Polymer compositions with improved dent and particle release properties

Abstract

The composition includes from about 50 wt% to about 85 wt% of a liquid crystalline polymer resin, from about 0.1 wt% to about 15 wt% of a polyetherimide polymer, from about 0.05 wt% to about 8 wt% of a compatibilizer, and from about 2 wt% to about 25 wt% of a mineral filler. A 50 mm x 60 mm sample molded from the composition having a thickness of 0.6 mm exhibits an anti-dent property characterized by a dent depth of 30 to 40 microns as measured using a three-dimensional surface profilometer; and using a drop tester to test the sample by using a 1.6 mm-diameter steel ball which drops from a height of 50 mm and has a weight of 50 g. Articles including the compositions are also described, including components for moving a compact camera module.

Description

Technical Field

[0001] The present disclosure relates to a liquid crystal polymer composition that provides enhanced dent resistance for certain applications, including compact camera modules. Background Art

[0002] Liquid crystal polymers (“LCPs”) are a class of polymers known for a variety of uses. LCPs are generally thermoplastic polymers, but they can also be used as thermosetting materials through functionalization or by compounding with thermosetting materials such as epoxy resins. These polymers can provide a desired combination of properties for various applications. Although liquid crystal polymers exhibit many advantages, such as dielectric and barrier properties, the use of liquid crystal polymers may be limited by a lack of sufficient melt strength and poor processability. More specifically, the processing window of LCPs may be narrow, and the tear strength of films formed from liquid crystal polymers in the machine direction may be poor, and the yield during film manufacturing and assembly processes may be low. Recently, attempts have been made to develop liquid crystal polymers with high heat resistance for the benefit of molded parts of compact camera modules (“CCMs”). Compact camera modules (“CCMs”) are commonly used in mobile phones, laptop computers, digital cameras, digital video cameras, etc., and include plastic lens barrels mounted on a base. One of the components of a CCM is a ball guide actuator. This component is prone to denting and is preferably formed from a material that can resist these dents upon impact.

[0003] Accordingly, there remains a need in the art for liquid crystal polymer-based materials suitable for applications in compact camera modules that exhibit improved dent and fracture resistance. Summary of the Invention

[0004] Aspects of the present disclosure relate to a composition comprising: about 50 wt% to about 85 wt% of a liquid crystal polymer resin; about 0.1 wt% to about 15 wt% of a polyetherimide polymer; about 0.05 wt% to about 8 wt% of a compatibilizer; and about 2 wt% to about 25 wt% of a mineral filler. The combined weight percentage values of all components do not exceed 100 wt%, and all weight percentage values are based on the total weight of the composition. A 50 mm x 60 mm sample having a thickness of 0.6 mm (millimeters) molded from the composition exhibits dent resistance characterized by a dent depth of 30 - 40 μm (micrometers) as measured using a three-dimensional surface profiler, wherein the sample is tested using a drop tester with a 50-gram, 1.6-mm diameter steel ball dropped from a height of 50 mm.

[0005] Additional aspects of the present disclosure relate to a method of forming a composition, the method comprising: (a) combining the following to form a mixture: (i) from about 50 wt% to about 85 wt% of a liquid crystal polymer resin, (ii) from about 0.1 wt% to about 15 wt% of a polyetherimide polymer, (iii) from about 0.05 wt% to about 8 wt% of a compatibilizer, and (iv) from about 2 wt% to about 25 wt% of a mineral filler; and (b) extruding the mixture to form the composition. The combined weight percentage values of all components do not exceed 100 wt%, and all weight percentage values are based on the total weight of the composition. A 50 mm x 60 mm sample having a thickness of 0.6 mm molded from the composition exhibits indentation resistance characterized by an indentation depth of 30 - 40 microns as measured using a three-dimensional surface profiler, wherein the sample is tested using a drop tester with a 50 gram, 1.6 mm diameter steel ball dropped from a height of 50 mm.

[0006] The foregoing and other features are illustrated by the following detailed description, examples, and claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0007] The drawings incorporated in and forming a part of this specification illustrate several aspects and, together with the description, serve to explain the principles of the disclosure.

[0008] Figure 1 is a diagram showing the difference between a ball guide and a spring and wire configuration of a compact camera module.

[0009] Figure 2 Table 1 is presented, which shows the materials used for preparing the formulation.

[0010] Figure 3 Table 2 is presented, which shows the temperature profile of the compounding.

[0011] Figure 4 Table 3 is presented, which shows the injection molding profile.

[0012] Figure 5 Table 4 is presented, which shows the prepared formulation.

[0013] Figure 6A shows a VCM housing and a VCM carrier, and Figure 6B shows the assembled components.

[0014] Figure 7 Table 5 is presented, which shows the tool information of the housing.

[0015] Figure 8 Table 6 is presented, which shows the obtained particulate release measurement results.

[0016] Figure 9 is a graphical representation of the particulate release measurement results.

[0017] Figure 10A and 10B are scanning electron microscopy (SEM) images showing LCP resin and LCP / epoxy resin samples, respectively.

[0018] Figure 11 Table 7 is presented, which shows the observed dent resistance performance.

[0019] Figure 12 is a graphical representation of the dent resistance performance.

[0020] Figures 13A - 13D is an SEM image of the LCP / PEI formulation.

[0021] Figure 14 is the weld line strength graph of CE1, Ex5, and Ex6. Detailed Description

[0022] The present disclosure can be more easily understood by reference to the following detailed description of the desired aspects and the examples included therein. In the following specification and the subsequent claims, a number of terms will be referred to having the following meanings. Also, articles prepared by any of the methods described herein are within the scope of the present disclosure. For example, articles that can be produced using the materials and methods of the present disclosure include articles in the electrical field, such as computers, antennas, and lighting articles.

[0023] Liquid crystal polymers can provide a desired combination of properties for various applications. For example, films obtained from liquid crystal polymers can provide a barrier to oxygen and moisture, making the films effectively usable for packaging applications. Films formed from liquid crystal polymers are also attractive in circuit board applications due to their stability and good dielectric properties (such as low loss factor over a wide frequency range). Although liquid crystal polymers exhibit many desired properties, the use of liquid crystal polymers may be limited by a lack of sufficient melt strength and poor processability. The processing window of liquid crystal polymers may be narrow, and the tear strength of films formed from liquid crystal polymers in the machine direction may be poor, and the yield during film manufacturing and assembly processes may be low.

[0024] However, recently there have been attempts to use liquid crystal polymers with high heat resistance for molded parts of a compact camera module (CCM). A compact camera module ("CCM") is typically used in mobile phones, laptop computers, digital cameras, and digital video cameras, and includes a plastic lens barrel mounted on a base. Since conventional plastic lenses cannot withstand solder reflow, camera modules are typically not surface-mounted. Recently, the use of LCP in components of a CCM, such as a lens barrel or the base on which the lens barrel is mounted, may still suffer from poor performance. To improve the mechanical properties of such polymers, it is known to add plate-like substances (e.g., mineral fillers such as talc) and ground glass. Although the strength and elastic modulus can be improved in this way, problems still arise when attempting to use such materials in a compact camera module due to their small dimensional tolerances. For example, the mechanical properties are usually poor or non-uniform, which results in poor filling and a lack of dimensional stability of the molded parts. Further, increasing the amount of ground glass to improve the mechanical properties may result in a surface that is too rough, which may cause errors in camera performance and sometimes cause unwanted particle generation.

[0025] Aspects of the present disclosure can improve the application of LCP in a CCM, particularly for a ball guide actuator type of CCM. Generally, there are two methods for autofocus and optical image stabilization (OIS): the ball guide type and the spring and wire (or spring) type. In the ball type applicable here, ceramic balls are key components for achieving focusing and image stabilization. Examples of ball guide and spring type housing configurations and their corresponding characteristics are shown in Figure 1 which is adapted from "Camera Module", https: / / www.samsungsem.com / global / product / module / camera-module.do. In a conventional CCM housing including LCP and mica filler, using a ball guide housing may cause the ceramic balls to create dents on the inner surface of the CCM housing. The balls can move in the X, Y, and Z directions, thus causing dents and damage to the CCM actuator surface, ultimately resulting in autofocus and OIS failures.

[0026] In these CCM actuators, a large number of particles generated during vibration and drop may also result in poor quality. Through reliability tests such as vibration and free fall tests, it has been shown that conventional CCM actuators composed of LCP and mica filler generate a large number of particles upon impact. Such fine particles may be caused by the mineral filler.

[0027] Attempts have been made to achieve LCP compositions with different capabilities. Published international application WO 2022214927A2 describes the use of inorganic fillers with liquid crystal polymers, polyetherimides, and compatibilizers to achieve liquid crystal polymer compositions with balanced properties. Japanese patents describe a polymer alloy comprising a liquid crystal copolyester and a polyetherimide. US Patent US 5,366,663 discloses a mixture comprising a liquid crystal copolymer, a polyetherimide, and a compatibilizer to achieve a composition with improved tensile properties. Japanese Patent JP 04017394B2 discloses a resin composition comprising a synthetic resin and plate-like inorganic fillers such that the composition has improved mechanical strength, heat resistance, and low resin degradation. Japanese Published Patent Application JP 2001152036A also discloses a resin composition comprising a synthetic resin and synthetic mica to provide a composition with improved moldability and reduced resin degradation. Japanese Published Patent Application JP 2007197714A discloses a composition comprising a liquid crystal resin, a thermoplastic resin, and fine talc such that the composition exhibits improved minimum molding shrinkage and elongation flexure.

[0028] Other research has focused on formulations for compact camera modules. Published international application WO 2014143176A1 discloses a compact camera module formed from a composition comprising a liquid crystal polymer and a plurality of mineral fibers. US Published Patent Application US20200304694A1 discloses an actuator for a camera module, the actuator comprising a composition comprising an aromatic polymer and one or more mineral fillers. The disclosed compositions exhibit flexural strength and hardness properties such that the formulations have minimized indentation upon impact.

[0029] Aspects of the present disclosure can address many of the above technical limitations. Compared to conventional LCP materials comprising mica fillers, the compositions according to aspects of the present disclosure exhibit improved properties. As provided herein, the improved properties include, but are not limited to, improved indentation resistance and reduced particle generation. The compositions of the present disclosure can comprise from about 50 wt% to about 85 wt% of a liquid crystal polymer resin; from about 0.1 wt% to about 15 wt% of a polyetherimide polymer; from about 0.05 wt% to about 8 wt% of a compatibilizer; and from about 2 wt% to about 25 wt% of an inorganic mineral filler. The combined weight percentage values of all components do not exceed 100 wt%, and all weight percentage values are based on the total weight of the composition.

[0030] Prior to the disclosure and description of the compounds, compositions, articles, systems, devices, and / or methods of the present invention, it is to be understood that, unless otherwise specified, they are not limited to particular synthetic methods or, unless otherwise specified, to particular reagents, and thus can of course be varied. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. The present disclosure encompasses various combinations of the elements of the present disclosure, such as combinations of elements from the dependent claims that depend on the same independent claim.

[0031] Furthermore, it is to be understood that, unless otherwise expressly stated, any method set forth herein is in no way to be construed as requiring that its steps be performed in a particular order. Accordingly, where a method claim does not actually recite an order to be followed by its steps or where no particular order is otherwise specifically set forth in the claims or in the specification, no order is to be inferred in any respect. This applies to any possible basis of non-explicit interpretation, including logical issues regarding the arrangement of steps or the sequence of operations; simple meaning derived from grammatical organization or punctuation; and the number or type of aspects described in the specification.

[0032] LCP composition

[0033] The disclosed compositions can include a liquid crystal polymer resin, a polyetherimide polymer, a compatibilizer, and an inorganic mineral filler. In certain aspects, the compositions include blends of LCP polymer resins.

[0034] Compared to mica-filled LCP or mica-filled LCP with polyetherimide, the compositions according to aspects of the present disclosure have improved properties. A particular combination of components achieves certain improved performance in terms of dent resistance and particulate release. More specifically, a 50 mm x 60 mm sample with a thickness of 0.6 mm (millimeter) molded from the composition exhibits dent resistance characterized by a dent depth of 30 - 40 micrometers (μm) as measured using a three-dimensional surface profiler, and the sample is tested using a drop tester with a 1.6 mm diameter steel ball weighing 50 grams dropped from a height of 50 mm. The CCM VCM housing formed from the disclosed composition can exhibit less particulate release compared to a second CCM VCM housing formed from a reference composition. The reference composition includes the same liquid crystal polymer resin and mica filler but does not include the polyetherimide polymer, and the CCM VCM housing is 12 mm x 12 mm x 7 mm with a cavity of 1×2 mm.

[0035] The liquid crystal polymer resin can be derived from 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid. The polyetherimide can be derived from bisphenol A dianhydride, metaphenylenediamine, and aniline capping agent. The compatibilizer can include ethylene-glycidyl methacrylate copolymer. In some aspects, the mineral filler can include mica.

[0036] Liquid crystal polymer resin

[0037] In various aspects, the disclosed compositions can include a liquid crystal polymer (LCP) resin. Due to the nature of the repeating units in the polymer chain, LCPs are considered to have a fixed molecular shape, such as linear. The repeating units typically include rigid molecular elements. The rigid molecular elements (mesogens) are generally rod-like or disc-like in shape and are typically aromatic and often heterocyclic. The rigid molecular elements can be present in one or both of the polymer backbone (skeleton) and the side chains. The rigid molecular elements can be separated by more flexible molecular elements (sometimes called spacers).

[0038] Both lyotropic liquid crystal polymers and thermotropic liquid crystal polymers can be used in the present disclosure. In one aspect, the liquid crystal polymer can be a thermotropic liquid crystal polymer, which can include liquid crystal polyesters, liquid crystal polycarbonates, liquid crystal poly(ether ether ketone), liquid crystal poly(ether ketone ketone), and liquid crystal polyesterimides. The thermotropic liquid crystal polymers can also include: polymers that include polymer segments (as part of one of its polymer chains) capable of forming an anisotropic molten phase, and polymer segments (as the remainder of the polymer chain) that cannot form an anisotropic molten phase; and composites of various thermotropic liquid crystal polymers.

[0039] Examples of monomers that can be used to form thermotropic liquid crystal polymers can include: (a) aromatic dicarboxylic acid compounds, (b) aromatic hydroxycarboxylic acid compounds, (c) aromatic diol compounds, (d) sulfur-containing compounds such as aromatic dithiols (d1), aromatic thiophenols (d2), and aromatic thiol carboxylic acid compounds (d3), and (e) amine compounds such as aromatic hydroxyamine compounds and aromatic diamine compounds. The monomers can be used alone or in combination, such as (a) and (c); (a) and (d); (a), (b), and (c); (a), (b), and (e); (a), (b), (c), and (e); and so on.

[0040] Examples of the aromatic dicarboxylic acid compound (a) include aromatic dicarboxylic acids such as terephthalic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-triphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylether-4,4'-dicarboxylic acid, diphenoxyethane-4,4'-dicarboxylic acid, diphenoxybutane-4,4'-dicarboxylic acid, diphenylethane-4,4'-dicarboxylic acid, isophthalic acid, diphenylether-3,3'-dicarboxylic acid, diphenoxyethane-3,3'-dicarboxylic acid, diphenylethane-3,3'-dicarboxylic acid, and 1,6-naphthalenedicarboxylic acid; and alkyl, alkoxy, and halogen-substituted derivatives of the above aromatic dicarboxylic acids such as chloroterephthalic acid, dichloroterephthalic acid, bromoterephthalic acid, methylterephthalic acid, dimethylterephthalic acid, ethylterephthalic acid, methoxyterephthalic acid, and ethoxyterephthalic acid.

[0041] Examples of the aromatic hydroxycarboxylic acid compound (b) include aromatic hydroxycarboxylic acids such as 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and 6-hydroxy-1-naphthoic acid; and alkyl, alkoxy, and halogen-substituted derivatives of the aromatic hydroxycarboxylic acids such as 3-methyl-4-hydroxybenzoic acid, 3,5-dimethyl-4-hydroxybenzoic acid, 6-hydroxy-5-methyl-2-naphthoic acid, 6-hydroxy-5-methoxy-2-naphthoic acid, 2-chloro-4-hydroxybenzoic acid, 3-chloro-4-hydroxybenzoic acid, 2,3-dichloro-4-hydroxybenzoic acid, 3,5-dichloro-4-hydroxybenzoic acid, 2,5-dichloro-4-hydroxybenzoic acid, 3-bromo-4-hydroxybenzoic acid, 6-hydroxy-5-chloro-2-naphthoic acid, 6-hydroxy-7-chloro-2-naphthoic acid, and 6-hydroxy-5,7-dichloro-2-naphthoic acid.

[0042] Examples of the aromatic diol compound (c) include aromatic diols such as 4,4'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 4,4'-dihydroxytriphenyl, hydroquinone, resorcinol, 2,6-naphthalenediol, 4,4'-dihydroxybiphenyl ether, bis(4-hydroxyphenoxy)ethane, 3,3'-dihydroxydiphenyl ether, 1,6-naphthalenediol, 2,2-bis(4-hydroxyphenyl)propane, and bis(4-hydroxyphenyl)methane; and alkyl, alkoxy, and halogen-substituted derivatives of the aromatic diols such as chlorohydroquinone, methylhydroquinone, tert-butylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4-chlororesorcinol, and 4-methylresorcinol.

[0043] Examples of the aromatic dithiols (d1) include benzene-1,4-dithiol, benzene-1,3-dithiol, 2,6-naphthalene-dithiol, and 2,7-naphthalene-dithiol. Examples of the aromatic thiophenols (d2) include 4-hydroxythiophenol, 3-hydroxythiophenol, and 6-hydroxythiophenol. Examples of the aromatic mercaptocarboxylic acids (d3) include 4-mercaptobenzoic acid, 3-mercaptobenzoic acid, 6-mercapto-2-naphthoic acid, and 7-mercapto-2-naphthoic acid.

[0044] Examples of the aromatic hydroxyamine compounds and aromatic diamine compounds (e) include 4-aminophenol, N-methyl-4-aminophenol, 1,4-benzenediamine, N-methyl-1,4-benzenediamine, N,N'-dimethyl-1,4-benzenediamine, 3-aminophenol, 3-methyl-4-aminophenol, 2-chloro-4-aminophenol, N-acetyl-p-aminophenol, 4-amino-1-naphthol, 4-amino-4'-hydroxybiphenyl, 4-amino-4'-hydroxydiphenyl ether, 4-amino-4'-hydroxydiphenylmethane, 4-amino-4'-hydroxydiphenyl sulfide, 4,4'-diaminodiphenyl sulfide (thiodiphenylamine), 4,4'-diaminodiphenyl sulfone, 2,5-diaminotoluene, 4,4'-ethylenedianiline, 4,4'-diaminodiphenoxyethane, 4,4'-diaminodiphenylmethane (methylenedianiline), and 4,4'-diaminodiphenyl ether (oxydianiline).

[0045] The thermotropic liquid crystal polymer can be used alone or can be used as a mixture of at least two of them. In one aspect, the composition can include a thermotropic liquid crystal polymer, such as an aromatic polyester having a melting point of at least 290 °C.

[0046] In some aspects, the liquid crystal polymer can include a liquid crystal polyester. The liquid crystal polyester can be derived from aromatic hydroxycarboxylic acids (such as p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid), aromatic dicarboxylic acids (such as terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid), aromatic dihydroxy compounds (such as hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, and 2,6-dihydroxynaphthalene), or a combination including at least one of the above. Based on the total number of moles of (I), (II), (III), and any other aromatic compounds in the polycondensation reaction, the aromatic liquid crystal polyester can be obtained by condensing 80 mol% to 100 mol% (mol%) of p-hydroxybenzoic acid (I), terephthalic acid (II), and 4,4'-dihydroxybiphenyl (III) (including its derivatives) (where the sum of (I) and (II) is 60 mol% or more) with 0 mol% to 20 mol% of other aromatic compounds capable of undergoing a polycondensation reaction with any one of (I), (II), and (III).

[0047] In another aspect, the liquid crystal polymer can be derived from 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid. In one aspect, the liquid crystal polymer is derived from 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, naphthalenedicarboxylic acid, and hydroquinone.

[0048] Examples of specific commercial liquid crystal polymers that can be used include, but are not limited to, VECTRA TM and ZENITE TM (both of which are commercially available from Celanese), XYDAR TM (commercially available from Solvay Specialty Polymers), liquid crystal polymers available from RTP Co. (e.g., RTP-3400 series liquid crystal polymers), and liquid crystal polymers available from UENO Fine Chemicals Industry, Ltd. (e.g., LCP-A 5000 and LCP-A 6000).

[0049] Based on the total weight of the composition, the liquid crystal polymer can be present in the composition in an amount of 50 wt% to 85 wt%. Within this range, based on the total weight of the composition, the liquid crystal polymer can be present in an amount of at least 50 wt%, at least 55 wt%, at least 58 wt%, at least 60 wt%, at least 62 wt%, at least 64 wt%, at least 66 wt%, at least 68 wt%, at least 70 wt%, at least 72 wt%, at least 74 wt%, up to 85 wt%, up to 83 wt%, up to 80 wt%, up to 78 wt%, up to 76 wt%, up to 74 wt%, up to 72 wt%, up to 70 wt%, up to 68 wt%, up to 66 wt%, or up to 64 wt%.

[0050] Polyetherimide polymer

[0051] In one aspect, the polymer composition can include a polyimide polymer, such as polyetherimide. The polyimide includes more than 1, for example 5 to 1000 or 5 to 500 or 10 to 100 structural units of formula (1)

[0052]

[0053] where each V is the same or different and is a substituted or unsubstituted tetravalent C 4-40 hydrocarbyl group, such as a substituted or unsubstituted C 6-20 aromatic hydrocarbyl group, a substituted or unsubstituted straight-chain or branched-chain, saturated or unsaturated C 2-20 aliphatic group, or a substituted or unsubstituted C 4-8An alicyclic group, especially a substituted or unsubstituted C 6-20 aromatic hydrocarbon group. Aromatic

[0054] Examples of the hydrocarbon group may include any one of the hydrocarbon groups of the following formula (1).

[0055]

[0056] Wherein W is -O-; -S-; -C(O)-; -SO2-; -SO-; a C1-18 hydrocarbon moiety, which may be cyclic, acyclic, aromatic or non-aromatic; -P(R a )(=0)-, wherein R a is a C 1-18 alkyl or a C 6-12 aryl; -C y H 2y -, wherein y is an integer from 1 to 5; or a halogenated derivative thereof (which includes a perfluoroalkylene); or a group of the formula -O-Z-O- as described in T of the following formula (3).

[0057] Each R in formula (1) may be the same or different and may be a substituted or unsubstituted divalent organic group, such as a C 6-20 aromatic hydrocarbon group or a halogenated derivative thereof, a straight-chain or branched C 2-20 alkylene or a halogenated derivative thereof, a C 3-8 cycloalkylene or a halogenated derivative thereof, especially a divalent group of formula (2)

[0058]

[0059] Wherein Q 1 is -0-; -S-; -C(O)-; -SO2-; -SO-; -P(R a )(=0)-, wherein R a is a C 1-8 alkyl or a C 6-12 aryl; -C y H 2y -, wherein y is an integer from 1 to 5; or a halogenated derivative thereof (which includes a perfluoroalkylene); or -(C6H 10 ) z -, wherein z is an integer from 1 to 4. In one aspect, R is m-phenylene, p-phenylene or a diaryl sulfone.

[0060] The polyetherimide can also be classified as a type of polyimide, which includes more than 1, for example, 10 to 1000 or 10 to 500 structural units of formula (3)

[0061]

[0062] Each R is the same or different and is as described in formula (1).

[0063] Further, in formula (3), T can be -O- or a group of the formula -O-Z-O-, where the double bond of the -O- or -O-Z-O- group is in the 3,3', 3,4', 4,3' or 4,4' position. The group Z in -O-Z-O- of formula (3) is a substituted or unsubstituted divalent organic group and can be an aromatic C 6-24 monocyclic or polycyclic moiety, said monocyclic or polycyclic moiety being optionally substituted by 1 to 6 C 1-8 alkyl groups, 1 to 8 halogen atoms or a combination comprising at least one of the foregoing, provided that the valence of Z is not exceeded. Examples of Z can include groups derived from dihydroxy compounds of formula (4)

[0064]

[0065] wherein R a and R b can be the same or different and are, for example, a halogen atom or a monovalent C 1-6 alkyl group; p and q are each independently an integer from 0 to 4; c is from 0 to 4; and X a is a bridging group connecting a hydroxy-substituted aromatic group, wherein the bridging group of each C6 arylene and the hydroxy substituent are ortho, meta or para (especially para) to each other on the C6 arylene. The bridging group X a can be a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)- or a C 1-18 organic bridging group. The C 1-18 organic bridging group can be cyclic or acyclic, aromatic or non-aromatic, and can further include heteroatoms such as halogen, oxygen, nitrogen, sulfur, silicon or phosphorus. The C 1-18 organic group can be arranged such that the C6 arylenes to which it is attached are each connected to a common alkylene carbon or a different carbon of the C 1-18 organic bridging group. In some aspects, the polyetherimide can be a copolymer, such as a polyetherimide sulfone copolymer, which includes a structural unit of formula (1), wherein at least 50 mole % of the R groups have the formula (2), wherein Q 1 is -SO2-, and the remaining R groups are independently p-phenylene or m-phenylene or a combination comprising at least one of the foregoing; and Z is 2,2'-(4-phenylene) isopropylidene.

[0066] Alternatively, the polyetherimide copolymer optionally includes additional structural imide units, such as imide units of formula (1), wherein R and V are as in formula (1), for example V is wherein W is a single bond; -O-; -S-; -C(O)-; -SO2-; -SO-; C1-18 a hydrocarbon moiety, which can be cyclic, acyclic, aromatic or non-aromatic; -P(R a )(=O)-, where R a is C 1-8 alkyl or C 6-12 aryl; or -C y H 2y -, where y is an integer from 1 to 5; or a halogenated derivative thereof (which includes perfluoroalkylene). Polyimides and polyetherimides can be prepared by any method known to those skilled in the art and further described, for example, in International Application WO 2021009727.

[0067] In various aspects, the polyimide polymer can include copolymers, such as poly(siloxane-etherimide) copolymers, which include polyetherimide units of formula (1) and siloxane blocks of formula (6)

[0068]

[0069] where the average value of E is from 2 to 100, 2 to 31, 5 to 75, 5 to 60, 5 to 15 or 15 to 40, and each R' is independently a C 1-13 monovalent hydrocarbon group. For example, each R' can

[0070] independently be C 1-13 alkyl, C 1-13 alkoxy, C 2-13 alkenyl, C2-13 alkenoxy, C 3-6 cycloalkyl, C 3-6 cycloalkoxy, C 6-14 aryl, C 6-10 aryloxy, C 7-13 aralkyl, C 7-13 aralkoxy, C 7-13 alkylaryl or C 7-13 alkylaryloxy. Examples of specific poly(siloxane-etherimide) are described in U.S. Pat. Nos. 4,404,350, 4,808,686 and 4,690,997. The relative amounts of the polysiloxane units and the etherimide units in the poly(siloxane-etherimide) depend on the desired properties and are selected using the guidelines provided herein. Specifically, as described above, the block or graft poly(siloxane-etherimide) copolymer is selected to have a certain average value of E and the amounts selected and used effectively provide the desired wt% of polysiloxane units in the composition. In one aspect, based on the total weight of the poly(siloxane-etherimide), the poly(siloxane-etherimide) includes 10 to 50 wt%, 10 to 40 wt% or 20 to 35 wt% of polysiloxane units. In one aspect, polyetherimide-siloxane can be excluded from the composition.

[0071] The melt index of the disclosed polyetherimide polymer can be from 0.1 to 10 grams per minute (g / min), as measured by American Society for Testing and Materials (ASTM) D1238 at 340 to 370 °C using a 6.7 kilogram (kg) weight. In one aspect, the weight average molecular weight (Mw) of the polyetherimide is from 1,000 to 150,000 grams per mole (Daltons), as measured by gel permeation chromatography using polystyrene standards. In one aspect, the Mw of the polyetherimide is from 10,000 to 80,000 Daltons. The inherent viscosity of such polyetherimides is typically greater than 0.2 deciliters per gram (dl / g) or more specifically from 0.35 to 0.7 dl / g, as measured in m-cresol at 25 °C. Some examples of such polyetherimides can include but are not limited to Ultem TM 1000 (number average molecular weight (Mn) 21,000; weight average molecular weight (Mw) 54,000; dispersity 2.5), Ultem TM 1010 (Mn 19,000; Mw 47,000; dispersity 2.5); Ultem TM 1040 (Mn 12,000; Mw 34,000 - 35,000; dispersity 2.9) or mixtures thereof.

[0072] In some aspects, the polymer composition can include from about 0.1 wt% to about 15 wt% of the polyetherimide polymer. Within this range, based on the total weight of the polymer composition, the composition can include at least 0.15 wt%, at least 0.5 wt%, at least 0.8 wt%, at least 1 wt%, at least 2 wt%, at least 3 wt%, at least 4 wt%, at least 5 wt%, at least 6 wt%, at least 7 wt%, at least 7.5 wt%, at least 8 wt%, at least 9 wt%, at least 10 wt%, up to 15 wt%, up to 14 wt%, up to 13 wt%, up to 12 wt%, up to 11 wt%, up to 10 wt%, up to 9 wt%, up to 8 wt%, up to 7 wt%, up to 6 wt% or up to 5 wt% of the polyetherimide polymer.

[0073] Compatibilizer or impact modifier

[0074] In various aspects, the disclosed compositions can include a compatibilizer. As used herein, a "compatibilizer" refers to an additive used to improve the miscibility of a copolymer or to improve the miscibility between a polymer or polymer phase and a filler. A compatibilizer can be configured to improve the blend compatibility of the components of a polymer composition. For example, a compatibilizer can improve the compatibility of LCP and PEI. In one aspect, a suitable polymer compatibilizer can have, for example, a weight-average molecular weight greater than 1,000 grams per mole or greater than 10,000 grams per mole, the weight-average molecular weight being determined using gel permeation chromatography in a suitable solvent and relative to a suitable standard, each standard being determinable without undue experimentation.

[0075] In certain aspects, the compatibilizer can include a polyepoxide, such as an epoxy-functionalized block copolymer. The epoxy-functional block copolymer can further include additional units, such as C 1-4 alkyl (meth)acrylate units. In one aspect, the impact modifier is a terpolymer including a polyethylene block, a methyl acrylate block, and a glycidyl methacrylate block. A specific compatibilizer can be a copolymer or terpolymer including ethylene, glycidyl methacrylate (GMA), and methyl acrylate units. For example, the compatibilizer can include repeating units derived from: ethylene and glycidyl methacrylate; ethylene, C 1-6 alkyl acrylate, and glycidyl acrylate; ethylene, methyl acrylate, and glycidyl methacrylate; ethylene, butyl acrylate, and glycidyl methacrylate; or ethylene, vinyl acetate, and glycidyl methacrylate. In one aspect, the polyepoxide can be an ethylene-glycidyl methacrylate copolymer, an ethylene-glycidyl methacrylate-methyl acrylate terpolymer, or an ethylene-glycidyl methacrylate-vinyl acetate terpolymer. In one aspect, the polyepoxide can be an ethylene-glycidyl methacrylate copolymer including, based on the total moles of the polyepoxide, from 1 mol% to 5 mol% glycidyl methacrylate groups. Examples of polyepoxides can include Igetabond TM (commercially available from Sumitomo), Bondfast E TM (commercially available from Sumitomo), and Lotader TM (commercially available from Arkema).

[0076] Examples of impact modifiers include an ethylene-methyl acrylate-glycidyl methacrylate terpolymer containing 8 wt% or about 8 wt% glycidyl methacrylate units, the terpolymer being available under the trade name LOTADER TMThe AX8900 is obtained from Arkema. Another epoxy-functional block copolymer that can be used in the composition includes an ethylene acrylate available from Rohm and Haas (Dow Chemical) under the trade name Paraloid TM EXL-3330, for example, an ethylene-ethyl acrylate copolymer with an ethyl acrylate content of less than 20%. It will be recognized that combinations of compatibilizers can be used.

[0077] In one example, the epoxy-functional block copolymer can include units derived from C 2-20 olefins and units derived from glycidyl (meth)acrylate. Examples of olefins include ethylene, propylene, butene, etc. The olefin units can be present in the copolymer in block form, such as in the form of polyethylene, polypropylene, polybutene, etc. blocks. It is also possible to use mixtures of olefins, i.e., blocks of mixtures containing ethylene and propylene units or polyethylene blocks together with polypropylene blocks.

[0078] In various aspects, the compatibilizer can include an epoxy-functionalized block copolymer. For example, the compatibilizer can include a functionalized polyolefin ethylene-acrylate terpolymer, such as ethylene-acrylate-maleic anhydride (MAH) or glycidyl methacrylate (GMA). The functionalized terpolymer can optionally contain repeating units derived from monomers containing an anhydride group (such as maleic anhydride) in its main chain. In another case, the functionalized terpolymer contains an anhydride moiety grafted onto the polymer in a post-polymerization step.

[0079] In a further aspect, the polyepoxide can include structural units having epoxy side groups. In one aspect, each molecule of the polyepoxide includes three or more epoxy groups. In one aspect, the polyepoxide includes an addition polymer of an ethylenically unsaturated epoxide (also known as an epoxy-functional elastomer) or a novolak resin epoxide. In some aspects, the polyepoxide can be an epoxy-functional elastomer. The epoxy-functional elastomer includes a copolymer derived from an α-olefin and a glycidyl ester of an a,b-unsaturated carboxylic acid. Suitable α-olefins can include ethylene, propylene, 1-butene, etc. Ethylene can be preferred. The glycidyl ester of the a,b-unsaturated carboxylic acid can have the formula (8)

[0080]

[0081] where R 10 can be hydrogen or C 1-6An alkyl group, preferably a methyl group. Examples of glycidyl esters of a,b-unsaturated carboxylic acids can include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethyl acrylate. The epoxy-functional olefin elastomer is preferably an olefin copolymer that contains 60 wt% to 99.5 wt% of an a-olefin and 0.5 wt% to 40 wt% of a glycidyl ester of an a,b-unsaturated carboxylic acid, preferably 3 wt% to 30 wt%, based on the weight of the epoxy-functional olefin elastomer.

[0082] In one aspect, the polyepoxide can be a novolak-type epoxy resin. The novolak-type epoxy resin can be obtained by reacting a novolak-type phenolic resin with epichlorohydrin.

[0083] In one aspect, the compatibilizer includes poly(ester-carbonate). Such polycarbonates include repeating carbonate units of formula (9) and repeating ester units of formula (10)

[0084]

[0085] wherein R 1 At least 60% of the total number of groups is aromatic, or each R 1 contains at least one Ce-30 aromatic group. Preferably, each R 1 can be derived from a dihydroxy compound, such as an aromatic dihydroxy compound or a bisphenol. Specific dihydroxy compounds include resorcinol, 2,2-bis(4-hydroxyphenyl)propane (“bisphenol A” or “BPA”), 3,3-bis(4-hydroxyphenyl)phthalimide, 2-phenyl-3,3'-bis(4-hydroxyphenyl)phthalimide (also known as N-phenylphthalein bisphenol, “PPPBP” or 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one), 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (isophorone bisphenol).

[0086] J in formula (10) can be a divalent group derived from an aromatic dihydroxy compound (including its reactive derivatives) (such as a bisphenol, for example bisphenol A); and T is a divalent group derived from an aromatic dicarboxylic acid (including its reactive derivatives) (preferably isophthalic acid or terephthalic acid, where the weight ratio of isophthalic acid to terephthalic acid is 91:9 to 2:98). Copolyesters containing a combination of different T or J groups can be used. The polyester units can be branched or linear.

[0087] Aromatic dicarboxylic acids that can be used to prepare polyester units include isophthalic acid or terephthalic acid, 1,2-bis(p-carboxyphenyl)ethane, 4,4'-dicarboxydiphenyl ether, 4,4'-bibenzoic acid, or combinations thereof. Acids containing condensed rings can also be present, such as 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, or 2,6-naphthalenedicarboxylic acid. Specific dicarboxylic acids include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, or combinations thereof. Specific dicarboxylic acids include combinations of isophthalic acid and terephthalic acid, wherein the weight ratio of isophthalic acid to terephthalic acid is from 91:9 to 2:98. A portion (e.g., up to 20 mol%) of the T groups can be aliphatic, such as those derived from 1,4-cyclohexanedicarboxylic acid. Preferably, all T groups are aromatic. The molar ratio of ester units to carbonate units in the polycarbonate can vary widely, e.g., from 1:99 to 99:1, or from 10:90 to 90:10, or from 25:75 to 75:25, or from 2:98 to 15:85, depending on the desired properties of the final composition.

[0088] Specific poly(ester-carbonate)s are those that include bisphenol A carbonate units and isophthalate / terephthalate-bisphenol A ester units, i.e., poly(bisphenol A carbonate)-co-(bisphenol A-phthalate-ester) of formula (11)

[0089]

[0090] wherein x and y represent the weight percentages of bisphenol A carbonate units and isophthalate / terephthalate-bisphenol A ester units, respectively. Generally, the units are present in block form. In one aspect, the weight ratio of carbonate units x to ester units y in the polycarbonate is from 1:99 to 50:50, or from 5:95 to 25:75, or from 10:90 to 45:55. The copolymer of formula (11) is commonly referred to as poly(carbonate-ester) (PCE), and the copolymer comprises 35 wt% to 45 wt% of carbonate units and 55 wt% to 65 wt% of ester units, wherein the molar ratio of isophthalate to terephthalate in the ester units is from 45:55 to 55:45. Copolymers comprising 15 wt% to 25 wt% of carbonate units and 75 wt% to 85 wt% of ester units are commonly referred to as poly(phthalate-carbonate) (PPC), wherein the molar ratio of isophthalate to terephthalate in the ester units is from 98:2 to 88:12.

[0091] In another aspect, the poly(ester-carbonate) is poly(carbonate-co-monoarylate ester) of formula (12), which comprises aromatic carbonate units and repeating monoarylate ester units

[0092]

[0093] wherein R 1As defined in formula (8). Each R h can independently be C 1-4 alkyl, and n is from 0 to 3, from 0 to 1, or 0. The molar ratio of carbonate unit x to ester unit z can be from 99:1 to 1:99, or from 98:2 to 2:98, or from 90:10 to 10:90. In one aspect, the molar ratio of x:z is from 50:50 to 99:1, or from 1:99 to 50:50.

[0094] Suitable polyester-carbonates can include bisphenol A carbonate units, and ITR ester units derived from terephthalic acid, isophthalic acid, and resorcinol, i.e., poly(bisphenol A carbonate-co-isophthalate / terephthalate-resorcinol ester) of formula (13)

[0095]

[0096] where the molar ratio of x:z is from 98:2 to 2:98, or from 90:10 to 10:90. In one aspect, the molar ratio of x:z is from 50:50 to 99:1, or from 1:99 to 50:50. Based on the total molar amount of ester units in the copolymer, the ITR ester units can be present in poly(bisphenol A carbonate-co-isophthalate-terephthalate-resorcinol ester) in an amount of greater than or equal to 95 mol%, preferably greater than or equal to 99 mol%, and still more preferably greater than or equal to 99.5 mol%.

[0097] Based on the total molar amount of units in the copolymer, other carbonate units, other ester units, or combinations thereof can be present in a total amount of 1 mol% to 20 mol%, such as monoaryl carbonate units of formula (14) and bisphenol ester units of formula (15):

[0098]

[0099] where in the above formulas, R h are each independently CHO hydrocarbyl, n is 0 - 4, R a and R b are each independently C 1-12 alkyl, p and q are each independently integers from 0 - 4, and X a is a single bond, -O-, -S-, -S(O)-, -S(0)2-, -C(O)-, or a C c alkylene of formula -C(R d )(R 1-13 )(where R c and R d are each independently hydrogen or C 1-12 alkyl) or a group of formula -C(=R e )(where R e is divalent C1-12 (hydrocarbyl). The bisphenol ester unit can be a bisphenol A phthalate unit of formula (16)

[0100]

[0101] In one aspect, the poly(bisphenol A carbonate-co-isophthalate / terephthalate-resorcinol ester) comprises from 1 mol% to 90 mol% of bisphenol A carbonate units, from 10 mol% to 99 mol% of isophthalic acid-terephthalic acid-resorcinol ester units, and optionally from 1 mol% to 60 mol% of resorcinol carbonate units, isophthalic acid-terephthalic acid-bisphenol A phthalate units or combinations thereof. In another aspect, the poly(bisphenol A carbonate-co-isophthalate / terephthalate-resorcinol ester) comprises from 10 mol% to 20 mol% of bisphenol A carbonate units, from 20 mol% to 98 mol% of isophthalic acid-terephthalic acid-resorcinol ester units, and optionally from 1 mol% to 60 mol% of resorcinol carbonate units, isophthalic acid-terephthalic acid-bisphenol A phthalate units or combinations thereof.

[0102] The weight-average molecular weight (Mw) of the poly(ester-carbonate) can be from 2,000 g / mol to 100,000 g / mol, preferably from 3,000 g / mol to 75,000 g / mol, more preferably from 4,000 g / mol to 50,000 g / mol, more preferably from 5,000 g / mol to 35,000 g / mol, and still more preferably from 17,000 g / mol to 30,000 g / mol. Molecular weight determination is performed using GPC, using a crosslinked styrene-divinylbenzene column, at a sample concentration of 1 mg / mL and calibrated with a bisphenol A homopolycarbonate standard. The sample is eluted with dichloromethane as the eluent at a flow rate of 1.0 mL / min.

[0103] The compatibilizer can be present in the composition in an amount of from 0.05 wt% to 8 wt%. Within this range, the composition can comprise at least 0.05 wt%, at least 0.5 wt%, at least 0.8 wt%, at least 1.0 wt%, at least 1.2 wt%, at least 1.4 wt%, at least 1.6 wt%, at least 1.8 wt%, at least 2.0 wt%, at least 2.2 wt%, at least 2.4 wt%, up to 8 wt%, up to 7.5 wt%, up to 7.0 wt%, up to 6.5 wt%, up to 6.0 wt%, up to 5.5 wt%, up to 5.0 wt%, up to 4.5 wt%, up to 4.0 wt%, up to 3.5 wt% or up to 3.0 wt% of the compatibilizer.

[0104] Filler

[0105] The compositions of the present disclosure may include fillers. In various aspects, the fillers are inorganic or mineral fillers. Examples of inorganic or mineral fillers may include, but are not limited to, mica, clay, feldspar, quartz, quartzite, perlite, diatomaceous rock, diatomaceous earth, aluminum silicate (mullite), synthetic calcium silicate, fused silica, calcined silica, sand, boron nitride powder, boron silicate powder, calcium sulfate, calcium carbonate (such as chalk, limestone, marble, and synthetic precipitated calcium carbonate), talc (including fibrous, modular, acicular, and lamellar talc), wollastonite, hollow or solid glass spheres, silicate spheres, hollow microspheres, aluminosilicates or armospheres, kaolin, silicon carbide, alumina, boron carbide, whiskers of iron, nickel, or copper, continuous and chopped carbon or glass fibers, molybdenum disulfide, zinc sulfide, barium titanate, barium ferrite, barium sulfate, barite, TiO2, alumina, magnesia, granular or fibrous aluminum, bronze, zinc, copper, or nickel, glass flakes, flake silicon carbide, flake aluminum diboride, flake aluminum, steel flakes, natural fillers such as wood flour, fibrous cellulose, cotton, sisal, jute, starch, lignin, peanut shells, or rice husks, reinforcing organic fibrous fillers such as poly(ether ketone), polyimide, polybenzoxazole, poly(phenylene sulfide), polyester, polyethylene, aromatic polyamide, aromatic polyimide, polyetherimide, polytetrafluoroethylene, and poly(vinyl alcohol), and combinations comprising at least one of the foregoing fillers or reinforcements.

[0106] In some aspects, the polymer composition may include inorganic / mineral fillers such as titanium dioxide, titanates, or combinations thereof. In certain aspects, the composition includes mica.

[0107] In certain instances, the composition includes from 2 wt% to 30 wt% of mineral filler. Within this range, the composition may include at least 2 wt%, at least 3 wt%, at least 4 wt%, at least 5 wt%, at least 6 wt%, at least 7 wt%, at least 8 wt%, at least 9 wt%, at least 10 wt%, at least 11 wt%, at least 12 wt%, at least 13 wt%, at least 14 wt%, at least 15 wt%, at least 16 wt%, at least 17 wt%, at least 18 wt%, at least 19 wt%, at least 20 wt%, up to 30 wt%, up to 29 wt%, up to 28 wt%, up to 27 wt%, up to 26 wt%, up to 25 wt%, up to 24 wt%, up to 23 wt%, up to 22 wt%, up to 21 wt%, up to 20 wt%, up to 19 wt%, up to 18 wt%, up to 17 wt%, up to 16 wt%, up to 15 wt%, up to 14 wt%, up to 13 wt%, up to 12 wt%, or up to 11 wt% of mineral filler.

[0108] Additives

[0109] The composition may include various additives typically incorporated into polymer compositions of this type, provided that the choice of additives does not have a significant adverse effect on the desired properties of the thermoplastic composition (such as good compatibility). Such additives can be mixed at an appropriate time during the mixing of the components to form the composition. Based on the total weight of the composition, the total amount of all additional additives in the polymer composition can be, for example, from about 0.001 wt% to about 12 wt%, which is sufficient to make up the balance for the amounts of LCP, filler, compatibilizer, and to keep the total mass of the composition at 100 wt%. Suitable additives can include ultraviolet agents, ultraviolet stabilizers, heat stabilizers, antistatic agents, antimicrobial agents, anti-dripping agents, radiation stabilizers, pigments, dyes, fibers, fillers, plasticizers, fibers, flame retardants, antioxidants, lubricants, wood, glass, and metal, and combinations thereof.

[0110] The composite materials disclosed herein can include one or more additional fillers. The filler can be selected to impart additional impact strength and / or provide additional properties that can be based on the final selection of the polymer composition. In certain aspects, the composite material can include glass fiber fillers. In yet other aspects, the composite material can be free or substantially free of glass fillers.

[0111] In a specific aspect, the polymer composition can include a pigment or colorant. The polymer composition can include a colorant, pigment, or dye as the color to be dispersed.

[0112] Suitable pigments include, for example, inorganic pigments such as metal oxides and mixed metal oxides; sulfides such as zinc sulfide, etc.; aluminates; sodium sulfosilicate; sulfates and chromates; zinc ferrite; ultramarine blue; pigment brown 24; pigment red 101; pigment yellow 119; organic pigments; pigment blue 60, pigment red 122, pigment red 149, pigment red 177, pigment red 179, pigment red 202, pigment violet 29, pigment blue 15, pigment green 7, pigment yellow 147, and pigment yellow 150, or combinations including at least one of the above pigments. Suitable dyes can include, for example, organic dyes, hydrocarbon and substituted hydrocarbon dyes; phthalocyanine dyes and pigments; oxazine dyes; carboxystyryl dyes; porphyrin dyes; acridine dyes; anthraquinone dyes; arylmethane dyes; azo dyes; diazo compound dyes. Suitable colorants can include, for example, titanium dioxide, anthraquinone, perylene, perinone, indanthrone, quinacridone, xanthene, oxazine, oxazoline, thioxanthene, indigo, thioindigo, naphthalimide, cyanine, xanthene, methylene, lactone, coumarin, bis(benzoxazolyl)thiophene (BBOT), naphthalenetetracarboxylic acid derivatives, monoazo and bisazo pigments, triarylmethane, aminoketone, bis(styryl)biphenyl derivatives, etc., and combinations including at least one of the above colorants. In some instances, the polymer composition can include carbon black.

[0113] Heat stabilizer additives include organic phosphites (e.g., triphenyl phosphite, tris(2,6-dimethylphenyl) phosphite, tris(mixed mono- and di-nonylphenyl) phosphite, etc.), phosphonates (e.g., xylene phosphonate, etc.), phosphates (e.g., trimethyl phosphate, etc.) or combinations including at least one of the above heat stabilizers. The heat stabilizer can be tris(2,4-di-tert-butylphenyl) phosphate obtained in the form of IRGAPHOS TM 168.

[0114] There is a significant overlap among plasticizers, lubricants and release agents, which include, for example, glyceryl tristearate (GTS), phthalates (e.g., octyl 4,5-epoxy-hexahydrophthalate), tris(2-ethylhexyl) isocyanurate, tristearin, difunctional or polyfunctional aromatic phosphates (e.g., resorcinol tetraphenyl diphosphate (RDP), bis(diphenyl) phosphate of hydroquinone and bis(diphenyl) phosphate of bisphenol A); poly-α-olefins; epoxidized soybean oil; silicones, including silicone oils (e.g., poly(dimethyldiphenylsiloxane); esters, such as fatty acid esters (e.g., alkyl stearoyl esters, such as methyl stearate, stearoyl stearate, etc.), waxes (e.g., beeswax, montan wax, paraffin wax, etc.) or combinations including at least one of the above plasticizers, lubricants and release agents.

[0115] Light stabilizers (especially ultraviolet (UV) absorption additives, also known as UV stabilizers) include hydroxybenzophenones (e.g., 2-hydroxy-4-n-octyloxybenzophenone), hydroxybenzotriazoles, cyanoacrylates, oxanilides, benzoxazinones (e.g., 2,2'-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one, which can be commercially obtained under the trade name CYASORB TM UV-3638 from Cytec Industries Inc., Woodland, NJ), aryl salicylates, hydroxybenzotriazoles (e.g., 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole and 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol, which can be commercially obtained under the trade name CYASORB TM 5411 from Cytec Industries Inc. in Woodland, NJ) or combinations including at least one of the above light stabilizers.

[0116] Antioxidant additives include organic phosphites such as tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite; alkylated monophenols or polyphenols; alkylated reaction products of polyphenols with dienes such as tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane; butylated reaction products of p-cresol or dicyclopentadiene; alkylated hydroquinones; hydroxylated thiodiphenyl ethers; alkylene-bisphenols; benzyl compounds; esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid with mono- or polyhydric alcohols; esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with mono- or polyhydric alcohols; esters of thioalkyl or thioaryl compounds such as distearyl thiodipropionate, dilauryl thiodipropionate, bis(tridecyl) thiodipropionate, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid or combinations comprising at least one of the above antioxidants.

[0117] Useful flame retardants include organic compounds containing phosphorus, bromine, and / or chlorine. For regulatory reasons, non-brominated and non-chlorinated phosphorus-containing flame retardants may be preferred in certain applications, such as organic phosphates and organic compounds containing phosphorus-nitrogen bonds.

[0118] Anti-dripping agents can also be used in the composition, such as fibrillating or non-fibrillating fluoropolymers like polytetrafluoroethylene (PTFE). The anti-dripping agent can be encapsulated by a rigid copolymer such as styrene-acrylonitrile copolymer (SAN). PTFE encapsulated in SAN is called TSAN. Based on the total weight of the encapsulated fluoropolymer, TSAN includes 50 wt% PTFE and 50 wt% SAN. Based on the total weight of the copolymer, SAN can include, for example, 75 wt% styrene and 25 wt% acrylonitrile.

[0119] In some aspects, the composition comprises from about 0.001 wt% to about 12 wt% of an additive. Within this range, the composition can comprise at least 0.001 wt%, at least 0.01 wt%, at least 0.1 wt%, at least 0.2 wt%, at least 0.3 wt%, at least 0.4 wt%, at least 0.5 wt%, at least 0.6 wt%, at least 0.7 wt%, at least 0.8 wt%, at least 0.9 wt%, at least 1.0 wt%, at least 1.5 wt%, at least 2.0 wt%, at least 2.5 wt%, at least 3 wt%, at least 4 wt%, at least 5 wt%, up to 12 wt%, up to 11 wt%, up to 10 wt%, up to 9 wt%, up to 8 wt%, up to 7 wt%, up to 6 wt%, up to 5 wt%, up to 4 wt% or up to 3 wt% of the additive.

[0120] Manufacturing method

[0121] The composition can be formed by techniques known to those skilled in the art. For example, extrusion and mixing techniques can be used to combine the components of the resin composition.

[0122] The resin compositions of the present disclosure can be blended with the foregoing ingredients by a variety of methods that involve intimately mixing the materials with any additional additives desired in the formulation. Due to the availability of melt blending equipment in commercial polymer processing facilities, melt processing methods are generally preferred. Illustrative examples of equipment used in such melt processing methods include: co-rotating and counter-rotating extruders, single screw extruders, co-kneaders, disk pack processors, and various other types of extrusion equipment. Preferably, the melt temperature in the method of the present invention is minimized to avoid excessive degradation of the resin. It is generally desirable to maintain the melt temperature in the molten resin composition between about 230 °C and about 350 °C, although higher temperatures can be used provided that the residence time of the resin in the processing equipment remains short. In some aspects, the melt processed composition exits the processing equipment, such as an extruder, through small exit holes in a die. The resulting molten resin strands are cooled by passing the strands through a water bath. The cooled strands can be chopped into pellets for packaging and further processing.

[0123] Aspects of the present disclosure further relate to methods of preparing thermoplastic compositions. One or any of the foregoing components described herein can be dry blended with each other first, or dry blended with any combination of the foregoing components, and then fed from one or more feeders into an extruder, or fed separately from one or more feeders into an extruder. According to various aspects, the disclosed compositions can be prepared by compounding on a twin screw extruder. The materials can be blended together and fed by a main feeder. The extruded composition strands can be processed into pellets and dried for further molding and evaluation. The pellets and molded parts are tested.

[0124] In one aspect, the present disclosure relates to plastic components, e.g., plastic components that are at least partially formed, shaped, or molded from the compositions described herein. Also provided are plastic components that include a resin composition formed according to the methods for forming resin compositions of the present disclosure.

[0125] The components can also be mixed together and then melt blended to form a polymer composition. Melt blending of the components involves the use of shear forces, tensile forces, compressive forces, ultrasonic energy, electromagnetic energy, thermal energy, or a combination including at least one of the foregoing force or energy forms. If the resin is a semi-crystalline organic polymer, the barrel temperature on the extruder during compounding can be set at a temperature at which at least a portion of the polymer has reached a temperature above or equal to about the melting temperature, or if the resin is an amorphous resin, the barrel temperature can be set at a temperature at which at least a portion of the polymer has reached a temperature above or equal to about the flow point (e.g., glass transition temperature). If desired, mixtures including the foregoing components can undergo multiple blending and forming steps. The method can further include processing the composition to provide a molded part having a desired thickness and / or size, such as a component of a compact camera module.

[0126] Properties and Articles

[0127] The disclosed compositions include a liquid crystal polymer, a polyetherimide polymer, a compatibilizer, and an inorganic mineral filler. The polymer composition can exhibit improved dent resistance and particle dispersion while maintaining desired mechanical properties, particularly mechanical properties related to a compact camera module and / or its housing.

[0128] The compositions of the present disclosure exhibit improved dent resistance, characterized by a dent depth less than the dent depth of the original liquid crystal polymer resin, or less than the dent depth of a liquid crystal polymer resin composition and a polyetherimide polymer in the absence of a compatibilizer and / or an inorganic mineral filler. As an example, a 50 mm x 60 mm sample having a thickness of 0.6 mm molded from the composition exhibits dent resistance characterized by a dent depth of 30 - 40 microns as measured using a three-dimensional surface profiler, where the sample is tested using a drop tester with a 50 gram, 1.6 mm diameter steel ball dropped from a height of 50 mm.

[0129] A CCM VCM housing formed from the disclosed composition can exhibit less particulate release than a comparative CCM VCM housing formed from a reference composition, where the reference composition includes the same liquid crystal polymer resin and mica filler but does not include a polyetherimide polymer.

[0130] The compositions of the present disclosure can also exhibit less particulate release or less particle generation upon impact. As an example, compared to reference compositions comprising neat or pure LCP or a combination of neat or pure LCP and the same mineral filler, molded samples comprising the compositions can exhibit less particle generation and greater weld line strength upon impact. The advantageous features of the compositions disclosed herein can make them suitable for a range of uses. Thus, these compositions are suitable candidates for consumer electronic applications (such as compact camera modules) due to their lower particle generation upon impact and improved dent resistance. In various aspects, the present disclosure provides compositions for compact camera modules. Articles of the present disclosure can include compact camera modules formed from the disclosed compositions by any means known in the art.

[0131] The present disclosure encompasses various combinations of elements of the present disclosure, such as combinations of elements from dependent claims that depend from the same independent claim.

[0132] Definitions

[0133] It should also be understood that the terms used herein are for the purpose of describing particular aspects only and are not intended to be limiting. As used in the specification and the claims, the term "comprising" can include aspects "consisting of" and "consisting essentially of". Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. In this specification and the following claims, many terms will be referred to that should be defined herein. As used in this specification and the appended claims, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a thermoplastic polymer component" includes mixtures of two or more thermoplastic polymer components. As used herein, the term "combination" includes blends, mixtures, alloys, reaction products, and the like.

[0134] Ranges can be expressed herein as from one value (the first value) to another value (the second value). When such a range is expressed, the range in some aspects includes one or both of the first value and the second value. Similarly, when a value is expressed as an approximation by use of the antecedent "about", it should be understood that the particular value forms another aspect. It should be further understood that each endpoint of each range in the range is significant both in relation to the other endpoint and independently of the other endpoint. It should also be understood that many values are disclosed herein, and in addition to the value itself, each value is also disclosed herein as "about" the particular value. For example, if the value "10" is disclosed, then "about 10" is also disclosed. It should also be understood that each unit between two particular units is also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.

[0135] As used herein, the terms "about" and "or about" mean that the quantity or value being discussed can be the specified value, approximately the specified value, or about the same as the specified value. In general, it should be understood that, as used herein, unless otherwise indicated or inferred, a nominal value indicates a variation of ±10%. The terms are intended to convey that similar values promote equivalent results or functions recited in the claims. That is, it should be understood that quantities, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximated and / or greater or less as desired, reflecting tolerances, conversion factors, rounding, measurement error, and other factors known to those of ordinary skill in the art. In general, a quantity, size, formulation, parameter, or other quantity or characteristic is "about" or "approximate" whether or not expressly stated as such. It should be understood that when "about" is used before a quantitative value, the parameter also includes the specific quantitative value itself unless otherwise specifically stated.

[0136] As used herein, the term "optional" or "optionally" means that the subsequent described event or circumstance may or may not occur, and the description includes both the case where the event or circumstance occurs and the case where the event or circumstance does not occur. For example, the phrase "optional additional process" means that an additional process may or may not be included, and the described method includes both the method that includes the additional process and the method that does not include the additional process.

[0137] Components for preparing the compositions of the present disclosure and the compositions themselves for use in the methods disclosed herein are disclosed. These and other materials are disclosed herein, and it should be understood that while specific references to each and every individual and collective combination and permutation of these compounds cannot be explicitly disclosed, each combination and permutation is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed, and numerous modifications that can be made to a plurality of molecules including the compound are discussed, then each combination and permutation of the compound and possible modifications are specifically contemplated unless specifically stated to the contrary. Thus, if a class of molecules A, B, and C and a class of molecules D, E, and F are disclosed, and an example of the combination molecule A-D is disclosed, then each combination is separately and collectively contemplated even if each combination is not separately recited, meaning that combinations A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are considered to be disclosed. Similarly, any subset or combination of these combinations is also disclosed. Thus, for example, sub-groups A-E, B-F, and C-E are considered to be disclosed. This concept applies to all aspects of the present application, including but not limited to the steps in the methods of making and using the compositions of the present disclosure. Thus, if there are various additional steps that can be performed, it should be understood that each of these additional steps can be performed in the context of any particular aspect or combination of aspects of the methods of the present disclosure.

[0138] References in the specification and concluding portions to the weight portions of specific elements or components in a composition or article represent the weight relationships between said element or component and any other element or component in the composition or article, which are expressed in weight portions. Thus, in a compound containing 2 weight portions of component X and 5 weight portions of component Y, X and Y are present in a weight ratio of 2:5, and this ratio exists regardless of whether other components are also present in the compound. Unless specifically stated to the contrary, the weight percentages of the components are based on the total weight of the preparation or composition including said components.

[0139] The terms "residue" and "structural unit" as used with respect to the composition of polymers are synonymous throughout the specification.

[0140] As used herein, unless otherwise specified, the terms "weight percentage", "wt%", and "wt.%" are interchangeable and indicate the weight percentage of a given component based on the total weight of the composition. That is, unless otherwise specified, all wt% values are based on the total weight of the composition. It should be understood that the sum of the wt% values of all components in the disclosed composition or preparation is 100.

[0141] Unless otherwise stated to the contrary herein, all test standards are the latest valid standards at the time of filing this application.

[0142] As used herein, the terms "number average molecular weight" or "Mn" are interchangeable and refer to the statistical average molecular weight of all polymer chains in a sample and are defined by the following formula:

[0143]

[0144] where M i is the molecular weight of the chain, and N i is the number of chains of said molecular weight. The M of a polymer (such as a polycarbonate polymer) can be determined by methods well known to those of ordinary skill in the art using molecular weight standards (such as polycarbonate standards or polystyrene standards, preferably certified or traceable molecular weight standards). n .

[0145] As used herein, the terms "weight average molecular weight" or "Mw" are interchangeable and are defined by the following formula:

[0146]

[0147] where M i is the molecular weight of the chain, and N i is the number of chains of said molecular weight. Compared with M n , M wThe molecular weight of a given chain is considered when determining its contribution to the average molecular weight. Thus, the greater the molecular weight of a given chain, the greater its contribution to M w . The M of a polymer (such as a polycarbonate polymer) can be determined by methods well known to those of ordinary skill in the art using molecular weight standards (such as polycarbonate standards or polystyrene standards, preferably certified or traceable molecular weight standards). w .

[0148] In one aspect, "substantially free of" can be less than about 0.5 weight percent (wt%). In another aspect, substantially free of can be less than about 0.1 wt%. In another aspect, substantially free of can be less than about 0.01 wt%. In yet another aspect, substantially free of can be less than about 100 ppm. In yet another aspect, substantially free of can mean an amount below the detectable level, if present. In one aspect, the compositions of the present disclosure are free or substantially free of carbon fillers or carbon-based fillers. In certain aspects, to maintain the colorability of the disclosed compositions, the compositions can be free or substantially free of carbon black, carbon fiber, and / or graphite.

[0149] Each material in the materials disclosed herein is commercially available and / or its production method is known to those skilled in the art. It should be understood that the compositions disclosed herein have certain functions. Certain structural requirements for performing the disclosed functions are disclosed herein, and it should be understood that there are various structures that can perform the same functions associated with the disclosed structures, and these structures generally achieve the same results.

[0150] Aspects of the present disclosure

[0151] In various aspects, the present disclosure relates to and includes at least the following aspects.

[0152] Aspect 1. A composition comprising:

[0153] About 50 wt% to about 85 wt% of a liquid crystal polymer resin;

[0154] About 0.1 wt% to about 15 wt% of a polyetherimide polymer;

[0155] About 0.05 wt% to about 8 wt% of a compatibilizer; and

[0156] About 2 wt% to about 25 wt% of a mineral filler,

[0157] wherein the combined weight percentage values of all components do not exceed 100 wt%, all weight percentage values are based on the total weight of the composition, and

[0158] A 50 mm x 60 mm sample with a thickness of 0.6 mm (millimeter) molded from the composition exhibits indentation resistance, which is characterized by an indentation depth of 30 - 40 μm (micrometer) as measured using a three-dimensional surface profiler, where the sample is tested using a drop tester with a 1.6 mm diameter steel ball weighing 50 grams dropped from a height of 50 mm.

[0159] Aspect 2. The composition according to aspect 1, wherein the liquid crystal polymer resin comprises a polyether resin.

[0160] Aspect 3. The composition according to aspect 1, wherein the liquid crystal polymer resin comprises a liquid crystal polyether resin derived from 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid.

[0161] Aspect 4. The composition according to any one of aspects 1 to 3, wherein the mineral filler comprises talc, clay, mica, wollastonite, titanium dioxide, or a combination thereof.

[0162] Aspect 5. The composition according to any one of aspects 1 to 3, wherein the mineral filler is mica.

[0163] Aspect 6. The composition according to any one of aspects 1 to 4, wherein the weight average molecular weight of the polyetherimide is 47,000 g / mol and the number average molecular weight is 19,000 g / mol.

[0164] Aspect 7. The composition according to any one of aspects 1 to 6, wherein the polyetherimide is present in an amount of about 7.5 wt% to about 10 wt%.

[0165] Aspect 8. The composition according to any one of aspects 1 to 7, wherein the compatibilizer comprises an epoxy-functionalized block copolymer.

[0166] Aspect 9. The composition according to any one of aspects 1 to 7, wherein the compatibilizer comprises an ethylene-glycidyl methacrylate (EGMA) copolymer.

[0167] Aspect 10. The composition according to any one of aspects 1 to 7, wherein the compatibilizer comprises repeating units derived from: (a) ethylene and glycidyl methacrylate; (b) ethylene, C 1-6 alkyl acrylate and glycidyl acrylate; (c) ethylene, methyl acrylate and glycidyl acrylate; (d) ethylene, butyl acrylate and glycidyl acrylate; or (e) ethylene, vinyl acetate or glycidyl acrylate.

[0168] Aspect 11. The composition according to any one of Aspects 1 to 7, wherein the compatibilizer comprises an ethylene-glycidyl methacrylate copolymer, an ethylene-glycidyl methacrylate-methyl acrylate terpolymer, an ethylene-glycidyl methacrylate-vinyl acetate terpolymer, or an ethylene-glycidyl methacrylate copolymer.

[0169] Aspect 12. The composition according to any one of Aspects 1 to 11, further comprising an additive material selected from the group consisting of: metal deactivators; acid scavengers; antioxidants; colorants; dyes; flow promoters; flow modifiers; impact modifiers; lubricants; mold release agents; pigments; quenchers; heat stabilizers; ultraviolet (UV) absorbers; UV reflectors; UV stabilizers; flame retardants; and combinations thereof.

[0170] Aspect 13. The composition according to Aspect 12, wherein the additive material comprises a pigment.

[0171] Aspect 14. The composition according to Aspect 13, wherein the pigment comprises carbon black.

[0172] Aspect 15. An article formed from the composition according to any one of Aspects 1 to 14.

[0173] Aspect 16. The article according to Aspect 15, wherein the article is a component of a mobile compact camera module.

[0174] Aspect 17. A method of forming a composition, the method comprising:

[0175] (a) Combining the following to form a mixture:

[0176] i. From about 50 wt% to about 85 wt% of a liquid crystal polymer resin,

[0177] ii. From about 0.1 wt% to about 15 wt% of a polyetherimide polymer,

[0178] iii. From about 0.05 wt% to about 8 wt% of a compatibilizer, and

[0179] iv. From about 2 wt% to about 25 wt% of a mineral filler; and

[0180] (b) Extruding the mixture to form the composition,

[0181] wherein the combined weight percentage values of all components do not exceed 100 wt%, and all weight percentage values are based on the total weight of the composition, and

[0182] A 50 mm x 60 mm sample with a thickness of 0.6 mm, molded from the composition, exhibits indentation resistance, which is characterized by an indentation depth of 30 - 40 microns as measured using a 3D surface profiler, where the sample is tested using a drop tester with a 1.6 mm diameter steel ball weighing 50 grams dropped from a height of 50 mm.

[0183] Aspect 18. The method according to aspect 17, wherein the composition formed according to the method has one or more of the components, features, or properties according to any one of aspects 2 to 14.

[0184] Examples

[0185] The following examples are presented to provide a complete disclosure and description to one of ordinary skill in the art of how to make and evaluate the compounds, compositions, articles, devices, and / or methods claimed herein, and are intended to be merely exemplary and not intended to limit the disclosure. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperatures, etc.), but some error and deviation should be accounted for. Unless otherwise indicated, parts are parts by weight, temperature is in °C or at ambient temperature, and pressure is at or near atmospheric pressure. Unless otherwise indicated, percentages of compositions are by wt%. There are many variations and combinations of blending conditions, such as component concentrations, extruder design, feed rate, screw speed, temperature, pressure, and other blending ranges and conditions that can be used to optimize the purity and yield of the product obtained from the described processes. Only reasonable and routine experimentation will be required to optimize such process conditions.

[0186] Various compositions were prepared by compounding from the raw materials shown in Table 1( Figure 2 ) on a 37 mm twin - screw extruder. Preparations were made by compounding on a 25 mm Werner Pfleiderer ZSK co - rotating twin - screw extruder having a vacuum - vented mixing screw operating at a screw speed of 300 rpm. The temperature profile is given in Table 2. Prior to pelletizing, the strands were cooled through a water bath. Test parts were molded using an Engel 45,75,90 molding machine for standard physical property testing. Prior to injection molding, the pellets were dried in a forced - air circulation oven at 90 - 110 °C for 3 - 4 hours. Table 2( Figure 3 ) lists the temperature profile of the molding conditions. The injection molding conditions are shown in Table 3( Figure 4 ). Test parts were molded using an Engel 45,75,90 molding machine for standard physical property testing. Prior to injection molding, the pellets were dried in a forced - air circulation oven at 90 - 110 °C for 3 - 4 hours. Table 4( Figure 5) Presents the prepared formulations, which include LCP, polyetherimide, mineral filler, pigment, and compatibilizer. Evaluate the particulate release and dent resistance properties of the formulations.

[0187] Particulate release. The molded samples formed from the composition are evaluated to determine the amount of particulates or particles released upon impact. To measure the particles released due to external impact, the samples are molded into a shape or tool designed to be comparable or similar to the design of a commercially available CCM actuator or housing. Generally, a camera module consists of a lens, a holder, a voice coil motor (VCM), an infrared filter, a sensor, and a flexible printed circuit (FPC). Figure 6A An angled view of the design with corresponding dimensions is shown, which depicts the VCM housing and the VCM carrier. The VCM housing 102 and the lens carrier 104 are shown. Figure 6B An assembled component including the VCM housing 100 and the lens carrier 102 is shown, and the component has undergone a particle release test. Table 5( Figure 7 ) shows additional characteristics of the housings prepared from each formulation. The VCM housing 102 has dimensions of approximately 12 x 12 x 7 mm, and the VCM lens carrier 104 has dimensions of approximately 10.7 x 9.9 x 6 mm.

[0188] According to an internal method, an actual particle / particulate release is counted using a liquid particle counter. The particle release upon impact is tested using a Multisizer 3 Coulter counter with an orifice size of 280 μm (test range from 5.6 to 168 μm), and the electrolyte volume is 200 ml, with a pure water volume of 25 ml. Table 6( Figure 8 ) presents the particle release results. A comparative sample CE1 formed from an LCP resin and mica filler (25 wt%) is also observed. Figure 9 Is a graphical representation of these results.

[0189] As shown in Table 6, compared to pure LCP containing the said amount of mica filler, the total number of particles in the formulations characterized by LCP and PEI shows less particle generation. See the comparison between CE1 and Ex2. Compared to CE1, Ex2 to E6 show less particle generation, indicating that replacing part of the LCP with PEI can help reduce particle generation. The performance of Ex6 is improved by 54%, indicating that reducing the mineral filler loading has a negative impact on particle release (increasing it), but compensating the balance with a PEI composition can improve particle release by reducing the mica filler loading amount.

[0190] Without wishing to be bound by any particular theory, it is believed that the layer orientation within the LCP affects particle release. Particles are generated due to the binding force between the LCP layer and the filler. Formulations including a suitable functional elastomer are thought to alter the orientation of the LCP to make it more isotropic, or more specifically less oriented. Scanning electron microscopy (SEM) images reveal changes in morphology in the presence of the functional elastomer. Figure 10A and 10B show an LCP resin molded bar and an LCP / epoxy - elastomer molded bar, respectively. As Figure 10A and 10B shown, it can be seen that the morphology of the LCP is more isotropic. In Figure 10B , adding an elastomer interferes with the orientation of the resin. It is believed that the disclosed LCP resin blends exhibit improved binding forces between LCP layers or domains and between LCP - filler interfaces, thus reducing particle generation.

[0191] Indentation resistance. The indentation depth of each formulation was measured. A 1.6 mm, 50 - gram steel ball was dropped from a height of 50 mm onto a 50 mm x 60 mm x 0.6 mm thick molded sample using a DuPont drop tester. The indentation depth was measured using a three - dimensional (3D) profiler and the values are shown in Table 7 ( Figure 11 ). Figure 12 is a graphical representation of these results. As shown, the depth performance of Ex5 and Ex6 was improved by 64% and 48%, respectively. These values indicate that reducing the mica filler loading promotes optimal indentation resistance.

[0192] In Figures 13A - 13D , SEM imaging further demonstrates these results. Above Figure 10A shows that CE1 has gaps (dark regions) and defects between the layers or domains of the LCP. Without wishing to be bound by any particular theory, these gaps or spaces may lead to the formation of indentations. Figure 13A presents the morphology of the LCP / PEI blend, which exhibits a denser structure (fewer gaps), and Figure 13B further reveals an island distribution of PEI spheres in an enhanced image. Figure 13C and 13D are magnified to show additional details. It is believed that when the material surface is subjected to a sudden external force (such as a ball drop), the LCP / PEI morphology balances the stiffness and ductility of the formulation. The dispersed PEI domains can act as energy absorbers because the PEI resin is more ductile than the LCP. Additionally, due to the elasticity of the polymer, PEI is thought to contribute to surface elasticity.

[0193] Weld line strength. The weld line strength (as a measure of fracture stress) of 8 mm wide and 0.6 mm thick samples of CE1, Ex5, and Ex6 was tested using a universal testing machine (UTM) at 5 millimeters per second (mm / s). The values are shown in Figure 14 . Both Ex5 and Ex6 showed an improvement in weld line strength compared to CE1. Ex5 showed a 16% improvement compared to CE1.

[0194] A specific combination of LCP, PEI, a compatibilizer, and a specific amount of filler (such as mica) provides a balanced material that achieves improved dent resistance, particle release, and weld line properties.

[0195] The above description is intended to be illustrative and not restrictive. For example, the above examples (or one or more aspects thereof) may be used in combination with each other. Other aspects may be used as would be apparent to one of ordinary skill in the art upon review of the above description. The abstract is provided to allow the reader to quickly ascertain the nature of the technical disclosure. The abstract is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims. Also, in the above detailed description, various features may be grouped together in order to streamline the disclosure. This should not be interpreted as intending that the disclosed features not claimed are essential to any claim. Rather, the subject matter of the invention may lie in less than all of the features of a particular disclosed aspect. Accordingly, the appended claims are hereby incorporated into the detailed description as examples or aspects, where each claim stands on its own as a separate aspect, and it is contemplated that such aspects may be combined with each other in various combinations or permutations. The scope of the present disclosure should be determined with reference to the appended claims and the full scope of equivalents to which such claims are entitled.

[0196] It will be apparent to those skilled in the art that various modifications and variations can be made in the present disclosure without departing from the scope or spirit of the disclosure. Other aspects of the disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure herein. The specification and examples are only to be considered as exemplary, with the true scope and spirit of the disclosure being indicated by the following claims.

[0197] The scope of the patentable subject matter of the present disclosure is defined by the claims and may include other examples that would be contemplated by one of ordinary skill in the art. If such other examples have structural elements that are not different from the literal language of the claims, or if the examples include equivalent structural elements that do not materially differ from the literal language of the claims, then such examples are intended to be within the scope of the claims. It should be understood that the compositions disclosed herein have certain functions. Certain structural requirements for performing the disclosed functions are disclosed herein, and it should be understood that there are various structures that can perform the same function associated with the disclosed structure, and these structures will generally achieve the same result.

Claims

1. A composition comprising: about 50 wt % to about 85 wt % of a liquid crystal polymer resin; about 0.1 wt % to about 15 wt % of a polyetherimide polymer; From about 0.05 wt % to about 8 wt % of a compatibilizer; and about 2 wt % to about 25 wt % of a mineral filler, wherein the combined weight percentage value of all components does not exceed 100 wt %, and all weight percentage values ​​are based on the total weight of the composition, and A 50 mm x 60 mm sample having a thickness of 0.6 mm (millimeter) molded from the composition exhibits dent resistance characterized by a dent depth of 30-40 μm (micrometers) as measured using a three-dimensional surface profiler, wherein the sample is tested using a drop tester using a 1.6 mm diameter steel ball weighing 50 grams dropped from a height of 50 mm. 2 . The composition according to claim 1 , wherein the liquid crystal polymer resin comprises a polyether resin. 3 . The composition according to claim 1 , wherein the liquid crystal polymer resin comprises a liquid crystal polyether resin derived from 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid.

4. The composition of any one of claims 1 to 3, wherein the mineral filler comprises talc, clay, mica, wollastonite, titanium dioxide or a combination thereof.

5. The composition according to any one of claims 1 to 3, wherein the mineral filler is mica.

6. The composition of any one of claims 1 to 4, wherein the polyetherimide has a weight average molecular weight of 47,000 g / mol and a number average molecular weight of 19,000 g / mol.

7. The composition of any one of claims 1 to 6, wherein the polyetherimide is present in an amount of about 7.5 wt% to about 10 wt%.

8. The composition of any one of claims 1 to 7, wherein the compatibilizer comprises an epoxy-functional block copolymer.

9. The composition of any one of claims 1 to 7, wherein the compatibilizer comprises ethylene-glycidyl methacrylate (EGMA) copolymer.

10. The composition of any one of claims 1 to 7, wherein the compatibilizer comprises repeating units derived from: (a) ethylene and glycidyl methacrylate; (b) ethylene, acrylic acid, 1-6 (c) ethylene, methyl acrylate and glycidyl acrylate; (d) ethylene, butyl acrylate and glycidyl acrylate; or (e) ethylene, vinyl acetate or glycidyl acrylate.

11. The composition of any one of claims 1 to 7, wherein the compatibilizer comprises ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-methyl acrylate terpolymer, ethylene-glycidyl methacrylate-vinyl acetate terpolymer, or ethylene-glycidyl methacrylate copolymer.

12. The composition of any one of claims 1 to 11, further comprising an additive material selected from the group consisting of: metal deactivators; acid scavengers; antioxidants; colorants; dyes; flow promoters; flow modifiers; impact modifiers; lubricants; mold release agents; pigments; quenchers; thermal stabilizers; ultraviolet (UV) absorbers; UV reflectors; UV stabilizers; flame retardants; and combinations thereof.

13. The composition of claim 12, wherein the additive material comprises a pigment comprising carbon black.

14. An article formed from the composition of any one of claims 1 to 13, wherein the article is a component of a mobile compact camera module.

15. A method of forming a composition, the method comprising: (a) combining the following to form a mixture: i. about 50 wt % to about 85 wt % of a liquid crystal polymer resin, ii. about 0.1 wt % to about 15 wt % of a polyetherimide polymer, iii. about 0.05 wt % to about 8 wt % of a compatibilizer, and iv. about 2 wt % to about 25 wt % of a mineral filler; and (b) extruding the mixture to form the composition, wherein the combined weight percentage value of all components does not exceed 100 wt %, and all weight percentage values ​​are based on the total weight of the composition, and A 50 mm x 60 mm sample having a thickness of 0.6 mm molded from the composition exhibits dent resistance characterized by a dent depth of 30-40 microns as measured using a three-dimensional surface profiler, wherein the sample is tested using a drop tester using a 1.6 mm diameter steel ball having a weight of 50 grams dropped from a height of 50 mm.

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