultrahigh molecular weight polydimethylsiloxane and fumed silica can be incorporated in the polymer composition.
- Such a pre-formed mixture is available as Genioplast ® Pellet S from Wacker Chemie, AG.
- the tribological formulation may also contain other components that can help the resulting polymer composition to achieve a good combination of low friction and good wear resistance.
- the tribological formulation may also contain other components that can help the resulting polymer composition to achieve a good combination of low friction and good wear resistance.
- the resulting polymer composition may also contain other components that can help the resulting polymer composition to achieve a good combination of low friction and good wear resistance.
- the resulting polymer composition may also contain other components that can help the resulting polymer composition to achieve a good combination of low friction and good wear resistance.
- the resulting polymer composition may also contain other components that can help the resulting polymer composition to achieve a good combination of low friction and good wear resistance.
- tribological formulation may employ a fluorinated additive in combination with the siloxane polymer.
- the fluorinated additive can, among other things, improve the processing of the composition, such as by providing better mold filling, internal lubrication, mold release, etc.
- the weight ratio of the fluorinated additive to the siloxane polymer is typically from about 0.5 to about 12, in some embodiments from about 0.8 to about 10, and in some embodiments, from about 1 to about 6.
- the fluorinated additive may constitute from about 0.1 to about 20 parts, in some embodiments from about 0.5 to about 15 parts, and in some embodiments, from about 1 to about 10 parts per 100 parts of aromatic polymer(s) employed in the composition.
- the fluorinated additive may include a fluoropolymer, which contains a hydrocarbon backbone polymer in which some or all of the hydrogen atoms are substituted with fluorine atoms.
- the backbone polymer may polyolefinic and formed from fluorine-substituted, unsaturated olefin monomers.
- the fluoropolymer can be a homopolymer of such fluorine- substituted monomers or a copolymer of fluorine-substituted monomers or mixtures of fluorine-substituted monomers and non-fluorine-substituted
- fluoropolymer can also be substituted with other halogen atoms, such as chlorine and bromine atoms.
- Representative monomers suitable for forming fluoropolymers for use in this invention are tetrafluoroethylene, vinylidene fluoride, hexafluoropropylene,
- fluoropolymers include polytetrafluoroethylene, perfluoroalkylvinyl ether, poly(tetrafluoroethylene-co-perfluoroalkyvinylether), fluorinated ethylene- propylene copolymer, ethylene-tetrafluoroethylene copolymer, polyvinylidene fluoride, polychlorotrifluoroethylene, etc., as well as mixtures thereof.
- the fluorinated additive may contain only the fluoropolymer, or it may also include other ingredients, such as those that aid in its ability to be uniformly dispersed within the polymer composition.
- the fluorinated additive may include a fluoropolymer in combination with a plurality of carrier particles. In such embodiments, for instance, the
- Silicate particles are particularly suitable for this purpose, such as talc (Mg3SUOio(OH)2), halloysite (AI 2 Si20 5 (0H) 4 ), kaolinite (AI 2 Si20 5 (0H) 4 ), illite ((K, H 3 0)(AI, Mg, Fe) 2
- Mg)2SUOio(OH)277H20 vermiculite ((MgFe, AI)s(AI, Si)40io(OH) 2 -4H 2 0), palygorskite ((Mg, AI)2SUOio(OFI)-4(Fl20)), pyrophyllite (Al2SUOio(OFI)2), calcium silicate, aluminum silicate, mica, diatomaceous earth, wollastonite, and so forth.
- Mica for instance, may be a particularly suitable mineral for use in the present invention. There are several chemically distinct mica species with considerable variance in geologic occurrence, but all have essentially the same crystal structure.
- the term“mica” is meant to generically include any of these species, such as muscovite (KAl2(AISi3)Oio(OFI)2), biotite
- the carrier particles may have an average particle size of from about 5 to about 50 micrometers, and in some embodiments, from about 10 to 20 micrometers. If desired, the carrier particles may also be in the shape of plate-like particles in that the ratio of its major axis to thickness is 2 or more.
- an inorganic filler may be employed for improving certain properties of the polymer composition.
- the present inventor has discovered that the use of inorganic fillers with a certain hardness value can improve the mechanical strength, adhesive strength, and surface smoothness of a part containing the composition.
- the resulting polymer composition may also be able to achieve less delamination of the polymer skin layer, which enables it to be uniquely suited for very small parts.
- the inorganic filler may be employed in the polymer composition in an amount of from about 10 to about 95 parts, in some embodiments from about 20 to about 90 parts, and in some embodiments, from about 50 to about 85 parts by weight per 100 parts of the aromatic polymer(s) employed in the polymer composition.
- the inorganic filler may constitute from about 10 wt.% to about 70 wt.%, in some embodiments from about 20 wt.% to about 60 wt.%, and in some embodiments, from about 30 wt.% to about 60 wt.% of the polymer composition.
- inorganic filler particles may be employed having a certain hardness value to help improve the surface properties of the composition.
- the hardness values may be about 2.5 or more, in some embodiments about 3.0 or more, in some embodiments from about 3.0 to about 11.0, in some embodiments from about 3.5 to about 11.0, and in some embodiments, from about 4.5 to about 6.5 based on the Mohs hardness scale.
- Such particles may include, for instance, carbonates, such as calcium carbonate (CaC03, Mohs hardness of 3.0) or a copper carbonate hydroxide
- phosphates such as calcium pyrophosphate ((Ca2P207,
- Mohs hardness of 5.0 anhydrous dicalcium phosphate (CaFIP04, Mohs hardness of 3.5), or hydrated aluminum phosphate (AIPO4 2FI2O, Mohs hardness of 4.5); silicates, such as silica (S1O2, Mohs hardness of 6.0), potassium aluminum silicate
- borates such as calcium borosilicate hydroxide (Ca2B5Si09(0FI)5, Mohs hardness of 3.5); alumina (AIO2, Mohs hardness of 10.0); sulfates, such as calcium sulfate (CaS04, Mohs hardness of 3.5) or barium sulfate (BaS04, Mohs hardness of from 3 to 3.5); and so forth, as well as combinations thereof.
- borates such as calcium borosilicate hydroxide (Ca2B5Si09(0FI)5, Mohs hardness of 3.5); alumina (AIO2, Mohs hardness of 10.0
- sulfates such as calcium sulfate (CaS04, Mohs hardness of 3.5) or barium sulfate (BaS04, Mohs hardness of from 3 to 3.5); and so forth, as well as combinations thereof.
- the inorganic particles When employed, the inorganic particles typically have a median size (e.g., diameter) of from about 0.1 to about 35 micrometers, in some embodiments from about 2 to about 20 micrometers, in some embodiments from about 3 to about 15 micrometers, and in some embodiments, from about 7 to about 12 micrometers, such as determined using laser diffraction techniques in accordance with ISO 13320:2009 (e.g., with a Horiba LA-960 particle size distribution analyzer).
- the filler inorganic particles may also have a narrow size distribution. That is, at least about 70% by volume of the particles, in some embodiments at least about 80% by volume of the particles, and in some embodiments, at least about 90% by volume of the particles may have a size within the ranges noted above.
- the inorganic filler may also be fibers derived from a material having the desired hardness value.
- fibers for this purpose include those derived from minerals, including silicates, such as neosilicates, sorosilicates, inosilicates (e.g., calcium inosilicates, such as wollastonite; calcium magnesium inosilicates, such as tremolite; calcium magnesium iron inosilicates, such as actinolite; magnesium iron inosilicates, such as anthophyllite; etc.), phyllosilicates
- silicates such as neosilicates, sorosilicates, inosilicates (e.g., calcium inosilicates, such as wollastonite; calcium magnesium inosilicates, such as tremolite; calcium magnesium iron inosilicates, such as actinolite; magnesium iron inosilicates, such as anthophyllite; etc.
- phyllosilicates such as palygorskite
- tectosilicates etc.
- sulfates such as calcium sulfates (e.g., dehydrated or anhydrous gypsum); mineral wools
- fibers derived from inosilicates such as wollastonite (Mohs hardness of 4.5 to 5.0), which are commercially available from Nyco Minerals under the trade designation NYGLOS®
- the mineral fibers may have a median width (e.g., diameter) of from about 0.1 to about 35 micrometers, in some embodiments from about 2 to about 20 micrometers, in some
- the mineral fibers may also have a narrow size distribution. That is, at least about 70% by volume of the fibers, in some embodiments at least about 80% by volume of the fibers, and in some
- At least about 90% by volume of the fibers may have a size within the ranges noted above.
- the mineral fibers may also have an aspect ratio of from about 1 to about 50, in some embodiments from about 2 to about 20, and in some embodiments, from about 4 to about 15.
- the volume average length of such mineral fibers may, for example, range from about 1 to about 200 micrometers, in some embodiments from about 2 to about 150 micrometers, in some embodiments from about 5 to about 100 micrometers, and in some embodiments, from about 10 to about 50 micrometers.
- an impact modifier may also be employed in the polymer composition to help improve the impact strength and flexibility of the polymer composition.
- the present inventor has discovered that the impact modifier can actually make the surface of a molded part smoother and minimize the likelihood that a skin layer is peeled therefrom during use.
- the impact modifier typically constitutes from about 0.1 to about 20 parts, in some embodiments from about 0.2 to about 10 parts, and in some embodiments, from about 0.5 to about 5 parts by weight per 100 parts of the aromatic polymer(s) employed in the polymer composition.
- the impact modifier may constitute from about 0.1 wt.% to about 10 wt.%, in some embodiments from about 0.2 wt.% to about 8 wt.%, and in some embodiments, from about 0.5 wt.% to about 4 wt.% of the polymer composition.
- One particularly suitable type of impact modifier may include, for instance, an olefin copolymer that is“epoxy-functionalized” in that it contains, on average, two or more epoxy functional groups per molecule.
- the copolymer generally contains an olefinic monomeric unit that is derived from one or more a- olefins. Examples of such monomers include, for instance, linear and/or branched a-olefins having from 2 to 20 carbon atoms and typically from 2 to 8 carbon atoms.
- Specific examples include ethylene, propylene, 1 -butene; 3-methyl-1 -butene; 3,3- dimethyl-1 -butene; 1 -pentene; 1 -pentene with one or more methyl, ethyl or propyl substituents; 1 -hexene with one or more methyl, ethyl or propyl substituents; 1- heptene with one or more methyl, ethyl or propyl substituents; 1-octene with one or more methyl, ethyl or propyl substituents; 1 -nonene with one or more methyl, ethyl or propyl substituents; ethyl, methyl or dimethyl-substituted 1 -decene; 1 -dodecene; and styrene.
- a-olefin monomers are ethylene and propylene.
- the copolymer may also contain an epoxy-functional monomeric unit.
- One example of such a unit is an epoxy-functional (meth)acrylic monomeric component.
- the term“(meth)acrylic” includes acrylic and methacrylic
- suitable epoxy-functional (meth)acrylic monomers may include, but are not limited to, those containing 1 ,2-epoxy groups, such as glycidyl acrylate and glycidyl methacrylate.
- suitable epoxy-functional monomers include allyl glycidyl ether, glycidyl ethacrylate, and glycidyl itoconate.
- Other suitable monomers may also be employed to help achieve the desired molecular weight.
- the copolymer may also contain other monomeric units as is known in the art.
- another suitable monomer may include a
- (meth)acrylic monomers may include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, s-butyl acrylate, i-butyl acrylate, t-butyl acrylate, n-amyl acrylate, i-amyl acrylate, isobornyl acrylate, n-hexyl acrylate, 2- ethylbutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, methylcyclohexyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, n-propyl
- the copolymer may be a terpolymer formed from an epoxy-functional (meth)acrylic monomeric component, a-olefin monomeric component, and non-epoxy functional (meth)acrylic monomeric component.
- the copolymer may, for instance, be poly(ethylene-co-butylacrylate-co-glycidyl methacrylate), which has the following structure:
- the relative portion of the monomeric component(s) may be selected to achieve a balance between epoxy-reactivity and melt flow rate. More
- epoxy-functional (meth)acrylic can result in good reactivity with the matrix polymer, but too high of a content may reduce the melt flow rate to such an extent that the copolymer adversely impacts the melt strength of the polymer blend.
- the epoxy-functional (meth)acrylic in most embodiments, can result in good reactivity with the matrix polymer, but too high of a content may reduce the melt flow rate to such an extent that the copolymer adversely impacts the melt strength of the polymer blend.
- the a-olefin monomer(s) may likewise constitute from about 55 wt.% to about 95 wt.%, in some embodiments from about 60 wt.% to about 90 wt.%, and in some embodiments, from about 65 wt.% to about 85 wt.% of the copolymer.
- other monomeric components may constitute from about 5 wt.% to about 35 wt.%, in some embodiments from about 8 wt.% to about 30 wt.%, and in some embodiments, from about 10 wt.% to about 25 wt.% of the copolymer.
- the result melt flow rate is typically from about 1 to about 30 grams per 10 minutes (“g/10 min”), in some embodiments from about 2 to about 20 g/10 min, and in some embodiments, from about 3 to about 15 g/10 min, as determined in accordance with ASTM D1238-13 at a load of 2.16 kg and temperature of 190°C.
- LOTADER® AX8840 One example of a suitable epoxy-functionalized copolymer that may be used in the present invention is commercially available from Arkema under the name LOTADER® AX8840.
- LOTADER® AX8840 for instance, has a melt flow rate of 5 g/10 min and has a glycidyl methacrylate monomer content of 8 wt.%.
- ELVALOY® PTW is a terpolymer of ethylene, butyl acrylate, and glycidyl methacrylate and has a melt flow rate of 12 g/10 min and a glycidyl methacrylate monomer content of 4 wt.% to 5 wt.%.
- An antistatic filler may also be employed in the polymer composition to help reduce the tendency to create a static electric charge during a molding operation, transportation, collection, assembly, etc.
- Such fillers when employed, typically constitute from about 0.1 to about 20 parts, in some embodiments from about 0.2 to about 10 parts, and in some embodiments, from about 0.5 to about 5 parts by weight per 100 parts of the aromatic polymer(s) employed in the polymer composition.
- the antistatic filler may constitute from about 0.1 wt.% to about 10 wt.%, in some embodiments from about 0.2 wt.% to about 8 wt.%, and in some embodiments, from about 0.5 wt.% to about 4 wt.% of the polymer composition.
- antistatic fillers may generally be employed in the polymer composition to help improve its antistatic characteristics.
- suitable antistatic fillers may include, for instance, metal particles (e.g., aluminum flakes), metal fibers, carbon particles (e.g., graphite, expanded graphite, grapheme, carbon black, graphitized carbon black, etc.), carbon nanotubes, carbon fibers, and so forth.
- Carbon fibers and carbon particles are particularly suitable.
- suitable carbon fibers may include pitch- based carbon (e.g., tar pitch), polyacrylonitrile-based carbon, metal-coated carbon, etc.
- the carbon fibers have a high purity in that they possess a relatively high carbon content, such as a carbon content of about 85 wt.% or more, in some embodiments about 90 wt.% or more, and in some embodiments, about 93 wt.% or more.
- the carbon content can be at least about 94% wt., such as at least about 95% wt., such as at least about 96% wt., such at least about 97% wt., such as even at least about 98% wt.
- the carbon purity is generally less than 100 wt.%, such as less than about 99 wt.%.
- the density of the carbon fibers is typically from about 0.5 to about 3.0 g/cm 3 , in some embodiments from about 1.0 to about 2.5 g/cm 3 , and in some embodiments, from about 1.5 to about 2.0 g/cm 3 .
- the carbon fibers are incorporated into the matrix with minimal fiber breakage.
- the volume average length of the fibers after molding can generally be from about 0.1 mm to about 1 mm even when using a fiber having an initial length of about 3 mm.
- the average length and distribution of the carbon fibers can also be selectively controlled in the final polymer composition to achieve a better connection and electrical pathway within the liquid crystalline polymer matrix.
- the average diameter of the fibers can be from about 0.5 to about 30 micrometers, in some embodiments from about 1 to about 20 micrometers, and in some embodiments, from about 3 to about 15 micrometers.
- the carbon fibers may be at least partially coated with a sizing agent that increases the compatibility of the carbon fibers with the liquid crystalline polymer.
- the sizing agent may be stable so that it does not thermally degrade at temperatures at which the liquid crystalline polymer is molded.
- the sizing agent may include a polymer, such as an aromatic polymer.
- the aromatic polymer may have a thermal decomposition temperature of greater than about 300°C, such as greater than about 350°C, such as greater than about 400°C.
- the thermal decomposition temperature of a material is the temperature at which the material losses 5% of its mass during thermogravimeteric analysis as determined in accordance with ASTM Test E 1131 (or ISO Test 11358).
- the sizing agent can also have a relatively high glass transition temperature.
- the glass transition temperature of the sizing agent can be greater than about 300°C, such as greater than about 350°C, such as greater than about 400°C.
- Particular examples of sizing agents include polyimide polymers, aromatic polyester polymers including wholly aromatic polyester polymers, and high temperature epoxy polymers.
- the sizing agent may include a liquid crystalline polymer.
- the sizing agent can be present on the fibers in an amount of at least about 0.1 % wt., such as in an amount of at least 0.2% wt., such as in an amount of at least about 0.1 % wt.
- the sizing agent is generally present in an amount less than about 5% wt., such as in an amount of less than about 3% wt.
- Another suitable antistatic filler is an ionic liquid.
- the ionic liquid can also exist in liquid form during melt processing, which allows it to be more uniformly blended within the polymer matrix. This improves electrical connectivity and thereby enhances the ability of the composition to rapidly dissipate static electric charges from its surface.
- the ionic liquid is generally a salt that has a low enough melting temperature so that it can be in the form of a liquid when melt processed with the liquid crystalline polymer.
- the melting temperature of the ionic liquid may be about 400°C or less, in some embodiments about 350°C or less, in some embodiments from about 1 °C to about 100°C, and in some embodiments, from about 5°C to about 50°C.
- the salt contains a cationic species and counterion.
- the cationic species contains a compound having at least one heteroatom (e.g., nitrogen or phosphorous) as a“cationic center.” Examples of such heteroatom ic compounds include, for instance, quaternary oniums having the following structures:
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are independently selected from the group consisting of hydrogen; substituted or unsubstituted C1-C10 alkyl groups (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n- pentyl, etc.); substituted or unsubstituted C3-C14 cycloalkyl groups (e.g., adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclooctyl, cyclohexenyl, etc.); substituted or unsubstituted C1-C10 alkenyl groups (e.g., ethylene, propylene, 2- methypropylene, pentylene, etc.); substituted or
- the cationic species may be an ammonium compound having the structure N + R 1 R 2 R 3 R 4 , wherein R 1 , R 2 , and/or R 3 are independently a C1-C6 alkyl
- the cationic component may be tri- butylmethylammonium, wherein R 1 , R 2 , and R 3 are butyl and R 4 is methyl.
- Suitable counterions for the cationic species may include, for example, halogens (e.g., chloride, bromide, iodide, etc.); sulfates or sulfonates
- borates e.g., tetrafluoroborate, tetracyanoborate, bis[oxalato]borate, bis[salicylato]borate, etc.
- phosphates or phosphinates e.g., hexafluorophosphate, diethylphosphate, bis(pentafluoroethyl)phosphinate, tris(pentafluoroethyl)-trifluorophosphate, tris(nonafluorobutyl)trifluorophosphate, etc.
- antimonates e.g., hexafluoroantimonate
- aluminates e.g.,
- fatty acid carboxylates e.g., oleate, isostearate,
- hydrophobic counterions may include, for instance,
- a wide variety of additional additives can also be included in the polymer composition, such as lubricants, thermally conductive fillers, pigments, antioxidants, stabilizers, surfactants, waxes, flame retardants, anti-drip additives, and other materials added to enhance properties and processability.
- Lubricants for example, may be employed in the polymer composition that are capable of withstanding the processing conditions of the liquid crystalline polymer without substantial decomposition. Examples of such lubricants include fatty acids esters, the salts thereof, esters, fatty acid amides, organic phosphate esters, and hydrocarbon waxes of the type commonly used as lubricants in the processing of engineering plastic materials, including mixtures thereof.
- Suitable fatty acids typically have a backbone carbon chain of from about 12 to about 60 carbon atoms, such as myristic acid, palmitic acid, stearic acid, arachic acid, montanic acid, octadecinic acid, parinric acid, and so forth.
- Suitable esters include fatty acid esters, fatty alcohol esters, wax esters, glycerol esters, glycol esters and complex esters.
- Fatty acid amides include fatty primary amides, fatty secondary amides, methylene and ethylene bisamides and alkanolamides such as, for example, palmitic acid amide, stearic acid amide, oleic acid amide, N,N'- ethylenebisstearamide and so forth.
- the metal salts of fatty acids such as calcium stearate, zinc stearate, magnesium stearate, and so forth;
- hydrocarbon waxes including paraffin waxes, polyolefin and oxidized polyolefin waxes, and microcrystalline waxes.
- Particularly suitable lubricants are acids, salts, or amides of stearic acid, such as pentaerythritol tetrastearate, calcium stearate, or
- the lubricant(s) typically constitute from about 0.05 wt.% to about 1.5 wt.%, and in some embodiments, from about
- one beneficial aspect of the present invention is that good mechanical properties may be achieved without adversely impacting the
- the polymer composition remains substantially free of conventional fibrous fillers, such as glass fibers.
- such fibers typically constitute no more than about 10 wt.%, in some embodiments no more than about 5 wt.%, and in some
- the aromatic polymer, tribological formulation, and other optional additives may be melt processed or blended together.
- the components may be supplied separately or in combination to an extruder that includes at least one screw rotatably mounted and received within a barrel (e.g., cylindrical barrel) and may define a feed section and a melting section located downstream from the feed section along the length of the screw.
- the extruder may be a single screw or twin screw extruder.
- the speed of the screw may be selected to achieve the desired residence time, shear rate, melt processing temperature, etc.
- the screw speed may range from about 50 to about 800 revolutions per minute (“rpm”), in some embodiments from about 70 to about 150 rpm, and in some embodiments, from about 80 to about 120 rpm.
- the apparent shear rate during melt blending may also range from about 100 seconds 1 to about 10,000 seconds -1 , in some embodiments from about 500 seconds 1 to about 5000 seconds 1 , and in some embodiments, from about 800 seconds 1 to about 1200 seconds 1 .
- the apparent shear rate is equal to 4Q/nR 3 , where Q is the
- volumetric flow rate (“m 3 /s”) of the polymer melt and R is the radius (“m”) of the capillary (e.g., extruder die) through which the melted polymer flows.
- the melt viscosity of the polymer composition may be low enough so that it can readily flow into the cavity of a mold having small dimensions.
- the polymer composition may have a melt viscosity of from about 1 to about 200 Pa-s, in some embodiments from about 5 to about 180 Pa-s, in some embodiments from about 10 to about 150 Pa-s, and in some embodiments, from about 60 to about 120 Pa-s, determined at a shear rate of 1000 seconds 1 .
- Melt viscosity may be determined in accordance with ISO Test No. 11443:2005 at a temperature that is
- Shaped parts may be formed from the polymer composition using a variety of different techniques. Suitable techniques may include, for instance, injection molding, low-pressure injection molding, extrusion compression molding, gas injection molding, foam injection molding, low-pressure gas injection molding, low-pressure foam injection molding, gas extrusion compression molding, foam extrusion compression molding, extrusion molding, foam extrusion molding, compression molding, foam compression molding, gas compression molding, etc.
- an injection molding system may be employed that includes a mold within which the polymer composition may be injected. The time inside the injector may be controlled and optimized so that polymer matrix is not pre-solidified. When the cycle time is reached and the barrel is full for discharge, a piston may be used to inject the composition to the mold cavity.
- Compression molding systems may also be employed. As with injection molding, the shaping of the polymer composition into the desired article also occurs within a mold.
- the composition may be placed into the compression mold using any known technique, such as by being picked up by an automated robot arm.
- the temperature of the mold may be maintained at or above the solidification temperature of the polymer matrix for a desired time period to allow for solidification.
- the molded product may then be solidified by bringing it to a temperature below that of the melting temperature.
- the resulting product may be de-molded.
- the cycle time for each molding process may be adjusted to suit the polymer matrix, to achieve sufficient bonding, and to enhance overall process productivity.
- relatively thin shaped parts e.g., injection molded parts
- injection molded parts may have a thickness of about 10 millimeters or less, in some embodiments about 5 millimeters or less, and in some embodiments, from about 0.2 to about 4 millimeters (e.g., 0.3 or 3 millimeters).
- a relatively high“spiral flow length” can be achieved.
- the term“spiral flow length” generally refers to the length reached by the flow of the composition in a spiral flow channel when it is injected at constant injection temperature and injection pressure from a central gate of a mold in which the spiral flow channel is formed.
- the spiral flow length may, for instance, be about 15 millimeter or more, in some embodiments about 20 millimeters or more, in some embodiments about 22 millimeters or more, and in some embodiments, from about 25 to about 80 millimeters, as determined in accordance with ASTM D3121-09 at a barrel temperature of 230°C, molding temperature of 40°C to 60°C, and a maximum injection pressure of 860 bar.
- the polymer composition can also remain dimensionally stable when shaped into a part, and thus exhibit a relatively low degree of warpage.
- the degree of warpage may be characterized by low“flatness values” as determined by the test described in more detail below. More particularly, the polymer composition may exhibit a flatness value of about 1 millimeter or less, in some embodiments about 0.8 millimeters or less, and in some embodiments, from about 0.1 to about 0.7 millimeters.
- the composition may also maintain such a low warpage even after being conditioned at high temperatures and humidity levels (e.g., 85°C and 85% relative humidity) for a substantial period of time (e.g., 72 hours).
- the polymer composition may still exhibit a flatness value of about 2 millimeters or less, in some embodiments about 1.5 millimeters or less, and in some embodiments, from about 0.1 to about 1.2 millimeters.
- the polymer composition can be employed in lighting assemblies, battery systems, sensors and electronic components, portable electronic devices such as smart phones, MP3 players, mobile phones, computers, televisions, automotive parts, etc.
- the polymer composition may be employed in a camera module, such as those commonly employed in wireless communication devices (e.g., cellular telephone).
- the camera module may employ a base, carrier assembly mounted on the base, a cover mounted on the carrier assembly, etc.
- the base may have a thickness of about 500 micrometers or less, in some embodiments from about 10 to about 450 micrometers, and in some embodiments, from about 20 to about 400 micrometers.
- the carrier assembly may have a wall thickness of about 500 micrometers or less, in some embodiments from about 10 to about 450 micrometers, and in some embodiments, from about 20 to about 400 micrometers.
- a camera module 500 contains a carrier assembly 504 that overlies a base 506.
- the carrier assembly 504 may have any of a variety of configurations as is known in the art.
- the carrier assembly 504 may contain a hollow barrel that houses one or more lenses 604, which are in communication with an image sensor 602 positioned on the main board 508 and controlled by a circuit 601.
- the barrel may have any of a variety of shapes, such as rectangular, cylindrical, etc.
- the barrel may be formed from the polymer composition of the present invention and have a wall thickness within the ranges noted above. It should be understood that other parts of the camera module may also be formed from the polymer composition of the present invention.
- a cover may overly the carrier assembly 504 that includes, for example, a substrate 510 (e.g., film) and/or thermal insulating cap 502. In some embodiments, the substrate 510 and/or cap 502 may also be formed from the polymer composition.
- the degree of friction generated by a sample can be characterized by the average dynamic coefficient of friction (dimensionless) as determined according to VDA 230-206:2007 using a SSP-03 machine (Stick Slip test). Likewise, the degree of wear of a sample testing may also be determined in accordance with VDA 230-206:2007. More particularly, ball-shape specimens and plate shape specimens are prepared using a polymer product via injection molding process. The ball specimens is 0.5 inches in diameter. The plate specimen is obtained from middle part of ISO tensile bar by cutting two end areas of the tensile bars. The plate specimen is fixed on sample holder, and the ball specimen is moved in contact with the plate specimens at 150 mm/s and 15 N force. After 1000 cycles, the dynamic coefficient of friction is obtained. The depth of wear is obtained from ball specimens by measuring diameter of worn-out ball area. Based on the diameter of the worn-out area, the depth of worn-out the ball specimen is calculated and obtained.
- melt Viscosity The melt viscosity (Pa-s) may be determined in accordance with ISO Test No. 11443:2005 at a shear rate of 1000 s _1 and temperature 15°C above the melting temperature (e.g., 350°C) using a Dynisco LCR7001 capillary rheometer.
- the rheometer orifice (die) had a diameter of 1 mm, length of 20 mm, L/D ratio of 20.1 , and an entrance angle of 180°.
- the diameter of the barrel was 9.55 mm + 0.005 mm and the length of the rod was 233.4 mm.
- Tm The melting temperature (“Tm”) may be determined by differential scanning calorimetry (“DSC”) as is known in the art.
- the melting temperature is the differential scanning calorimetry (DSC) peak melt temperature as determined by ISO Test No. 11357-2:2013. Under the DSC procedure, samples were heated and cooled at 20°C per minute as stated in ISO Standard 10350 using DSC measurements conducted on a TA Q2000
- Deflection Temperature Under Load The deflection under load temperature may be determined in accordance with ISO Test No. 75-2:2013 (technically equivalent to ASTM D648-07). More particularly, a test strip sample having a length of 80 mm, thickness of 10 mm, and width of 4 mm may be subjected to an edgewise three-point bending test in which the specified load (maximum outer fibers stress) was 1.8 Megapascals. The specimen may be lowered into a silicone oil bath where the temperature is raised at 2°C per minute until it deflects 0.25 mm (0.32 mm for ISO Test No. 75-2:2013).
- Tensile Modulus, Tensile Stress, and Tensile Elongation Tensile properties may be tested according to ISO Test No. 527:2012 (technically equivalent to ASTM D638-14). Modulus and strength measurements may be made on the same test strip sample having a length of 80 mm, thickness of 10 mm, and width of 4 mm. The testing temperature may be 23°C, and the testing speeds may be 1 or 5 mm/min.
- Flexural Modulus and Flexural Stress Flexural properties may be tested according to ISO Test No. 178:2010 (technically equivalent to ASTM D790-10). This test may be performed on a 64 mm support span. Tests may be run on the center portions of uncut ISO 3167 multi-purpose bars. The testing temperature may be 23°C and the testing speed may be 2 mm/min.
- Unotched and Notched Charpy Impact Strength Charpy properties may be tested according to ISO Test No. ISO 179-1 :2010) (technically equivalent to ASTM D256-10, Method B). This test may be run using a Type 1 specimen size (length of 80 mm, width of 10 mm, and thickness of 4 mm). When testing the notched impact strength, the notch may be a Type A notch (0.25 mm base radius). Specimens may be cut from the center of a multi-purpose bar using a single tooth milling machine. The testing temperature may be 23°C.
- Rockwell hardness is a measure of the indentation resistance of a material and may be determined in accordance with ASTM D785-08 (Scale M). Testing is performed by first forcing a steel ball indentor into the surface of a material using a specified minor load. The load is then increased to a specified major load and decreased back to the original minor load. The Rockwell hardness is a measure of the net increase in depth of the indentor, and is calculated by subtracting the penetration divided by the scale division from 130.
- the surface and volume resistivity values are generally determined in accordance with IEC 60093 (similar to ASTM D257-07). According to this procedure, a standard specimen (e.g., 1 meter cube) is placed between two electrodes. A voltage is applied for sixty (60) seconds and the resistance is measured. The surface resistivity is the quotient of the potential gradient (in V/m) and the current per unit of electrode length (in A/m), and generally represents the resistance to leakage current along the surface of an insulating material.
- volume resistivity is also determined as the ratio of the potential gradient parallel to the current in a material to the current density. In SI units, volume resistivity is numerically equal to the direct-current resistance between opposite faces of a one- meter cube of the material (ohm-m).
- Weldline Strength The weldline strength may be determined by first forming an injection molded compact camera module from a polymer composition sample as is well known in the art. Once formed, the compact camera module may be placed on a sample holder. The weldline of the module may be subjected to a tensile force by a rod moving at a speed of 5.08 millimeters per minute. The maximum force at break (kgf) may be recorded as an estimate of the weldline strength.
- Spiral Flow Length generally refers to the length reached by the flow of the composition in a spiral flow channel
- the spiral flow length may be determined in accordance with ASTM D3121 -09 at a barrel temperature of 230°C, molding temperature of 40°C to 60°C, and a maximum injection pressure of 860 bar.
- the flatness value (warpage) of an LGA connector sample may be measured using an OGP Smartscope Quest 300 Optical
- XYZ Measurements may be taken across the specimen starting with X and Y values corresponding to 5, 22.5, 50, 57.5 and 75 mm. Z values may be normalized so that the minimum Z value corresponded to a height of zero. The flatness value is calculated as the average of the 25 normalized Z values.
- Samples 1 -6 are formed from various percentages of a liquid crystalline polymer, barium sulfate, impact modifier (Lotader® 8840), tribological formulation, black color masterbatch, and antistatic filler, as indicated in Table 1 below.
- the tribological formulation includes a combination of a high molecular weight siloxane polymer (Genioplast® Pellet S) and a fluorinated additive (Thor
- the black color masterbatch contains 80 wt.% liquid crystalline polymer and 20 wt.% carbon black.
- the antistatic filler is an ionic liquid— i.e. , tri-n- butylmethylammonium bis(trifluoromethanesulfonyl)-imide (FC-4400 from 3M).
- the liquid crystalline polymer (LCP 1 ) in Samples 1 -4 is formed from FIBA, HNA, TA, BP, and APAP, such as described in U.S. Patent No. 5,508,374 to Lee et al. while the liquid crystalline polymer (LCP 2) in Samples 5-6 is formed from HBA, HNA, and TA. Compounding is performed using an 18-mm single screw extruder. Parts are injection molded the samples into plaques (60 mm x 60 mm).
- Samples 7-12 are formed from various percentages of a liquid crystalline polymer, inorganic filler (barium sulfate or mica), impact modifier (Lotader® 8840), tribological formulation, and black color masterbatch, as indicated in Table 3 below.
- the tribological formulation includes a combination of a high molecular weight siloxane polymer (Genioplast® Pellet S) and a fluorinated additive (KT 300M PTFE).
- the black color masterbatch contains 80 wt.% liquid crystalline polymer and 20 wt.% carbon black.
- the liquid crystalline polymer (LCP 1 ) in Samples 10-12 is formed from HBA, HNA, TA, BP, and APAP, such as described in U.S. Patent No. 5,508,374 to Lee, et al, while the liquid crystalline polymer (LCP 2) in Samples 7-9 is formed from HBA, HNA, and TA.
- Compounding is performed using an 18-mm single screw extruder. Parts are injection molded the samples into plaques (60 mm x 60 mm).
- Samples 7-12 are also tested for thermal, mechanical, and wear properties. The results are set forth below in Table 4.
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Abstract
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| Application Number | Priority Date | Filing Date | Title |
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| JP2020531116A JP7372915B2 (en) | 2017-12-05 | 2018-11-28 | Aromatic polymer composition for use in camera modules |
| KR1020207019356A KR102627886B1 (en) | 2017-12-05 | 2018-11-28 | Aromatic polymer compositions for use in camera modules |
| CN201880075961.5A CN111417681B (en) | 2017-12-05 | 2018-11-28 | Aromatic polymer composition for camera module |
| JP2023125237A JP7659598B2 (en) | 2017-12-05 | 2023-08-01 | Aromatic polymer compositions for use in camera modules |
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| US201762594603P | 2017-12-05 | 2017-12-05 | |
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| WO2019112847A1 (en) * | 2017-12-05 | 2019-06-13 | Ticona Llc | Aromatic polymer composition for use in a camera module |
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| US11086200B2 (en) | 2019-03-20 | 2021-08-10 | Ticona Llc | Polymer composition for use in a camera module |
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- 2018-11-28 JP JP2020531116A patent/JP7372915B2/en active Active
- 2018-11-28 CN CN201880075961.5A patent/CN111417681B/en active Active
- 2018-12-04 TW TW107143360A patent/TWI809011B/en active
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2020
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|---|---|
| JP7372915B2 (en) | 2023-11-01 |
| US10829634B2 (en) | 2020-11-10 |
| CN111417681B (en) | 2023-08-22 |
| JP7659598B2 (en) | 2025-04-09 |
| JP2023145642A (en) | 2023-10-11 |
| US20190169427A1 (en) | 2019-06-06 |
| KR102627886B1 (en) | 2024-01-19 |
| TWI809011B (en) | 2023-07-21 |
| US20230348711A1 (en) | 2023-11-02 |
| CN111417681A (en) | 2020-07-14 |
| KR20200088489A (en) | 2020-07-22 |
| TW201930479A (en) | 2019-08-01 |
| JP2021505733A (en) | 2021-02-18 |
| US11725106B2 (en) | 2023-08-15 |
| US20210061994A1 (en) | 2021-03-04 |
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