WO2017197077A1 - Polyimide compositions and a polyimide test socket housing - Google Patents

Polyimide compositions and a polyimide test socket housing Download PDF

Info

Publication number
WO2017197077A1
WO2017197077A1 PCT/US2017/032093 US2017032093W WO2017197077A1 WO 2017197077 A1 WO2017197077 A1 WO 2017197077A1 US 2017032093 W US2017032093 W US 2017032093W WO 2017197077 A1 WO2017197077 A1 WO 2017197077A1
Authority
WO
WIPO (PCT)
Prior art keywords
titanium dioxide
polyimide
test socket
ppd
phenylenediamine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2017/032093
Other languages
English (en)
French (fr)
Inventor
John W. Simmons
Timothy D. Krizan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to JP2018558325A priority Critical patent/JP2019526163A/ja
Priority to EP17725815.9A priority patent/EP3455292B1/en
Priority to CN201780027829.2A priority patent/CN109071874B/zh
Priority to US16/095,434 priority patent/US20190136054A1/en
Priority to KR1020187034141A priority patent/KR20190008538A/ko
Publication of WO2017197077A1 publication Critical patent/WO2017197077A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
    • C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/08—Oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R1/00—Details of instruments or arrangements of the types included in groups G01R5/00 - G01R13/00 and G01R31/00
    • G01R1/02—General constructional details
    • G01R1/04—Housings; Supporting members; Arrangements of terminals
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R1/00—Details of instruments or arrangements of the types included in groups G01R5/00 - G01R13/00 and G01R31/00
    • G01R1/02—General constructional details
    • G01R1/04—Housings; Supporting members; Arrangements of terminals
    • G01R1/0408—Test fixtures or contact fields; Connectors or connecting adaptors; Test clips; Test sockets
    • G01R1/0433—Sockets for IC's or transistors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R12/00—Structural associations of a plurality of mutually-insulated electrical connecting elements, specially adapted for printed circuits, e.g. printed circuit boards [PCB], flat or ribbon cables, or like generally planar structures, e.g. terminal strips, terminal blocks; Coupling devices specially adapted for printed circuits, flat or ribbon cables, or like generally planar structures; Terminals specially adapted for contact with, or insertion into, printed circuits, flat or ribbon cables, or like generally planar structures
    • H01R12/70—Coupling devices
    • H01R12/7076—Coupling devices for connection between PCB and component, e.g. display
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/004—Additives being defined by their length
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
    • H01R13/02—Contact members
    • H01R13/22—Contacts for co-operating by abutting
    • H01R13/24—Contacts for co-operating by abutting resilient; resiliently-mounted
    • H01R13/2407—Contacts for co-operating by abutting resilient; resiliently-mounted characterized by the resilient means
    • H01R13/2421—Contacts for co-operating by abutting resilient; resiliently-mounted characterized by the resilient means using coil springs
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R2201/00—Connectors or connections adapted for particular applications
    • H01R2201/20—Connectors or connections adapted for particular applications for testing or measuring purposes

Definitions

  • the disclosure generally relates to polyimide compositions, and articles such as test sockets and test sockets made from the aforementioned having improved mechanical properties.
  • polyimide compositions comprising a polyimide and a titanium dioxide filler and test socket housings made of compositions comprising a polyimide and a titanium dioxide filler.
  • Test sockets are used in back-end testing of finished and semi-finished semiconductor packages under a variety of stressed operational situations to evaluate performance characteristics of the semiconductor packages.
  • a test socket often includes a test socket housing that is disposed between pads of a semiconductor package and terminals of a test board.
  • a first aspect of the present invention relates to a test socket housing having through-holes vertically extending through the housing, wherein the housing comprises: a) 40 wt% - 80 wt% polyimide polymer; and b) 20 wt% - 60 wt% rutile titanium dioxide or acicular titanium dioxide.
  • a second aspect of the present invention relates to a test socket comprising: a test socket housing having through-holes vertically extending through the housing, wherein the housing comprises: a) 40 wt% - 80 wt% polyimide polymer; and b) 20 wt% - 60 wt% rutile titanium dioxide or acicular titanium dioxide.
  • a third aspect of the present invention relates to a polyimide composition
  • a polyimide composition comprising: a) 40 wt% - 80 wt% polyimide polymer; and b) 20 wt% - 60 wt% rutile titanium dioxide or acicular titanium dioxide.
  • a second aspect of the present invention relates to a polyimide composition comprising: a) 40 wt% - 80 wt% polyimide polymer; and b) 20 wt% - 60 wt% rutile titanium dioxide.
  • the terms “about” and “at or about”, when used to modify an amount or value, refers to an approximation of an amount or value that is more or less than the precise amount or value recited in the claims or described herein.
  • the precise value of the approximation is determined by what one of skill in the art would recognize as an appropriate approximation to the precise value.
  • the term conveys that similar values, not precisely recited in the claims or described herein, can bring about results or effects that are equivalent to those recited in the claims or described herein, for which one of skill in the art would acknowledge as acceptably brought about by the similar values.
  • the term “article” refers to an unfinished or finished item, thing, object, or an element or feature of an unfinished or finished item, thing or object.
  • the term “article” when an article is unfinished, the term “article” may refer to any item, thing, object, element, device, etc. that has a form, shape, configuration that may undergo further processing in order to become a finished article.
  • the term “preform” may refer to that form, shape, configuration, any part of which may undergo further processing to become finished.
  • FIG. 1 depicts an embodiment of a test socket, in accordance with the present disclosure
  • FIG. 2 depicts an embodiment of a test socket housing, in accordance with the present disclosure
  • FIG. 3 depicts another embodiment of a test socket housing, in accordance with the present disclosure
  • FIG. 4 depicts another embodiment of a test socket housing, in accordance with the present disclosure.
  • FIG. 5 depicts another embodiment of a test socket, in accordance with the present disclosure.
  • article refers to an item, thing, object, element, device, etc. that is in a form, shape, configuration that is suitable for a particular use/purpose without further processing of the entire entity or a portion of it.
  • the terms "about” and “at or about”, when used to modify an amount or value, refers to an approximation of an amount or value that is more or less than the precise amount or value recited in the claims or described herein.
  • the precise value of the approximation is determined by what one of skill in the art would recognize as an appropriate approximation to the precise value.
  • the term conveys that similar values, not precisely recited in the claims or described herein, can bring about results or effects that are equivalent to those recited in the claims or described herein, for which one of skill in the art would acknowledge as acceptably brought about by the similar values.
  • the term “article” refers to an unfinished or finished item, thing, object, or an element or feature of an unfinished or finished item, thing or object.
  • the term “article” when an article is unfinished, the term “article” may refer to any item, thing, object, element, device, etc. that has a form, shape, configuration that may undergo further processing in order to become a finished article.
  • the term “preform” may refer to that form, shape, configuration, any part of which may undergo further processing to become finished.
  • article refers to an item, thing, object, element, device, etc. that is in a form, shape, configuration that is suitable for a particular use/purpose without further processing of the entire entity or a portion of it.
  • An article may comprise one or more element(s) or subassembly(ies) that either are partially finished and awaiting further processing or assembly with other
  • article may refer to a system or configuration of articles.
  • any range set forth herein expressly includes its endpoints unless explicitly stated otherwise. Setting forth an amount, concentration, or other value or parameter as a range specifically discloses all possible ranges formed from any possible upper range limit and any possible lower range limit, regardless of whether such pairs of upper and lower range limits are expressly disclosed herein. Compounds, processes and articles described herein are not limited to specific values disclosed in defining a range in the description.
  • polyimide compositions comprising polyimides and titanium dioxide fillers address the industry needs described herein.
  • Semiconductor processes are performed on a wafer of silicon or other semi conductive material to form a plurality of semiconductor chips.
  • a packaging process is performed on the wafer to form semiconductor packages.
  • Electrical characteristics of the semiconductor package which is manufactured by the above-mentioned processes, are tested. Using typical test methods, the semiconductor package is loaded into a test chamber wherein the semiconductor package is held in a test socket. The semiconductor package in the test socket electrically makes contact with a test board. A test current is supplied to the semiconductor package through the test board to test the electrical characteristics of the semiconductor package.
  • test socket is used as a medium for connecting the semiconductor package to the test board and in particular, a test socket housing.
  • the test socket housing is disposed between the pads of the semiconductor package and the terminals of the test board to exchange signals between them via pins in contact with both.
  • test sockets that product accurate and reliable readings.
  • rapid and continuous insertions and removals of the semiconductor package into and from the test socket place extreme mechanical demands on it and in particular, the test socket housing such that dimensional stability, wear, and compression, -'-performance characteristics of the housing degrade and ultimately may affect the accuracy and reliability of the test socket's readings.
  • test socket housings that can withstand the rigors of semiconductor package testing, and have dimensional stability, wear, and compression.
  • test socket housings comprising polyimides and titanium dioxide fillers address the industry needs described herein.
  • test socket 2 is used to receive successive semiconductor packages 4 in order to perform various quality assurance tests described herein.
  • Semiconductor packages 4 typically include a plurality of electrical terminals 6 that are electrically connected to operative circuitry of the device. Examples of semiconductor packages 4 for use with the test socket of the present invention include but are not limited to ball array, bare die, leadless array, surface mount, and through hole.
  • Electrical terminals 6 of semiconductor packages 4 are made to be in contact with corresponding terminals (or pads) of a test board 8 via pins 10 in order to access the functionality of the operative circuitry.
  • An example of a test board is a printed circuit board (PCB).
  • Pins 10 include but are not limited to spring pins that compress and connect the circuit.
  • Test socket 2 is capable of releasably receiving semiconductor packages 4 and biasing electrical terminals 6 thereof against corresponding terminals of test board 8. Thus, quality assurance tests may be performed on a given semiconductor package 4 while in test socket 2 and semiconductor package 4 may be subsequently removed without suffering significant deformation.
  • Test socket 2 includes a test socket housing 12 that engages semiconductor package 4 and maintains its electrical terminals 6 in registration with the corresponding electrical terminals of test board 8 via pins 10.
  • Test socket 2 may also include a top assembly plate 20 and a bottom assembly plate 22. Plates 20 and 22 function to guide semiconductor package 4 and pins 10 of test socket housing 12 to the correct position for testing.
  • Test socket 2 may additionally include a lid 14 which is either hinged to top assembly plate 20 along one edge or clipped to top assembly plate 20 along several edges, either of which is intended to clamp semiconductor device 4 onto pinslO as lid 14 is closed.
  • test socket 2 may include guide holes 24 which for the top plates 20 and 22 to be aligned with test socket housing 12 via screws or securing pins (not shown).
  • Test sockets and their general design are well known in the industry. The common features of all test sockets are test board pins 10 and a test socket housing 12. The aforementioned is not meant to limit the type of test sockets encompassed by the present invention.
  • Test sockets encompassed by the present invention encompass those that may incorporate a test socket housing having through holes, and disposed between pads of a semiconductor package and terminals of a test board to exchange signals between them.
  • Examples of test sockets include but are not limited to burn-in, development, production, and test contactor sockets.
  • Other examples include ball array, bare die, leadless array, surface mount, and through hole.
  • Test socket housing 12 comprises a generally grid-shaped pattern with a plurality of through holes 18 that receive pins 10 and electrical terminals 6 of semiconductor chip package 4.
  • the dimensions of socket housing 12 may be matched with the dimensions of semiconductor package 4 and test socket 2. Dimensions include height, width, and depth. Other dimensional aspects include but are not limited to number of through holes, pitch, and through hole diameter. Therefore, when different sizes of semiconductor chip packages 4 are to be tested (as is common when non-standardized chip scale semiconductor packages are tested) and/or different types of test sockets are to be used, socket housing 12 may be changed and/or designed as necessary to match semiconductor chip package 4 and/or test socket 2 without undue experimentation.
  • test socket housing is not a standardized term but is synonymous with other descriptions in the art that include but are not limited to a floating guide, a contact plate, guide plate, and an electrical connector.
  • test socket housing encompasses a generally grid-shaped article having through holes, and for use in a test socket where the test socket housing is disposed between pads of a semiconductor package and terminals of a test board to exchange signals between them.
  • Test socket housing 12 may be made of polymeric resins such as polyimides.
  • the polyimide resins may also include fillers to increase the mechanical performance characteristics of the test socket housing 12 so as to withstand the rigors of semiconductor insertion and removal, and to ultimately allow test socket 2 to make accurate and reliable reading.
  • compositions of the present invention may comprise a polyimide powder and a titanium dioxide filler.
  • Polyimides as described herein and for use in articles may contain the
  • the polyimide can be obtained, for example, from the reaction of monomers such as an organic tetracarboxylic acid, or the corresponding anhydride or ester derivative thereof, with an aliphatic or aromatic diamine.
  • a polyimide precursor as used to prepare a polyimide is an organic polymer that becomes the corresponding polyimide when the polyimide precursor is heated or chemically treated.
  • about 60 to 100 mole percent, preferably about 70 mole percent or more, more preferably about 80 mole percent or more, of the repeating units of the polymer chain thereof has a polyimide structure as represented, for example, by the following formula:
  • Ri is a tetravalent aromatic radical having 1 to 5 benzenoid-unsaturated rings of 6 carbon atoms, the four carbonyl groups being directly bonded to different carbon atoms in a benzene ring of the Ri radical and each pair of carbonyl groups being bonded to adjacent carbon atoms in the benzene ring of the Ri radical; and R2 is a divalent aromatic radical having 1 to 5 benzenoid-unsaturated rings of carbon atoms, the two amino groups being directly bonded to different carbon atoms in the benzene ring of the R2 radical.
  • Preferred polyimide precursors are aromatic, and provide, when imidized, polyimides in which a benzene ring of an aromatic compound is directly bonded to the imide group.
  • An especially preferred polyimide precursor includes a polyamic acid having a repeating unit represented, for example, by the following general formula, wherein the polyamic acid can be either a homopolymer or copolymer of two or more of the repeating units:
  • R3 is a tetravalent aromatic radical having 1 to 5 benzenoid-unsaturated rings of 6 carbon atoms, the four carbonyl groups being directly bonded to different carbon atoms in a benzene ring of the R3 radical and each pair of carbonyl groups being bonded to adjacent carbon atoms in the benzene ring of the R3 radical; and R 4 is a divalent aromatic radical having 1 to 5 benzenoid-unsaturated rings of carbon atoms, the two amino groups being directly bonded to different carbon atoms in the benzene ring of the R 4 radical.
  • Typical examples of a polyamic acid having a repeating unit represented by the general formula above are those obtained from pyromellitic dianhydride ("PMDA”) and diaminodiphenyl ether (“ODA”) and 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • a typical example of a polyimide prepared by a solution imidization process is a rigid, aromatic polyimide composition having the recurring unit:
  • polyimide prepared by a solution imidization process is a rigid, aromatic polyimide composition wherein R5 is greater than 60 to about 85 mole percent p phenylene diamine (“PPD”) units and about 15 to less than 40 mole percent m phenylene diamine (“MPD”) units.
  • PPD p phenylene diamine
  • MPD mole percent m phenylene diamine
  • tetracarboxylic acids preferably employed in the practice of the invention, or those from which derivatives useful in the practice of this invention can be prepared, are those having the general formula:
  • A is a tetravalent organic group and R 6 to R9, inclusive, comprise hydrogen or a lower alkyl, and preferably methyl, ethyl, or propyl.
  • the tetravalent organic group A preferably has one of the following structures:
  • X comprises at least one of -(CO)-, -0-, -S-, -SO2-, -CH2-, -C(CH 3 ) 2 -, and -C(CF 3 ) 2 - .
  • aromatic tetracarboxylic acid component there can be mentioned aromatic tetracarboxylic acids, acid anhydrides thereof, salts thereof and esters thereof.
  • aromatic tetracarboxylic acids include 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, pyromellitic acid, 3,3',4,4'- benzophenonetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane, bis(3,4- dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)ether, bis(3,4- dicarboxyphenyl)thioether, bis(3,4-dicarboxyphenyl)phosphine, 2,2-bis(3',4'- dicarboxyphenyl)hexafluoropropane, 2,2-bis[4-(3',4'- di
  • aromatic tetracarboxylic acids can be employed singly or in combination.
  • Preferred is an aromatic tetracarboxylic dianhydride, and particularly preferred are 3,3',4,4'-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 3, 3', 4,4'- benzophenonetetracarboxylic dianhydride, and mixtures thereof.
  • an organic aromatic diamine use is preferably made of one or more aromatic and/or heterocyclic diamines, which are themselves known to the art.
  • aromatic diamines can be represented by the structure: H2N-R10- H2, wherein Rio is an aromatic group containing up to 16 carbon atoms and, optionally, containing up to one heteroatom in the ring, the heteroatom comprising -N-, -0-, or -S-. Also included herein are those Rio groups wherein Rio is a diphenylene group or a diphenylmethane group.
  • diamines are 2,6-diaminopyridine, 3,5-diaminopyridine, m- phenylenediamine, p-phenylene diamine, ⁇ , ⁇ '-methylene dianiline, 2,6-diaminotoluene, and 2,4-diaminotoluene.
  • aromatic diamine components include benzene diamines such as 1,4-diaminobenzene, 1,3-diaminobenzene, and 1,2-diaminobenzene; diphenyl(thio)ether diamines such as 4,4'- diaminodiphenylether, 3,4'-diaminodiphenylether, 3,3'-diaminodiphenylether, and 4,4'- diaminodiphenylthioether; benzophenone diamines such as 3,3'-diaminobenzophenone and 4,4'-diaminobenzophenone; diphenylphosphine diamines such as 3,3'- diaminodiphenylphosphine and 4,4'-diaminodiphenylphosphine; diphenylalkylene diamines such as 3,3'-diaminodiphenylme
  • Other useful diamines have at least one non-heteroatom containing aromatic rings or at least two aromatic rings bridged by a functional group.
  • aromatic diamines can be employed singly or in combination.
  • aromatic diamine component are 1,4-diaminobenzene, 1,3- diaminobenzene, 4,4'-diaminodiphenylether, and mixtures thereof.
  • a polyamic acid can be obtained by polymerizing an aromatic diamine component and an aromatic tetracarboxylic acid component preferably in substantially equimolar amounts in an organic polar solvent.
  • the amount of all monomers in the solvent can be in the range of about 5 to about 40 weight percent, more preferably in the range of about 6 to about 35 weight percent, and most preferably in the range of about 8 to about 30 weight percent.
  • the temperature for the reaction generally is not higher than about 100 °C, preferably in the range of about 10 °C to 80 °C.
  • the time for the polymerization reaction generally is in the range of about 0.2 to 60 hours.
  • the process by which a polyimide is prepared can also vary according to the identity of the monomers from which the polymer is made up.
  • the monomers form a complex salt at ambient temperature. Heating of such a reaction mixture at a moderate temperature of about 100 to about 150°C yields low molecular weight oligomers (for example, a polyamic acid), and these oligomers can, in turn, be transformed into higher molecular weight polymer by further heating at an elevated temperature of about 240 to about 350°C.
  • a solvent such as dimethylacetamide or N-methylpyrrolidinone is typically added to the system.
  • An aliphatic diamine and dianhydride also form oligomers at ambient temperature, and subsequent heating at about 150 to about 200°C drives off the solvent and yields the corresponding polyimide.
  • an aromatic diamine is typically polymerized with a dianhydride in preference to a tetracarboxylic acid, and in such a reaction a catalyst is frequently used in addition to a solvent.
  • a nitrogen-containing base, phenol, or amphoteric material can be used as such a catalyst. Longer periods of heating can be needed to polymerize an aromatic diamine.
  • the ring closure can also be effected by conventionally used methods such as a heat treatment or a process in which a cyclization agent such as pyridine and acetic anhydride, picoline and acetic anhydride, 2,6-lutidine and acetic anhydride, or the like is used.
  • a cyclization agent such as pyridine and acetic anhydride, picoline and acetic anhydride, 2,6-lutidine and acetic anhydride, or the like is used.
  • Preferred the polyimides used herein are infusible polyimides. In some preferred polyimides essentially all of the connecting groups are imide groups. Preferred polyimides include those made from: a tetracarboxylic anhydride (for example pyromellitic dianhydride and/or 3,3',4,4'-biphenyltetracarboxylic dianhydride) and about 60 to about 85 mole percent p-phenylenediamine and about 15 to about 40 mole percent m-phenylenediamine (see U.S.
  • a tetracarboxylic anhydride for example pyromellitic dianhydride and/or 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • Patent 5,886, 129 which is hereby included by reference); 3,3',4,4'-biphenyltetracarboxylic dianhydride and m-phenylenediamine, maleic anhydride and bis(4-aminophenyl)methane; 3,3',4,4'-benzophenone tetracarboxylic dianhydride, toluenediamine and m-phenylenediamine, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, bis(4-aminophenyl)methane and nadic anhydride; trimellitic anhydride and m-phenylenediamine; trimellitic anhydride and bis(4-aminophenyl)ether; 3,3 ',4,4'- biphenyltetracarboxylic dianhydride and bis(4-aminophenyl)ether; 3, 3', 4,4'- biphenyltetracarboxylic
  • An especially preferred polyimide is a polyimide made from a tetracarboxylic anhydride (for example pyromellitic dianhydride and/or 3,3',4,4'-biphenyltetracarboxylic dianhydride) and about 60 to about 85 mole percent p-phenylenediamine and about 15 to about 40 mole percent m-phenylenediamine.
  • a tetracarboxylic anhydride for example pyromellitic dianhydride and/or 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • the polyimide composition may comprise from about 40 wt% to about 80 wt% polyimide powder.
  • the polyimide composition comprises 50 wt%, 60 wt%, 70 wt%, and 80 wt% polyimide powder.
  • the polyimide powder may be a polyimide polymer that is a rigid polyaromatic polyimide derived from 3, 3', 4,4'- biphenyltetracarboxylic acid dianhydride (BPDA) and /?-phenylenediamine (PPD).
  • BPDA 4,4'- biphenyltetracarboxylic acid dianhydride
  • PPD /?-phenylenediamine
  • the polyimide composition comprises from about 40 wt% to about 80 wt% polyimide powder that is a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) and /?-phenylenediamine (PPD).
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • PPD /?-phenylenediamine
  • the polyimides of test socket housing 12 may comprise 40 wt% to 80 wt% of a rigid polyaromatic polyimide derived from 3,3',4,4'- biphenyltetracarboxylic acid dianhydride (BPDA), m-phenylenediamine (MPD), and p- phenylenediamine (PPD).
  • the polyimides of test socket housing 12 may comprise 40 wt% to 60 wt% of a rigid polyaromatic polyimide derived from 3,3',4,4'- biphenyltetracarboxylic acid dianhydride (BPDA), m-phenylenediamine (MPD), and p- phenylenediamine (PPD).
  • BPDA 3,3',4,4'- biphenyltetracarboxylic acid dianhydride
  • MPD m-phenylenediamine
  • PPD p- phenylenediamine
  • the polyimide compositions described herein may include fillers.
  • the titanium dioxide described herein may be rutile acicular grade titanium dioxide and referred to herein as acicular titanium dioxide, or may be rutile grade titanium dioxide.
  • the term rutile refers to the crystal type of the titanium dioxide particles and the term acicular refers to the shape of the particles.
  • the rutile titanium dioxide particles described herein are different from acicular rutile titanium dioxide and do not encompass acicular rutile titanium dioxide particles. Both rutile and acicular are terms of art.
  • the acicular titanium dioxide may have a length of 1.7 microns to 5.15 microns. In an embodiment, the length is about 1.7 microns. In another embodiment, the length is about 2.9 microns.
  • the acicular titanium dioxide may have a diameter of 0.13 microns to 0.27 microns. In an embodiment, the diameter is about 0.13 microns. In another embodiment, the diameter is 0.21 microns.
  • the rutile titanium dioxide may have median particle size in range from about 0.25 microns to about 0.50 microns. In an embodiment, the median particle size is 0.36 microns.
  • the titanium dioxide, acicular and rutile may include surface treatment with alumina, silica, or both.
  • Various surface treatments of titanium dioxide are well known in the art.
  • the surface treatment is a coating.
  • the surface treatment is a continuous coating.
  • the titanium dioxide fillers described herein may be incorporated into the polyimide compositions described herein by adding at any stage during the preparation of polyamic acid.
  • the titanium dioxide filler may be added to the organic solvent prior event to the introduction of the diamine and the dianhydride. It also may be added to the solution in the organic solvent of one or both of the reactants before, during, or after the formation of the polyamic acid. In an embodiment, the titanium dioxide filler is added to a solution of polyamic acid.
  • the particles may represent from 20% wt% to 60 wt%, of the blend of titanium dioxide and polyimide.
  • the use of less than 5 wt% does not provide a significant increase in dielectric constant.
  • the use of amounts greater than 90 wt% and with some polyimides greater than about 70 wt% (about 200 wt% based on the weight of the polyimide) tends to weaken the product and does limit its usefulness.
  • the polyimide composition comprises 20% wt% to 60 wt% of acicular titanium dioxide. In another embodiment, the polyimide composition comprises 20% wt% to 60 wt% of rutile titanium dioxide. In another embodiment, the polyimide composition comprises 20% wt% to 60 wt% of acicular titanium dioxide. In another embodiment, the polyimide composition comprises 40% wt% to 60 wt% of rutile titanium dioxide.
  • acicular titanium dioxide suitable for use with the polyimide compositions described herein include but is not limited to FTL series of acicular titanium dioxide.
  • FTL-100, FTL-110, FTL-200, and FTL-300 [(Ishihara
  • rutile titanium dioxide suitable for use with the polyimide compositions described herein include but are not limited to Ti-PureTM grades of rutile titanium dioxide.
  • R-706 titanium dioxide [The Chemours Company, Wilmington, DE, USA).
  • the polyimide composition may comprise 40 wt% to 60 wt% of a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) and /?-phenylenediamine (PPD); and 20 wt% to 80 wt% of acicular titanium dioxide.
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • PPD /?-phenylenediamine
  • the polyimide composition comprises 50 wt% of a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) and /?-phenylenediamine (PPD) and 50 wt% acicular titanium dioxide.
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • PPD /?-phenylenediamine
  • polyimide composition comprises 60 wt% of a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) and /?-phenylenediamine (PPD); and 40% wt% acicular titanium dioxide.
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • PPD /?-phenylenediamine
  • the polyimide composition may comprise 40 wt% to 60 wt% of a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) and >-phenylenediamine (PPD); and 20 wt% to 80 wt% of rutile titanium dioxide.
  • the polyimide composition comprises 50 wt% of a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) and /?-phenylenediamine (PPD) and 50 wt% rutile titanium dioxide.
  • the polyimide composition comprises 70 wt% of a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) and /?-phenylenediamine (PPD) and 30 wt% rutile titanium dioxide.
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • PPD /?-phenylenediamine
  • the polyimide composition comprises 80 wt% of a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) and /?-phenylenediamine (PPD) and 20 wt% rutile titanium dioxide.
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • PPD /?-phenylenediamine
  • Test socket housing 12 may comprise a polyimide polymer and acicular titanium dioxide.
  • test socket housing 12 may comprise 40 wt% to 80 wt% of a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), m-phenylenediamine (MPD), and p-phenylenediamine (PPD); and 20 wt% to 60 wt% of acicular titanium dioxide.
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • MPD m-phenylenediamine
  • PPD p-phenylenediamine
  • test socket housing 12 may comprise 40 wt% to 60 wt% of a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), m-phenylenediamine (MPD), and p-phenylenediamine (PPD); and 40 wt% to 60 wt% of acicular titanium dioxide.
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • MPD m-phenylenediamine
  • PPD p-phenylenediamine
  • test socket housing 12 comprises 50 wt%, 52 wt%, 57 wt%, or 60 wt% of a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), m-phenylenediamine (MPD), and p-phenylenediamine (PPD).
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • MPD m-phenylenediamine
  • PPD p-phenylenediamine
  • test socket housing 12 comprises 50 wt%, 48 wt%, 43 wt%, or 40 wt% acicular titanium dioxide.
  • Test socket housing 12 may comprise 50 wt%, 52 wt%, 57 wt%, or 60 wt% of a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), m-phenylenediamine (MPD); and p-phenylenediamine (PPD) in combination with 50 w%, 48 wt%, 43 wt%, or 40 wt% acicular titanium dioxide.
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • MPD m-phenylenediamine
  • PPD p-phenylenediamine
  • test socket housing 12 comprises 50 wt% of a rigid
  • polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), m-phenylenediamine (MPD), and p-phenylenediamine (PPD); and 50% wt% acicular titanium dioxide.
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • MPD m-phenylenediamine
  • PPD p-phenylenediamine
  • test socket housing 12 comprises 52 wt% of a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), m-phenylenediamine (MPD), and p-phenylenediamine (PPD); and 48% wt% acicular titanium dioxide.
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • MPD m-phenylenediamine
  • PPD p-phenylenediamine
  • test socket housing 12 comprises 57 wt% of a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), m-phenylenediamine (MPD), and p-phenylenediamine (PPD); and 43% wt% acicular titanium dioxide.
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • MPD m-phenylenediamine
  • PPD p-phenylenediamine
  • test socket housing 12 comprises 60 wt% of a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), m-phenylenediamine (MPD), and p-phenylenediamine (PPD); and 40% wt% acicular titanium dioxide.
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • MPD m-phenylenediamine
  • PPD p-phenylenediamine
  • Test socket housing 12 may comprise a polyimide polymer and rutile titanium dioxide.
  • test socket housing 12 may comprise 40 wt% to 80 wt% of a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), w-phenylenediamine (MPD), and /?-phenylenediamine (PPD); and 20 wt% to 60 wt% of rutile titanium dioxide.
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • MPD w-phenylenediamine
  • PPD /?-phenylenediamine
  • test socket housing 12 may comprise 40 wt% to 60 wt% of a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), w-phenylenediamine (MPD), and ⁇ -phenylenedi amine (PPD); and 40 wt% to 60 wt% of rutile titanium dioxide.
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • MPD w-phenylenediamine
  • PPD ⁇ -phenylenedi amine
  • test socket housing 12 may comprise 70 wt% of a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), w-phenylenediamine (MPD), and /?-phenylenediamine (PPD); and 30 wt% of rutile titanium dioxide.
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • MPD w-phenylenediamine
  • PPD /?-phenylenediamine
  • test socket housing 12 comprises 50 wt% or 60 wt% of a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), w-phenylenediamine (MPD), and /?-phenylenediamine (PPD).
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • MPD w-phenylenediamine
  • PPD /?-phenylenediamine
  • test socket housing 12 comprises 50 wt% or 40 wt% rutile titanium di oxi de .
  • Test socket housing 12 may comprise 50 wt or 60 wt% of a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), m- phenylenediamine (MPD), and /?-phenylenediamine (PPD) in combination with 50 w% or 40 wt% rutile titanium dioxide.
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • MPD m- phenylenediamine
  • PPD /?-phenylenediamine
  • test socket housing 12 comprises 50 wt% of a rigid
  • polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), w-phenylenediamine (MPD), and /?-phenylenediamine (PPD); and 50% wt% rutile titanium dioxide.
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • MPD w-phenylenediamine
  • PPD /?-phenylenediamine
  • test socket housing 12 comprises 60 wt% of a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), w-phenylenediamine (MPD), and /?-phenylenediamine (PPD); and 40% wt% rutile titanium dioxide.
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • MPD w-phenylenediamine
  • PPD /?-phenylenediamine
  • titanium dioxide-filled polyimide compositions described herein may be made, and shapes and parts made from, by techniques normally used for making shapes and parts from infusible polymeric materials, namely by the application of heat and pressure to powder mixtures of various ingredients as described in U.S. Pat. No.
  • Blanks for testing may be prepared according to above and then machined to the final article dimensions as required.
  • One having ordinary skill in the art in the process of making blanks and machining them will recognize that various dimensions of articles may be formed without undo experimentation, and via blank forming and machining process commonly used in the industry. Examples
  • tensile strength, elongations %, modulus, and flex modulus are measured using ASTM D1708 and ASTM D790. All test pieces were molded from the titanium dioxide-filled polyimide compositions described herein using a procedure substantially according to the procedure described in U.S. Pat. No. 4,360,626 (especially column 2, lines 54-60).
  • BPDA 3,3',4,4'- biphenyltetracarboxylic anhydride
  • MPD m-phenylenediamine
  • PPD p- phenylenediamine
  • Acicular titanium dioxide filler used in the examples E described herein are from the FTL series of acicular titanium dioxide. In particular, FTL-100, FTL-110, FTL-200, and FTL-300 [(Ishihara Corporation, USA (ISK)].
  • Rutile titanium dioxide filler used in the examples E described herein are from Ti-PureTM grades of rutile titanium dioxide. In particular, R-706 titanium dioxide [The Chemours Company, Wilmington, DE, USA).
  • Polyamide Compositions BPDA, MPD, and PPD Derived with, Acicular Titanium Dioxide
  • Particles of a polyimide composition containing 52% of a polyimide made from BPDA, PPD, & MPD (1 : 1 molar ratio BPDA to combined PPD and MPD; and 70/30 wt% ratio of PPD/MPD) and 48 wt% acicular titanium dioxide (FTL-100) were prepared according to the method described in U.S. Pat. No. 5,886, 129 (specifically example 7). The particles were milled and passed through a 20 mesh screen and used to prepare tensile bar samples. Bars made were measured to have a tensile strength of 23763 MPa, elongation of 1.6%, modulus of 16073 MPa, and flex modulus of 13339 MPa.
  • Particles of a polyimide composition containing 60% of a polyimide made from BPDA, PPD, & MPD (1 : 1 molar ratio BPDA to combined PPD and MPD; and 70/30 wt% ratio of PPD/MPD) and 40 wt% acicular titanium dioxide (FTL-100) were prepared according to the method described in U.S. Pat. No. 5,886, 129 (specifically example 7). The particles were milled and passed through a 20 mesh screen and used to prepare tensile bar samples. Bars made were measured to have a tensile strength of 26304 MPa, elongation of 3%, modulus of 13259 MPa, and flex modulus of 13406 MPa.
  • Particles of a polyimide composition containing 50% of a polyimide made from BPDA, PPD, & MPD (1 : 1 molar ratio BPDA to combined PPD and MPD; and 70/30 wt% ratio of PPD/MPD) and 50 wt% acicular titanium dioxide (FTL-110) were prepared according to the method described in U.S. Pat. No. 5,886, 129 (specifically example 7). The particles were milled and passed through a 20 mesh screen and used to prepare tensile bar samples. Bars made were measured to have a tensile strength of 27096 MPa, elongation of 2.2%, modulus of 16334 MPa, and flex modulus of 17279 MPa.
  • Particles of a polyimide composition containing 57% of a polyimide made from BPDA, PPD, & MPD (1 : 1 molar ratio BPDA to combined PPD and MPD; and 70/30 wt% ratio of PPD/MPD) and 43 wt% acicular titanium dioxide (FTL-110) were prepared according to the method described in U.S. Pat. No. 5,886, 129 (specifically example 7). The particles were milled and passed through a 20 mesh screen and used to prepare tensile bar samples. Bars made were measured to have a tensile strength of 25908 MPa, elongation of 2.5%, modulus of 15463 MPa, and flex modulus of 14461 MPa.
  • Particles of a polyimide composition containing 50% of a polyimide made from BPDA, PPD, & MPD (1 : 1 molar ratio BPDA to combined PPD and MPD; and 70/30 wt% ratio of PPD/MPD) and 50 wt% acicular titanium dioxide (FTL-200) were prepared according to the method described in U.S. Pat. No. 5,886, 129 (specifically example 7). The particles were milled and passed through a 20 mesh screen and used to prepare tensile bar samples. Bars made were measured to have a tensile strength of 2332 MPa, elongation of 2.1%, modulus of 13526 MPa, and flex modulus of 16503 MPa.
  • Particles of a polyimide composition containing 60% of a polyimide made from BPDA, PPD, & MPD (1 : 1 molar ratio BPDA to combined PPD and MPD; and 70/30 wt% ratio of PPD/MPD) and 40 wt% acicular titanium dioxide (FTL-300) were prepared according to the method described in U.S. Pat. No. 5,886, 129 (specifically example 7). The particles were milled and passed through a 20 mesh screen and used to prepare tensile bar samples. Bars made were measured to have a tensile strength of 23389 MPa, elongation of 2.5%, modulus of 12108 MPa, and flex modulus of 12569 MPa.
  • DuPontTMVespel®SCP-5000 grade resin (an unfilled polyimide resin) was used to prepare tensile bars. Bars made were measured to have a tensile strength of 22962 MPa, elongation of 6.2%, modulus of 5770 MPa, and flex modulus of 5630 MPa.
  • DuPontTMVespel®SCP-5000 grade resin is available from E.I. DuPont de Nemours & Co., Wilmington, DE, USA.
  • DuPontTMVespel®SCP-5050 grade resin is available from E.I. DuPont de Nemours & Co., Wilmington, DE, USA.
  • Polyamide Compositions BPDA, MPD, and PPD Derived, with Rutile Titanium Dioxide
  • exemplary and comparative are listed in Table 2.
  • Particles of a polyimide composition containing 50% of a polyimide made from BPDA, PPD, & MPD (1 : 1 molar ratio BPDA to combined PPD and MPD; and 70/30 wt% ratio of PPD/MPD) and 50 wt% rutile titanium dioxide (R-706) were prepared according to the method described in U.S. Pat. No. 5,886, 129 (specifically example 7). The particles were milled and passed through a 20 mesh screen and used to prepare tensile bar samples. Bars made were measured to have a tensile strength of 21252 MPa, elongation of 2.0%, modulus of 9701 MPa, and flex modulus of 11537 MPa.
  • Particles of a polyimide composition containing 50% of a polyimide made from BPDA, PPD, & MPD (1 : 1 molar ratio BPDA to combined PPD and MPD; and 70/30 wt% ratio of PPD/MPD) and 50 wt% rutile titanium dioxide (R-706) were prepared according to the method described in U.S. Pat. No. 5,886, 129 (specifically example 7). The particles were milled and passed through a 20 mesh screen and used to prepare tensile bar samples. Bars made were measured to have a tensile strength of 21252 MPa, elongation of 2.9%, modulus of 10802 MPa, and flex modulus of 11695 MPa.
  • Particles of a polyimide composition containing 60% of a polyimide made from BPDA, PPD, & MPD (1 : 1 molar ratio BPDA to combined PPD and MPD; and 70/30 wt% ratio of PPD/MPD) and 40 wt% rutile titanium dioxide (R-706) were prepared according to the method described in U.S. Pat. No. 5,886, 129 (specifically example 7). The particles were milled and passed through a 20 mesh screen and used to prepare tensile bar samples. Bars made were measured to have a tensile strength of 16938 MPa, elongation of 1.7%, modulus of 9352 MPa, and flex modulus of 9667 MPa.
  • Particles of a polyimide composition containing 63% of a polyimide made from BPDA, PPD, & MPD (1 : 1 molar ratio BPDA to combined PPD and MPD; and 70/30 wt% ratio of PPD/MPD) and 37 wt% rutile titanium dioxide (R-706) were prepared according to the method described in U.S. Pat. No. 5,886, 129 (specifically example 7). The particles were milled and passed through a 20 mesh screen and used to prepare tensile bar samples. Bars made were measured to have a tensile strength of 21857 MPa, elongation of 4.0%, modulus of 8316 MPa, and flex modulus of 8756 MPa.
  • Particles of a polyimide composition containing 70% of a polyimide made from BPDA, PPD, & MPD (1 : 1 molar ratio BPDA to combined PPD and MPD; and 70/30 wt% ratio of PPD/MPD) and 30 wt% rutile titanium dioxide (R-706) were prepared according to the method described in U.S. Pat. No. 5,886, 129 (specifically example 7). The particles were milled and passed through a 20 mesh screen and used to prepare tensile bar samples. Bars made were measured to have a tensile strength of 20939 MPa, elongation of 3.9%, modulus of 7306 MPa, and flex modulus of 7384 MPa.
  • DuPontTMVespel®SCP-5000 grade resin (an unfilled polyimide resin) was used to prepare tensile bars. Bars made were measured to have a tensile strength of 22962
  • DuPontTMVespel®SCP-5000 grade resin is available from E.I. DuPont de Nemours & Co., Wilmington, DE, USA.
  • DuPontTMVespel®SCP-5050 grade resin is available from E.I. DuPont de Nemours & Co., Wilmington, DE, USA.
  • Polyamide Compositions BPDA and PPD Derived, with Acicular Titanium Dioxide [00128]
  • the following examples for polyimide compositions having acicular titanium dioxide (exemplary and comparative) are listed in Tables 3 and 4.
  • Particles of a polyimide composition containing 50% of a polyimide made from BPDA & PPD (1 : 1 molar ratio BPDA to PPD; and 50 wt% acicular titanium dioxide (FTL-100) were prepared according to the method described in U.S. Pat. No. 5,886,129 (specifically example 7). The particles were milled and passed through a 20 mesh screen and used to prepare tensile bar samples. Bars made were measured to have a tensile strength of 16307 MPa, elongation of 0.9%, and tensile modulus of 2361944 PSI.
  • Particles of a polyimide composition containing 60% of a polyimide made from BPDA & PPD (1 : 1 molar ratio BPDA to PPD; and 40 wt% acicular titanium dioxide (FTL-110) were prepared according to the method described in U.S. Pat. No. 5,886,129 (specifically example 7). The particles were milled and passed through a 20 mesh screen and used to prepare tensile bar samples. Bars made were measured to have a tensile strength of 21403 MPa, elongation of 1.7%, tensile modulus of 1886882 PSI, and flex modulus of 13118 MPa.
  • Particles of a polyimide composition containing 50% of a polyimide made from BPDA & PPD (1 : 1 molar ratio BPDA to PPD; and and 50 wt% acicular titanium dioxide (FTL-110) were prepared according to the method described in U.S. Pat. No. 5,886,129 (specifically example 7). The particles were milled and passed through a 20 mesh screen and used to prepare tensile bar samples. Bars made were measured to have a tensile strength of 20665 MPa, elongation of 1.6%, tensile modulus of 2043845 PSI, and flex modulus of 15647 MPa.
  • Particles of a polyimide composition containing 50% of a polyimide made from BPDA & PPD (1 : 1 molar ratio BPDA to PPD; and 50 wt% acicular titanium dioxide (FTL-200) were prepared according to the method described in U.S. Pat. No. 5,886,129 (specifically example 7). The particles were milled and passed through a 20 mesh screen and used to prepare tensile bar samples. Bars made were measured to have a tensile strength of 17176 MPa, elongation of 1.2%, and tensile modulus of 1964772 PSI. COMPARATIVE EXAMPLE 5
  • Particles of a polyimide composition containing 97.6% of a polyimide made from BPDA & PPD (1 : 1 molar ratio BPDA to PPD; and 2.4 wt% synthetic graphite (bulk density of 0.100 g/cc; particle size of 5.0 ⁇ at a density of 1.81 g/cc; and d50 commercially available from Imerys Graphite & Carbon, Switzerland) were prepared according to the method described in U.S. Pat. No. 5,886, 129 (specifically example 7). The particles were milled and passed through a 20 mesh screen and used to prepare tensile bar samples. Bars made were measured to have a tensile strength of 18553 MPa, elongation of 2.9%, and tensile modulus of 951663 PSI.
  • Particles of a polyimide composition containing 70% of a polyimide made from BPDA & PPD (1 : 1 molar ratio BPDA to PPD; and 30 wt% synthetic graphite (bulk density of 0.100 g/cc; particle size of 5.0 ⁇ at a density of 1.81 g/cc; and d50 commercially available from Imerys Graphite & Carbon, Switzerland) were prepared according to the method described in U.S. Pat. No. 5,886, 129 (specifically example 7). The particles were milled and passed through a 20 mesh screen and used to prepare tensile bar samples. Bars made were measured to have a tensile strength of 13549 MPa, elongation of 2.9%, and tensile modulus of 1021216 PSI.
  • Particles of a polyimide composition containing 50% of a polyimide made from BPDA & PPD (1 : 1 molar ratio BPDA to PPD; and 50 wt% synthetic graphite (bulk density of 0.100 g/cc; particle size of 5.0 ⁇ at a density of 1.81 g/cc; and d50 commercially available from Imerys Graphite & Carbon, Switzerland) were prepared according to the method described in U.S. Pat. No. 5,886, 129 (specifically example 7). The particles were milled and passed through a 20 mesh screen and used to prepare tensile bar samples. Bars made were measured to have a tensile strength of 10603 MPa, elongation of 1.9%, and tensile modulus of 1243534 PSI.
  • Particles of a polyimide composition containing 100% of a polyimide made from BPDA & PPD (1 : 1 molar ratio BPDA to PPD were prepared according to the method described in U.S. Pat. No. 5,886, 129 (specifically example 7). The particles were milled and passed through a 20 mesh screen and used to prepare tensile bar samples. Bars made were measured to have a tensile strength of 19603 MPa and elongation of 3.2%. [00137] Table 3
  • Particles of a polyimide composition containing 50% of a polyimide made from BPDA & PPD (1 : 1 molar ratio BPDA to PPD; and 50 wt% rutile titanium dioxide (R- 706) were prepared according to the method described in U.S. Pat. No. 5,886, 129 (specifically example 7). The particles were milled and passed through a 20 mesh screen and used to prepare tensile bar samples. Bars made were measured to have a tensile strength of 18045 MPa, elongation of 1.7%, tensile modulus of 1572774 PSI, and flex modulus of 12790 MPa.
  • Particles of a polyimide composition containing 70% of a polyimide made from BPDA & PPD (1 : 1 molar ratio BPDA to PPD; and 30 wt% rutile titanium dioxide (R- 706) were prepared according to the method described in U.S. Pat. No. 5,886, 129 (specifically example 7). The particles were milled and passed through a 20 mesh screen and used to prepare tensile bar samples. Bars made were measured to have a tensile strength of 16776 MPa, elongation of 1.9%, and tensile modulus of 1333009 PSI.
  • Particles of a polyimide composition containing 80% of a polyimide made from BPDA & PPD (1 : 1 molar ratio BPDA to PPD; and 20 wt% rutile titanium dioxide (R- 706) were prepared according to the method described in U.S. Pat. No. 5,886, 129 (specifically example 7). The particles were milled and passed through a 20 mesh screen and used to prepare tensile bar samples. Bars made were measured to have a tensile strength of 14045 MPa, elongation of 1.5%, and tensile modulus of 1319481 PSI.
  • Comparative examples 5, 6, 7, and 8 are the same as in Table 4 above.
  • embodiment 1 is a test socket housing having through-holes vertically extending through the housing, wherein the housing comprises: a) 40 wt% - 80 wt% polyimide polymer; and b) 20 wt% - 60 wt% rutile titanium dioxide or acicular titanium dioxide.
  • Embodiment 2 is the test socket housing of embodiment 1, wherein the housing comprises: a) 40 wt% - 80 wt% polyimide polymer; and b) 20 wt% - 60 wt% rutile titanium dioxide.
  • Embodiment 3 is the test socket housing of embodiment 1, wherein the housing comprises: a) 40 wt% - 80 wt% polyimide polymer; and b) 20 wt% - 60 wt% acicular titanium dioxide.
  • Embodiment 4 is the test socket housing of embodiment 1, wherein the rutile titanium dioxide or the acicular titanium dioxide is in a range from 40 wt% to 60 wt%.
  • Embodiment 5 is the test socket housing of embodiment 1, wherein the rutile titanium dioxide is in a range from 40 wt% to 60 wt%.
  • Embodiment 6 is the test socket housing of embodiment 1, wherein the acicular titanium dioxide is in a range from 40 wt% to 60 wt%.
  • Embodiment 7 is the test socket housing of embodiment 1, wherein the polyimide polymer is a rigid polyaromatic polyimide derived from 3,3',4,4'- biphenyltetracarboxylic acid dianhydride (BPDA), w-phenylenediamine (MPD), and p- phenylenediamine (PPD).
  • BPDA 3,3',4,4'- biphenyltetracarboxylic acid dianhydride
  • MPD w-phenylenediamine
  • PPD p- phenylenediamine
  • Embodiment 8 is the test socket housing of embodiment 1, wherein the acicular titanium dioxide has a length of about 1.7 microns to about 5.15 microns.
  • Embodiment 9 is the test socket housing of embodiment 3, wherein the acicular titanium dioxide has a length of about 1.7 microns.
  • Embodiment 10 is the test socket housing of embodiment 3, wherein the acicular titanium dioxide has a length of about 2.9 microns.
  • Embodiment 11 is the test socket housing of embodiment 1, wherein the acicular titanium dioxide has a diameter of about 0.13 microns to about 0.27 microns.
  • Embodiment 12 is the test socket housing of embodiment 11, wherein the acicular titanium dioxide has a diameter of about 0.13 microns.
  • Embodiment 13 is the test socket housing of embodiment 11, wherein the acicular titanium dioxide has a diameter of about 0.21 microns.
  • Embodiment 14 is the test socket housing of embodiment 1, wherein the acicular titanium dioxide is surfaced treated with alumina.
  • Embodiment 15 is the test socket housing of embodiment 1, wherein the acicular titanium dioxide is surfaced treated with silica.
  • Embodiment 16 is the test socket housing of embodiment 1, wherein the acicular titanium dioxide is surfaced treated with alumina and silica.
  • Embodiment 17 is the test socket housing of embodiment 1, wherein the polyimide polymer is in a range from 40 wt% to 60 wt% of a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), m- phenylenediamine (MPD), and /?-phenylenediamine (PPD).
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • MPD m- phenylenediamine
  • PPD /?-phenylenediamine
  • Embodiment 18 is the test socket housing of embodiment 7, wherein the polyimide polymer is 50 wt%, 52 wt%, 57 wt%, or 60 wt%; and is a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), m- phenylenediamine (MPD), and /?-phenylenediamine (PPD).
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • MPD m- phenylenediamine
  • PPD /?-phenylenediamine
  • Embodiment 19 is the test socket housing of embodiment 1, wherein the acicular titanium dioxide is 50 wt%, 48 wt%, 43 wt%, or 40 wt%.
  • Embodiment 20 is the test socket housing of embodiment 1, wherein the polyimide polymer is 50 wt% and is a rigid polyaromatic polyimide derived from
  • Embodiment 21 is the test socket housing of embodiment 1, wherein the polyimide polymer is 52 wt% and is a rigid polyaromatic polyimide derived from
  • Embodiment 22 is the test socket housing of embodiment 1, wherein the polyimide polymer is 57 wt% and is a rigid polyaromatic polyimide derived from
  • Embodiment 23 is the test socket housing according to claim 1, wherein the polyimide polymer is 60 wt% and is a rigid polyaromatic polyimide derived from
  • embodiment 24 is a test socket comprising: a test socket housing having through-holes vertically extending through the housing and wherein the housing comprises: a) 40 wt% - 80 wt% polyimide polymer; and b) 20 wt% - 60 wt% rutile titanium dioxide or acicular titanium dioxide.
  • Embodiment 25 is the test socket housing of embodiment 24, wherein the housing comprises: a) 40 wt% - 80 wt% polyimide polymer; and b) 20 wt% - 60 wt% rutile titanium dioxide.
  • Embodiment 26 is the test socket housing of embodiment 24, wherein the housing comprises: a) 40 wt% - 80 wt% polyimide polymer; and b) 20 wt% - 60 wt% acicular titanium dioxide.
  • Embodiment 30 is the test socket housing of embodiment 24, wherein the rutile titanium dioxide or the acicular titanium dioxide is in a range from 40 wt% to 60 wt%.
  • Embodiment 28 is the test socket housing of embodiment 24, wherein the rutile titanium dioxide is in a range from 40 wt% to 60 wt%.
  • Embodiment 29 is the test socket housing of embodiment 24, wherein the acicular titanium dioxide is in a range from 40 wt% to 60 wt%.
  • Embodiment 30 is the test socket of embodiment 24, wherein the polyimide polymer is a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), w-phenylenediamine (MPD), and /?-phenylenediamine (PPD).
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • MPD w-phenylenediamine
  • PPD /?-phenylenediamine
  • Embodiment 31 is the test socket of embodiment 24, wherein the acicular titanium dioxide has a length of about 1.7 microns to about 5.15 microns.
  • Embodiment 32 is the test socket of embodiment 31, wherein the acicular titanium dioxide has a length of about 1.7 microns.
  • Embodiment 33 is the test socket of embodiment 31, wherein the acicular titanium dioxide has a length of about 2.9 microns.
  • Embodiment 34 is the test socket according of embodiment 24, wherein the acicular titanium dioxide has a diameter of about 0.13 microns to about 0.27 microns.
  • Embodiment 35 is the test socket of embodiment 34, wherein the acicular titanium dioxide has a diameter of about 0.13 microns.
  • Embodiment 36 is the test socket of embodiment 34, wherein the acicular titanium dioxide has a diameter of about 0.21 microns.
  • Embodiment 37 is the test socket of embodiment 24, wherein the acicular titanium dioxide is surfaced treated with alumina.
  • Embodiment 38 is the test socket of embodiment 24, wherein the acicular titanium dioxide is surfaced treated with silica.
  • Embodiment 39 is the test socket of embodiment 24, wherein the acicular titanium dioxide is surfaced treated with alumina and silica.
  • Embodiment 40 is the test socket of embodiment 24, wherein the test socket is selected from a group consisting of: ball array, bare die, leadless array, surface mount, and through hole.
  • Embodiment 41 is the test socket of embodiment 24, wherein the polyimide polymer is in a range from 40 wt% to 60 wt% and is a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), m- phenylenediamine (MPD), and /?-phenylenediamine (PPD).
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • MPD m- phenylenediamine
  • PPD /?-phenylenediamine
  • Embodiment 42 is the test socket of embodiment 29, wherein the polyimide polymer is 50 wt%, 52 wt%, 57 wt%, or 60 wt% and is a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), m- phenylenediamine (MPD), and /?-phenylenediamine (PPD).
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • MPD m- phenylenediamine
  • PPD /?-phenylenediamine
  • Embodiment 43 is the test socket of embodiment 24, wherein the acicular titanium dioxide is 50 wt%, 48 wt%, 43 wt%, or 40 wt%.
  • Embodiment 44 is the test socket of embodiment 24, wherein the polyimide polymer is 50 wt% and is a rigid polyaromatic polyimide derived from 3,3',4,4'- biphenyltetracarboxylic acid dianhydride (BPDA), w-phenylenediamine (MPD), and p- phenylenediamine (PPD) and; the acicular titanium dioxide is 50 wt%.
  • BPDA 3,3',4,4'- biphenyltetracarboxylic acid dianhydride
  • MPD w-phenylenediamine
  • PPD p- phenylenediamine
  • Embodiment 45 is the test socket of embodiment 24, wherein the polyimide polymer is 52 wt% and is a rigid polyaromatic polyimide derived from 3,3',4,4'- biphenyltetracarboxylic acid dianhydride (BPDA), w-phenylenediamine (MPD), and p- phenylenediamine (PPD) and; the acicular titanium dioxide is 48 wt%.
  • BPDA 3,3',4,4'- biphenyltetracarboxylic acid dianhydride
  • MPD w-phenylenediamine
  • PPD p- phenylenediamine
  • Embodiment 46 is the test socket of embodiment 24, wherein the polyimide polymer is 57 wt% and is a rigid polyaromatic polyimide derived from 3,3',4,4'- biphenyltetracarboxylic acid dianhydride (BPDA), w-phenylenediamine (MPD), and p- phenylenediamine (PPD) and; the acicular titanium dioxide is 43 wt%.
  • BPDA 3,3',4,4'- biphenyltetracarboxylic acid dianhydride
  • MPD w-phenylenediamine
  • PPD p- phenylenediamine
  • Embodiment 47 is the test socket of embodiment 24, wherein the polyimide polymer is 60 wt% and is a rigid polyaromatic polyimide derived from 3,3',4,4'- biphenyltetracarboxylic acid dianhydride (BPDA), w-phenylenediamine (MPD), and p- phenylenediamine (PPD) and; the acicular titanium dioxide is 40 wt%.
  • BPDA 3,3',4,4'- biphenyltetracarboxylic acid dianhydride
  • MPD w-phenylenediamine
  • PPD p- phenylenediamine
  • Embodiment 48 is the test socket housing of embodiment 1, wherein the rutile titanium dioxide has a median particle size in a range from 0.25 microns to 0.50 microns.
  • Embodiment 49 is the test socket housing of embodiment 48, wherein the rutile titanium dioxide has a median particle size of 0.36 microns.
  • Embodiment 50 is the test socket housing of embodiment 1, wherein the rutile titanium dioxide is surfaced treated with alumina.
  • Embodiment 51 is the test socket housing of embodiment 1, wherein the rutile titanium dioxide is surfaced treated with silica.
  • Embodiment 52 is the test socket housing of embodiment 1, wherein the rutile titanium dioxide is surfaced treated with alumina and silica.
  • Embodiment 53 is the test socket housing of embodiment 1, wherein the polyimide polymer is in a range from 40 wt% to 60 wt% and is a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), m- phenylenediamine (MPD), and /?-phenylenediamine (PPD.
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • MPD m- phenylenediamine
  • PPD /?-phenylenediamine
  • Embodiment 54 is the test socket housing of embodiment 1, wherein the polyimide polymer is 50 wt% or 60 wt%, and is a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), w-phenylenediamine (MPD), and ⁇ -phenylenediamine (PPD).
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • MPD w-phenylenediamine
  • PPD ⁇ -phenylenediamine
  • Embodiment 55 is the test socket housing of embodiment 1, wherein the rutile titanium dioxide is 50 wt% or 40 wt%.
  • Embodiment 56 is the test socket housing of embodiment claim 1, wherein the polyimide polymer is 50 wt% and is a rigid polyaromatic polyimide derived from
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • MPD w-phenylenediamine
  • PPD /?-phenylenediamine
  • rutile titanium dioxide 40 wt%.
  • Embodiment 57 is the test socket housing of embodiment 1, wherein the polyimide polymer is 60 wt% and is a rigid polyaromatic polyimide derived from
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • MPD w-phenylenediamine
  • PPD /?-phenylenediamine
  • rutile titanium dioxide 40 wt% 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • MPD w-phenylenediamine
  • PPD /?-phenylenediamine
  • Embodiment 58 is the test socket of embodiment 24, wherein the rutile titanium dioxide has a median particle size in a range from 0.25 microns to 0.50 microns.
  • Embodiment 59 is the test socket of embodiment 58, wherein the rutile titanium dioxide has a median particle size of 0.36 microns.
  • Embodiment 60 is the test socket of embodiment 24, wherein the rutile titanium dioxide is surfaced treated with alumina.
  • Embodiment 61 is the test socket of embodiment 24, wherein the rutile titanium dioxide is surfaced treated with silica.
  • Embodiment 62 is the test socket of embodiment 24, wherein the rutile titanium dioxide is surfaced treated with alumina and silica.
  • Embodiment 63 is the test socket of embodiment 24, wherein the test socket is selected from a group consisting of: ball array, bare die, leadless array, surface mount, and through hole.
  • Embodiment 64 it the test socket of embodiment 24, wherein the polyimide polymer is in a range from 40 wt% to 60 wt% and is a rigid polyaromatic polyimide derived from 3,3 ',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), m- phenylenediamine (MPD), and ?-phenylenediamine (PPD).
  • BPDA 3,3 ',4,4'-biphenyltetracarboxylic acid dianhydride
  • MPD m- phenylenediamine
  • PPD ?-phenylenediamine
  • Embodiment 65 is the test socket of embodiment 24, wherein the polyimide polymer is 50 wt% or 60 wt%, and is a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), w-phenylenediamine (MPD), and ⁇ -phenylenediamine (PPD).
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • MPD w-phenylenediamine
  • PPD ⁇ -phenylenediamine
  • Embodiment 66 is the test socket of embodiment 24, wherein the rutile titanium dioxide is present in 50 wt%, 40 wt%, 37 wt% or 30 wt%.
  • Embodiment 67 is the test socket of embodiment 24, wherein the polyimide polymer is 50 wt% and is a rigid polyaromatic polyimide derived from 3,3',4,4'- biphenyltetracarboxylic acid dianhydride (BPDA), w-phenylenediamine (MPD), and p- phenylenediamine (PPD) and; the rutile titanium dioxide is 50 wt%.
  • BPDA 3,3',4,4'- biphenyltetracarboxylic acid dianhydride
  • MPD w-phenylenediamine
  • PPD p- phenylenediamine
  • Embodiment 68 is the test socket of embodiment 24, wherein the polyimide polymer is 60 wt% and is a rigid polyaromatic polyimide derived from 3,3',4,4'- biphenyltetracarboxylic acid dianhydride (BPDA), w-phenylenediamine (MPD), and p- phenylenediamine (PPD) and; the rutile titanium dioxide is 40 wt% .
  • BPDA 3,3',4,4'- biphenyltetracarboxylic acid dianhydride
  • MPD w-phenylenediamine
  • PPD p- phenylenediamine
  • embodiment 69 is a polyimide composition comprising: a) 40 wt% - 60 wt% polyimide polymer; and b) 20 wt% - 60 wt% acicular titanium dioxide.
  • Embodiment 70 is the composition of embodiment 69, wherein the polyimide polymer is a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxyl acid dianhydride (BPDA) and /?-phenylenediamine (PPD).
  • BPDA 3,3',4,4'-biphenyltetracarboxyl acid dianhydride
  • PPD /?-phenylenediamine
  • Embodiment 71 is the composition of embodiment 69, wherein the acicular titanium dioxide has a length of about 1.7 microns to about 5.15 microns.
  • Embodiment 72 is the composition of embodiment 71, wherein the acicular titanium dioxide has a length of about 1.7 microns.
  • Embodiment 73 is the composition of embodiment 71, wherein the acicular titanium dioxide has a length of about 2.9 microns.
  • Embodiment 74 is the composition of embodiment 69, wherein the acicular titanium dioxide has a diameter of about 0.13 microns to about 0.27 microns.
  • Embodiment 75 is the composition of embodiment 74, wherein the acicular titanium dioxide has a diameter of about 0.13 microns.
  • Embodiment 76 is the composition of embodiment 73, wherein the acicular titanium dioxide has a diameter of about 0.21 microns.
  • Embodiment 77 is the composition of embodiment 69, wherein the acicular titanium dioxide is surfaced treated with alumina.
  • Embodiment 78 is the composition of embodiment 69, wherein the acicular titanium dioxide is surfaced treated with silica.
  • Embodiment 79 is the composition of embodiment 69, wherein the acicular titanium dioxide is surfaced treated with alumina and silica.
  • Embodiment 80 is the composition of embodiment 69, wherein the polyimide polymer is in a range from 40 wt% to 60 wt% of a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) and /?-phenylenediamine (PPD).
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • PPD /?-phenylenediamine
  • Embodiment 81 is composition of embodiment 70, wherein the polyimide polymer is 50 wt%, 52 wt%, 57 wt%, or 60 wt%; and is a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) and p- phenylenediamine (PPD).
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • PPD p- phenylenediamine
  • Embodiment 82 is the composition of embodiment 69, wherein the acicular titanium dioxide is 50 wt%, 48 wt%, 43 wt%, or 40 wt%.
  • Embodiment 83 is the composition of embodiment 69, wherein the polyimide polymer is 50 wt% and is a rigid polyaromatic polyimide derived from 3, 3', 4,4'- biphenyltetracarboxylic acid dianhydride (BPDA) and /?-phenylenediamine (PPD); and the acicular titanium dioxide is 50 wt%.
  • BPDA 4,4'- biphenyltetracarboxylic acid dianhydride
  • PPD /?-phenylenediamine
  • Embodiment 84 is the composition of embodiment 69, wherein the polyimide polymer is 52 wt% and is a rigid polyaromatic polyimide derived from 3,3',4,4'- biphenyltetracarboxylic acid dianhydride (BPDA) and /?-phenylenediamine (PPD); and the acicular titanium dioxide is 48 wt%.
  • BPDA 3,3',4,4'- biphenyltetracarboxylic acid dianhydride
  • PPD /?-phenylenediamine
  • Embodiment 85 is the composition of embodiment 69, wherein the polyimide polymer is 57 wt% and is a rigid polyaromatic polyimide derived from 3,3',4,4'- biphenyltetracarboxylic acid dianhydride (BPDA) and /?-phenylenediamine (PPD); and the acicular titanium dioxide is 43 wt%.
  • BPDA 3,3',4,4'- biphenyltetracarboxylic acid dianhydride
  • PPD /?-phenylenediamine
  • Embodiment 86 is the composition of embodiment 69, wherein the polyimide polymer is 60 wt% and is a rigid polyaromatic polyimide derived from 3,3',4,4'- biphenyltetracarboxylic acid dianhydride (BPDA) and /?-phenylenediamine (PPD); and the acicular titanium dioxide is 40 wt%.
  • BPDA 3,3',4,4'- biphenyltetracarboxylic acid dianhydride
  • PPD /?-phenylenediamine
  • Embodiment 87 is a composition comprising: a) 40 wt% - 60 wt% polyimide polymer; and b) 40 wt% - 60 wt% rutile titanium dioxide.
  • Embodiment 88 is the composition of embodiment 87, wherein the polyimide polymer is a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) and /?-phenylenediamine (PPD).
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • PPD /?-phenylenediamine
  • Embodiment 89 is the composition of embodiment 87, wherein the rutile titanium dioxide has a median particle size in a range from 0.25 microns to 0.50 microns.
  • Embodiment 90 is the composition of embodiment 89, wherein the rutile titanium dioxide has a median particle size of 0.36 microns.
  • Embodiment 91 is the composition of embodiment 87, wherein the rutile titanium dioxide is surfaced treated with alumina.
  • Embodiment 92 is composition of embodiment 87, wherein the rutile titanium dioxide is surfaced treated with silica.
  • Embodiment 93 is the composition of embodiment 87, wherein the rutile titanium dioxide is surfaced treated with alumina and silica.
  • Embodiment 94 is the composition of embodiment 87, wherein the polyimide polymer is in a range from 40 wt% to 60 wt% and is a rigid polyaromatic polyimide derived from 3,3 ',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) and p- phenylenediamine (PPD.
  • BPDA 3,3 ',4,4'-biphenyltetracarboxylic acid dianhydride
  • PPD p- phenylenediamine
  • Embodiment 95 is the composition of embodiment 87, wherein the polyimide polymer is 50 wt% or 60 wt%, and is a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) and /?-phenylenediamine (PPD).
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • PPD /?-phenylenediamine
  • Embodiment 96 is the composition of embodiment 87, wherein the rutile titanium dioxide is 50 wt% or 40 wt%.
  • Embodiment 97 is the composition of embodiment claim 87, wherein the polyimide polymer is 50 wt% and is a rigid polyaromatic polyimide derived from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) and /?-phenylenediamine (PPD); and the rutile titanium dioxide is 40 wt%.
  • BPDA 3,3',4,4'-biphenyltetracarboxylic acid dianhydride
  • PPD /?-phenylenediamine
  • Embodiment 98 is the composition of embodiment 87, wherein the polyimide polymer is 60 wt% and is a rigid polyaromatic polyimide derived from 3,3',4,4'- biphenyltetracarboxylic acid dianhydride (BPDA) and /?-phenylenediamine (PPD); and the rutile titanium dioxide 40 wt%.
  • BPDA 3,3',4,4'- biphenyltetracarboxylic acid dianhydride
  • PPD /?-phenylenediamine
  • titanium dioxide-filled polyimide parts especially test socket housings, have been provided that satisfy the advantages described herein.
  • acicular titanium dioxide-filled polyimide parts especially test socket housings, have been provided that satisfy the advantages described herein.
  • polyimide compositions especially those containing rutile titanium dioxide or acicular titanium dioxide, have been provided that satisfy the advantages described herein.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Engineering & Computer Science (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Measuring Leads Or Probes (AREA)
  • Connecting Device With Holders (AREA)
PCT/US2017/032093 2016-05-12 2017-05-11 Polyimide compositions and a polyimide test socket housing Ceased WO2017197077A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2018558325A JP2019526163A (ja) 2016-05-12 2017-05-11 ポリイミド組成物およびポリイミド試験ソケットハウジング
EP17725815.9A EP3455292B1 (en) 2016-05-12 2017-05-11 Polyimide compositions and a polyimide test socket housing
CN201780027829.2A CN109071874B (zh) 2016-05-12 2017-05-11 聚酰亚胺组合物以及聚酰亚胺测试插座壳体
US16/095,434 US20190136054A1 (en) 2016-05-12 2017-05-11 Polyimide compositions and a polyimide test socket housing
KR1020187034141A KR20190008538A (ko) 2016-05-12 2017-05-11 폴리이미드 조성물 및 폴리이미드 테스트 소켓 하우징

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US201662335229P 2016-05-12 2016-05-12
US201662335222P 2016-05-12 2016-05-12
US201662335225P 2016-05-12 2016-05-12
US62/335,222 2016-05-12
US62/335,225 2016-05-12
US62/335,229 2016-05-12

Publications (1)

Publication Number Publication Date
WO2017197077A1 true WO2017197077A1 (en) 2017-11-16

Family

ID=58772643

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2017/032093 Ceased WO2017197077A1 (en) 2016-05-12 2017-05-11 Polyimide compositions and a polyimide test socket housing

Country Status (6)

Country Link
US (1) US20190136054A1 (enExample)
EP (1) EP3455292B1 (enExample)
JP (1) JP2019526163A (enExample)
KR (1) KR20190008538A (enExample)
CN (2) CN109071874B (enExample)
WO (1) WO2017197077A1 (enExample)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201911133D0 (en) * 2019-08-05 2019-09-18 Qinetiq Ltd Materials and methods
KR102548091B1 (ko) * 2021-04-16 2023-06-27 주식회사 대림 폴리이미드를 포함하는 반도체 소자 테스트 소켓용 성형체 및 이의 제조방법

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4360626A (en) 1981-04-24 1982-11-23 E. I. Du Pont De Nemours And Company Oxidatively stable polyimide compositions
US5886129A (en) 1997-07-01 1999-03-23 E. I. Du Pont De Nemours And Company Oxidatively stable rigid aromatic polyimide compositions and process for their preparation
DE20316645U1 (de) * 2003-10-29 2005-03-10 Fan, Wei-Fang, Jwu Beei Modulare elastische Kontaktstiftgruppevorrichtung
EP2072581A1 (en) * 2006-10-11 2009-06-24 Sumitomo Electric Industries, Ltd. Polyimide tube, method for production thereof, method for production of polyimide varnish, and fixing belt
US20110056539A1 (en) * 2008-05-20 2011-03-10 E.I. Du Pont De Nemours And Company Assemblies comprising a thermally and dimensionally stable polyimide film, an electrode and an absorber layer, and methods relating thereto
WO2012050972A2 (en) * 2010-09-29 2012-04-19 E. I. Du Pont De Nemours And Company Polyimide resins for high temperature applications

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4331970A (en) * 1978-09-18 1982-05-25 General Electric Company Use of dispersed solids as fillers in polymeric materials to provide material for semiconductor junction passivation
DE68927376D1 (de) * 1988-12-27 1996-11-28 Mitsui Toatsu Chemicals Verfahren zur Herstellung einer Buchse für eine integrierte Schaltung
JP2000143984A (ja) * 1998-11-05 2000-05-26 Showa Denko Kk フッ素化ポリイミド樹脂組成物及びその製造方法
ATE441950T1 (de) * 2001-04-03 2009-09-15 Kureha Corp Ic-fassung
JP2004035825A (ja) * 2002-07-05 2004-02-05 Kanegafuchi Chem Ind Co Ltd 半導電性ポリイミドフィルムおよびその製造方法
US7876087B2 (en) * 2006-09-12 2011-01-25 Innoconnex, Inc. Probe card repair using coupons with spring contacts and separate atachment points
US8433029B2 (en) * 2007-12-14 2013-04-30 Global Nuclear Fuel—Americas, LLC Determination of safety limit minimum critical power ratio
CN102712753B (zh) * 2009-11-20 2015-08-26 E·I·内穆尔杜邦公司 热稳定的且尺寸稳定的聚酰亚胺薄膜及与其相关的方法
CN101805517B (zh) * 2010-03-02 2012-05-09 天津恒通时代电工材料科技有限公司 一种无机颗粒填充的聚酰亚胺薄膜的制造方法
CN101831175A (zh) * 2010-04-01 2010-09-15 辽宁科技大学 一种无色透明的聚酰亚胺纳米复合材料膜及其制备方法
WO2016053328A1 (en) * 2014-10-01 2016-04-07 E. I. Du Pont De Nemours And Company Spindle cover comprising non-thermoplstic polyimide as part of a beverage can printing unit

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4360626A (en) 1981-04-24 1982-11-23 E. I. Du Pont De Nemours And Company Oxidatively stable polyimide compositions
US5886129A (en) 1997-07-01 1999-03-23 E. I. Du Pont De Nemours And Company Oxidatively stable rigid aromatic polyimide compositions and process for their preparation
DE20316645U1 (de) * 2003-10-29 2005-03-10 Fan, Wei-Fang, Jwu Beei Modulare elastische Kontaktstiftgruppevorrichtung
EP2072581A1 (en) * 2006-10-11 2009-06-24 Sumitomo Electric Industries, Ltd. Polyimide tube, method for production thereof, method for production of polyimide varnish, and fixing belt
US20110056539A1 (en) * 2008-05-20 2011-03-10 E.I. Du Pont De Nemours And Company Assemblies comprising a thermally and dimensionally stable polyimide film, an electrode and an absorber layer, and methods relating thereto
WO2012050972A2 (en) * 2010-09-29 2012-04-19 E. I. Du Pont De Nemours And Company Polyimide resins for high temperature applications

Also Published As

Publication number Publication date
CN112920601A (zh) 2021-06-08
CN109071874A (zh) 2018-12-21
US20190136054A1 (en) 2019-05-09
CN109071874B (zh) 2021-02-05
KR20190008538A (ko) 2019-01-24
EP3455292B1 (en) 2021-06-23
EP3455292A1 (en) 2019-03-20
JP2019526163A (ja) 2019-09-12

Similar Documents

Publication Publication Date Title
EP1400552B1 (en) Polyimide compositions useful as dielectric substrates for electronic applications, and methods relating thereto
KR101485729B1 (ko) 폴리이미드 수지 조성물, 필름, 접착제 및 부품
US20090069532A1 (en) Polyimide Film
KR102317327B1 (ko) 폴리이미드 필름 및 그 제조방법
CN111742012A (zh) 聚酰亚胺前体树脂组合物
KR102362385B1 (ko) 고탄성 및 고내열 폴리이미드 필름 및 그 제조방법
WO2018051715A1 (ja) 難燃性樹脂組成物及び樹脂付き銅箔
JP7381197B2 (ja) 回路基板及び多層回路基板
US20050215715A1 (en) Blends of high temperature resins suitable for fabrication using powdered metal or compression molding techniques
JP2020055186A (ja) 金属張積層板及び回路基板
EP3455292B1 (en) Polyimide compositions and a polyimide test socket housing
JP2021070824A (ja) ポリイミド組成物、樹脂フィルム、積層体、カバーレイフィルム、樹脂付き銅箔、金属張積層板及び回路基板
KR100710099B1 (ko) 폴리이미드 필름 및 그의 제조 방법 및 그의 이용
EP0618269B1 (en) Thermosetting resin compositions and their use for making resin articles and thin film wiring boards
JP5090653B2 (ja) ポリイミド樹脂及びポリイミドフィルム
KR102548091B1 (ko) 폴리이미드를 포함하는 반도체 소자 테스트 소켓용 성형체 및 이의 제조방법
JP7045117B2 (ja) オリゴアミノマレイミド
CN109337070A (zh) 树脂组合物
WO2011086627A1 (ja) ポリイミドフィルム及びその製造方法
US20090011223A1 (en) Polyimide Film and Method for Production Thereof
JP7786044B2 (ja) フッ素樹脂基板積層体及びフッ素樹脂基板積層体の製造方法
KR20020065722A (ko) 폴리이미드 고내열 접착제 및 이를 이용한 접착테이프
WO2024211079A1 (en) Molded polyimide article
TWI574997B (zh) 聚醯胺酸組成物及其應用
JP2025032608A (ja) 接着フィルム、接着シート、及び接着シートの作製方法

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2018558325

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20187034141

Country of ref document: KR

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17725815

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017725815

Country of ref document: EP

Effective date: 20181212