TW202246406A - Composite particulate material, process for making the same and use - Google Patents

Abstract

The present disclosure relates to a composite particulate material comprising a fluoropolymer particle and an inorganic nanoparticle and a process for making the composite particulate. It further relates to a dielectric film comprising the fluoropolymer composite particulate and use of the composite particulate in electronic devices.

Description

Composite particulate material, its production method and use

The present disclosure relates to composite particulate materials comprising fluoropolymer particles and inorganic nanoparticles and methods for making the composite particulates. The present disclosure also relates to dielectric films comprising the fluoropolymer composite particles and uses of the composite particles in electronic devices.

Resin particulate materials are widely used in the microelectronics industry as fillers in resin compositions. The rapid development of the microelectronics industry has created a great demand for dielectric polymer materials with improved electrical properties for printed circuit boards (PCBs). Because the transmission of large amounts of data is expensive, computers and other electronic devices are moving to higher frequencies. Today, many systems operate at 1 to 10GHz, and new applications will operate at frequencies as high as 20GHz, or 30GHz, or higher than 100GHz.

Fluoropolymer particles have been used as fillers in polymer compositions for the manufacture of printed circuit boards because of their low dielectric constant (D _k ) and dissipation factor (D _f ), which are desirable in high frequency signal transmission . However, fluoropolymer particles have poor adhesion to polymer compositions due to their inert chemical nature, which results in lower mechanical properties. Surface modification of fluoropolymer particles is used to improve their compatibility with polymer compositions and thus improve mechanical properties. In some cases, inorganic particulate materials have been used to modify the nonstick surface of fluoropolymer particles and form composite particles. However, fluoropolymer particles or inorganic particles must be coated with a primer or adhesion promoter that is compatible with both fluoropolymer and inorganic particles.

Fluoropolymer composite particles are expected to be free of substances with high environmental impact. There is a need to manufacture fluoropolymer composite particles without using any primers or adhesion promoters, while uniformly and firmly attaching inorganic particulate material to fluoropolymer particulate material.

The present disclosure provides a fluoropolymer composite particle that is substantially free of primers or adhesion promoters including silane and hydroxyl functional groups. Fluoropolymer composite particles can be used as fillers in polymer compositions to form films that adhere uniformly to substrates and have excellent adhesion to substrates while maintaining low dielectric properties and good mechanical properties .

The drawings illustrate embodiments to improve understanding of the concepts presented herein.

Figure 1 is a photograph showing optical microscope observations of the results of film 2/copper foil laminates according to the present disclosure cut with a 355nm UV laser.

Figure 2 is a photograph showing the results of cutting with a 355nm UV laser of a Film 3/copper foil laminate according to the present disclosure under an optical microscope.

FIG. 3 is a photograph showing the optical microscope observation results of the film 5/copper foil laminate according to the present disclosure cut with a 355 nm UV laser.

FIG. 4 is a scanning electron microscope (SEM) photograph (magnification x 2000) showing the result of observing the cross-section of the film 11 according to the present disclosure.

FIG. 5 is a SEM photograph (magnification x 2000) showing the result of observing the cross-section of the film 13 according to the present disclosure.

As used throughout this specification, unless the context clearly indicates otherwise, the following abbreviations shall have the following meanings: °C = degree Celsius; g = gram; nm = nanometer; μm = micron (micron, micrometer); mm = millimeter; sec. = second; min. = minute; hr = hour; rpm = revolutions per minute; and kgf/ ^cm2 = kilogram-force/square centimeter. Unless otherwise indicated, all amounts are percent by weight ("wt.%") and all ratios are molar ratios. All numerical ranges are inclusive and combinable in any order, except where expressly such numerical ranges are constrained to add up to 100%. Unless otherwise indicated, all polymer and oligomer molecular weights are weight average molecular weights ("Mw") in g/mol or Daltons and were determined using gel permeation chromatography with polystyrene standards products for comparison.

The term "substantially free" means 5% or less, or 4% or less, or 3% or less, or 2% or less, or 1% or less silane or hydroxyl Functional groups are present in the composite particulate material.

Throughout this specification, the terms "film", "sheet" and "layer" are used interchangeably.

Throughout this specification, the terms "powder(s)", "particulates" and "particles" are used interchangeably.

In this specification, unless otherwise explicitly indicated or indicated to the contrary by the context of use, embodiments of the inventive subject matter are stated or described as comprising, including, including, When containing, having certain features or elements, composed of/constituted by certain features or elements, one or more features or elements other than those expressly stated or described may also be present in the In the implementation. Alternative embodiments of the disclosed subject matter are described as consisting essentially of certain features or elements in which embodiment features or elements that would materially alter the principle of operation or the distinguishing characteristics of the embodiments are absent. Another alternative embodiment of the inventive subject matter described is described as consisting of certain features or elements, in which embodiment, or in insubstantial variations thereof, only the features or elements specifically stated or described are present.

Also, "a/an" is used to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the invention, suitable methods and materials are described below. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

To the extent not described herein, many details regarding specific materials, processing behavior, and circuits are conventional and can be found in organic light-emitting diode displays, photodetectors, photovoltaic cells ( photovoltaic cell), and semiconductor building blocks are found in textbooks and other sources.

The present disclosure provides a composite particulate material comprising fluoropolymer particles and inorganic nanoparticles having an average particle size of less than 200 nm, wherein the composite particulate does not substantially contain silane or hydroxyl functional groups. In some embodiments, the composite particulate material comprises 5% or less, or 4% or less, or 3% or more Fewer, or 2% or less, or 1% or less silane or hydroxyl functional groups. In one embodiment, the composite particulate material comprises fluoropolymer particles as a core surrounded by inorganic nanoparticles.

For the purposes of this disclosure, the term fluoropolymer is intended to mean any polymer containing at least one, if not more, fluorine atoms within a repeating unit of the polymer structure. The term fluoropolymer or fluoropolymer component is also intended to mean a fluoropolymer resin (ie fluororesin). These terms are used interchangeably throughout this specification.

Typically, fluoropolymers are polymeric materials that contain fluorine atoms covalently bonded to or bonded to repeating molecules of the polymer. Suitable fluoropolymer components of the present disclosure may include:

1. "PFA" is poly(tetrafluoroethylene-co-perfluoro[alkyl vinyl ether]), including its variants or derivatives, having at least 50, 60, 70, 80, 85, 90 , 95, 96, 97, 98, 99 or about 100 weight percent of the following moiety:

Wherein R ₁ is C _n F _2n+1 , wherein n can be any natural number equal to or greater than 1 (including up to 20 or greater), typically n is equal to 1 to 3; x and y are mole fractions, wherein x is in the range of 0.95 to 0.99, typically 0.97; and y is in the range of 0.01 to 0.05, typically 0.03, and wherein the melt flow rate described in ASTM D 1238 is in the range of 1 to 100 (g/10min), or 1 to 50 (g/10min), or 2 to 30 (g/10min), or 5 to 25 (g/10min).

2. "FEP" is poly(tetrafluoroethylene-co-hexafluoropropylene) [also known as poly(tetrafluoroethylene-co-hexafluoropropylene) copolymer], derived in whole or in part from tetrafluoroethylene and hexafluoropropylene, including its variants or derivatives, having At least 50, 60, 70, 80, 85, 90, 95, 96, 97, 98, 99, or about 100 weight percent of the entire polymer of:

wherein x and y are mole fractions, wherein x is in the range of 0.85 to 0.95, or 0.92; y is in the range of 0.05 to 0.15, or 0.08; and wherein the melt flow rate described in ASTM D 1238 is Between 1 to 100 (g/10min), or 1 to 50 (g/10min), or 2 to 30 (g/10min), or 5 to 25 (g/10min). The FEP copolymers used in the present disclosure may be derived directly or indirectly from: (i.) 50, 55, 60, 65, 70 or 75 percent to about 75, 80, 85, 90 or 95 percent tetrafluoroethylene; and ( ii.) 5, 10, 15, 20 or 25 percent to about 25, 30, 35, 40, 45 or 50 percent (typically 7 to 27 percent) hexafluoropropylene.

3. "PTFE" means polytetrafluoroethylene, including its variants or derivatives, derived in whole or in part from tetrafluoroethylene and having at least 50, 60, 70, 80, 85, 90, 95, 96 , 97, 98, 99 or about 100 weight percent of the following moieties:

-(CF ₂ -CF ₂ ) _x -

where x is equal to any natural number from 50 to 500,000.

4. "ETFE" refers to poly(ethylene-co-tetrafluoroethylene), including its variants or derivatives, derived in whole or in part from ethylene and tetrafluoroethylene, and having at least 50, 60, 70, 80, 85, 90, 95, 96, 97, 98, 99 or about 100 weight percent of the following moieties:

-(CH ₂ -CH ₂ ) _x -(CF ₂ -CF ₂ ) _y -

wherein x and y are mole fractions, wherein x is in the range of 0.40 to 0.60, or 0.50; and y is in the range of 0.40 to 0.60, or 0.50; and wherein the melt flow rate described in ASTM D 1238 It is in the range of 1 to 100 (g/10min), or 1 to 50 (g/10min), or 2 to 30 (g/10min), or 5 to 25 (g/10min).

Fluoropolymer resins are generally known for their high temperature stability, chemical resistance, favorable electrical properties (especially high frequency properties), low moisture absorption, low friction properties and low viscosity. Other potentially useful fluoropolymers may include, but are not limited to, chlorotrifluoroethylene polymers (CTFE), tetrafluoroethylene-trifluorochloroethylene copolymers (TFE/CTFE), tetrafluoroethylene-perfluorodioxolane (tetrafluoroethylene- perfluorodioxolane) copolymer (TFE/PDD), polychlorotrifluoroethylene (PCTFE), ethylene chlorotrifluoroethylene copolymer (ECTFE), polyvinyl fluoride (PVF) and polyvinylidene fluoride (PVDF). Two or more of these fluoropolymers can be used in the present disclosure.

Fluoropolymer resins can be converted into micropowders or granules by grinding the resin in a hammer mill, or by using other mechanical means of particle size reduction. In one embodiment, the resin is cooled, such as with solidified carbon dioxide or liquid nitrogen, prior to grinding or other mechanical manipulation to reduce particle size. The fluoropolymer micropowders or particles of the present disclosure may have high molecular weight species and/or low molecular weight species. The average particle size of the fluoropolymer may vary between 0.05 to 100 μm, or 0.5 to 50 μm, or 0.5 to 20 μm, or 1 to 20 μm, or 1 to 18 μm, or 1 to 15 μm. Commercial products of fluoropolymer particles may include, but are not limited to, MJX-10000 (a perfluoroalkoxyalkane powder with an average particle size of 4.5 μm, available from Chemours-Mitsui Fluoroproducts Co., Tokyo, Japan, Ltd.)); 532G-9420 PFA POWDER CLEAR (a perfluoroalkoxyalkane powder with an average particle size of 7 μm, commercially available from The Chemours Company FC, LLC, Wilmington, Delaware). 3M ^™ Dyneon ^™ fluoroplastic powder FEP ^6322PZ (fluorinated ethylene propylene powder with an average particle size of 6.4 μm, commercially available from 3M Company (The 3M Company), St. 4 μm polytetrafluoroethylene powder, commercially available from Solvay SA, Brussels, Belgium); INOFLON PFA 8115 (perfluoroalkoxyalkane powder with an average particle size of 20 μm, available from Rock, Texas Dyer U.S. GFL Co., Ltd. (GFL America, LLC) commercially available); FEP micropowder TPD-700S (the fluorinated ethylene propylene powder of average particle size system 4-20 μ m, can be obtained from China Fuzhou Fuzhou Tuoda New Material Co., Ltd. (Fuzhou Topda New Material Co., Ltd.)); and FLUO 300 (polytetrafluoroethylene powder with an average particle size of 5-6 μm, commercially available from Micro Powders, Inc., Asphalt Village, New York).

In some embodiments, the inorganic nanoparticles are substantially uniformly distributed on the surface of the fluoropolymer particle. The inorganic nanoparticles comprise nanoparticles of at least one inorganic oxide, including, but not limited to, cesium oxide (ceria), silicon oxide (such as silicon dioxide), zirconium oxide (such as zirconia), aluminum oxide (such as aluminum oxide) , titanium oxide (such as titanium dioxide) and iron oxide. In some embodiments, two or more of the above-mentioned inorganic nanoparticles can be used. The ratio of the average particle size of the inorganic nanoparticles to the average particle size of the fluoropolymer particles can vary from 1/50 to 1/10,000, or 1/20 to 1/2000, or 1/10 to 1/5000. The average particle size of the inorganic nanoparticles may range from 1 to 195 nm, or 3 to 185 nm, or 5 to 175 nm, or 5 to 150 nm, or 5 to 100 nm, or 5 to 80 nm, or 5 to 70 nm.

In addition, the inorganic nanoparticles may be composite inorganic nanoparticles in which two or more kinds of inorganic nanoparticles as described above are composited. In one embodiment, the inorganic nanoparticles comprise composite inorganic nanoparticles comprising zirconia and ceria nanoparticles, wherein the ceria nanoparticles are adhered or bonded to the surface of the zirconia nanoparticles. In another embodiment, the inorganic nanoparticles comprise composite inorganic nanoparticles comprising titanium oxide nanoparticles having a silicon oxide layer on the surface. The amount of inorganic nanoparticles may be 0.1 to 10 wt%, based on the total weight of the composite particulate material. In some embodiments, the amount of inorganic nanoparticles may be 0.5 to 10 wt%, or 1 to 10 wt%, or 1.5 to 7 wt%, based on the total weight of the composite particulate material.

The present disclosure also relates to a method of making a composite particulate material, the method comprising the steps of: (a) providing fluoropolymer particles and inorganic nanoparticles having an average particle size of less than 200 nm; and (b) continuing at a rotational speed of 500 to 10,000 rpm The fluoropolymer particles and inorganic nanoparticles are mechanically mixed at a temperature below 200° C. for less than 30 minutes. In some embodiments, the fluoropolymer particles and inorganic nanoparticles can be mixed at a rotational speed of 1,000 to 9,000 rpm or 3,000 to 8,000 rpm. The fluoropolymer particles and inorganic nanoparticles can be mixed at a temperature below 150°C, or below 100°C, or below 70°C. Any high-performance powder processing machine suitable for nanoparticles can be used for mixing. RPM and time can vary depending on rotor size and processing machine. The inorganic nanoparticles are dispersed without agglomeration after mixing. No binder is required for mixing in the present disclosure. Examples of such mixers may include, but are not limited to, the Nobilta ^™ NOB Mini (commercially available from Hosokawa Micron Corporation, Osaka, Japan) and the Nara Hybridization System (available from Nara Machinery Co., Ltd., Tokyo, Japan). (Nara Machinery Co., LTD) commercially available).

The present disclosure further relates to a dielectric film comprising a polymer or resin and the composite particulate material of the present disclosure. The polymer or resin may be selected from the group consisting of polyimide (PI), polyamidoimide, polystyrene-block-poly(ethylene-random-butylene)-block-poly Styrene-graft-maleic anhydride (SEBS), epoxy resins, hydrocarbon resins, polyester resins, urea resins, silicone resins, polyphenylene ether resins, modified polyphenylene ether resins, liquid crystal polymer resins, and combinations thereof .

In one aspect, the dielectric films of the present disclosure can be made from a liquid composition comprising a polymer and a composite particulate material dissolved and/or dispersed in one or more organic solvents. In one embodiment, the liquid composition comprises composite particulate material, SEBS and an organic solvent such as toluene. In another embodiment, a liquid composition comprises a composite particulate material, polyimide, and an organic solvent.

In another aspect, the dielectric films of the present disclosure can be prepared by polymerizing and curing a liquid solution comprising: monomers and/or prepolymers and/or polymer precursors; composite particles materials; and one or more organic solvents. The composite particulate materials are the same as those previously described.

In one embodiment, the liquid solution may comprise dianhydride, diamine, composite particulate material, and one or more organic solvents. In another embodiment, the liquid solution may comprise polyamic acid, composite particulate material, and one or more organic solvents. "Dianhydride" as used herein is intended to include precursors or derivatives thereof, which may not technically be dianhydrides but which will still react with diamines to form polyamic acids (which in turn can be converted to polyimides). "Diamine" as used herein is intended to include precursors or derivatives thereof, which may not technically be diamines but which will still react with dianhydrides to form polyamic acids (which in turn can be converted to polyimides). "Polyamic acid" as used herein is intended to include any polyimide precursor derived from a combination of dianhydride and diamine monomers or a functional equivalent thereof and capable of being converted to a polyimide by a thermal or chemical conversion process material.

The dianhydride may be selected from the group consisting of: pyromellitic dianhydride (PMDA); 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA); 3,3',4,4 '-Benzophenone tetracarboxylic dianhydride; 3,3',4,4'-diphenone tetracarboxylic dianhydride; 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA ); cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA); cyclopentanetetracarboxylic dianhydride (CPDA); and combinations thereof. Optionally, the dianhydride may further include alicyclic dianhydride selected from the group consisting of: cyclobutene dianhydride; cyclohexane dianhydride; 1,2,3,4-cyclopentanetetracarboxylic dianhydride ; Hexahydro-4,8-oxoethyl-1H,3H-benzo[1,2-c:4,5-c']difuran-1,3,5,7-tetraone; 3-( Carboxymethyl)-1,2,4-cyclopentanetricarboxylic acid 1,4,2,3-dianhydride; meso-butane-1,2,3,4-tetracarboxylic dianhydride; 1,2 , 3,4,5-cyclohexanetetracarboxylic dianhydride; and combinations thereof.

The diamine may be selected from the group consisting of: 3,4'-diaminodiphenyl ether; 4,4'-diaminodiphenyl ether (ODA); 1,4-diaminobenzene; 1,3 - diaminobenzene; and 4,4'-diaminobiphenyl. Diamines can be Fluorinated aromatic diamines such as 2,2’-bis(trifluoromethyl)-1,1’-biphenyl-4,4’-diamine (TFDB). The diamines may further include aliphatic and/or cycloaliphatic diamines, if desired. Aliphatic diamines may be selected from the group consisting of: 1,2-diaminoethane; 1,4-diaminobutane; 1,5-diaminopentane; 1,6-diamino Hexane; 1,7-diaminoheptane; 1,8-diaminooctane; 1,9-diaminononane; 1,10-diaminodecane; 1,11-diaminodecane Undecane; 1,12-diaminododecane; 1,16-hexamethylenediamine; 1,3-bis(3-aminopropyl)-tetramethyldisiloxane; Phoronediamine; bicyclo[2.2.2]octane-1,4-diamine and combinations thereof. Cycloaliphatic diamines may be selected from the group consisting of: cis-1,3-diaminocyclobutane, trans-1,3-diaminocyclobutane; 6-amino-3-nitro Heterospiro[3.3]heptane; 3,6-diaminospiro[3.3]heptane; bicyclo[2.2.1]octane-1,4-diamine; 1,4-cyclohexanemethylenebis( cyclohexylamine); 4,4'-methylenebis(2-methyl-cyclohexylamine); bis(aminomethyl)norbornane and combinations thereof.

In some embodiments, a dielectric film can be made from a liquid composition comprising a composite particulate material, polyamide-imide, and one or more organic solvents. Polyamide-imides comprise copolymers derived from aromatic dianhydrides, aromatic diamines and aromatic dicarbonyl compounds. The aromatic dianhydride may be selected from the group consisting of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 4,4'-(hexafluoroisopropylidene) Phthalic anhydride (6FDA), cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA), cyclopentanetetracarboxylic dianhydride (CPDA), and combinations thereof. The aromatic diamine may be a fluorinated aromatic diamine, such as 2,2'-bis(trifluoromethyl)-1,1'-biphenyl-4,4'-diamine (TFDB). The aromatic dicarbonyl compound may be selected from the group consisting of p-terephthaloyl chloride (TPC), terephthalic acid, isophthaloyl chloride, and 4,4' benzoyl chloride. The polyamide-imide membranes and preparation are disclosed in US Patent Nos. 9,018,343 and 9,580,555, the entire contents of which are incorporated herein by reference.

Suitable organic solvents are those in which the polymer is soluble and/or dispersed. Exemplary organic solvents include, but are not limited to, polar protic and polar aprotic solvents such as benzene, toluene, xylene, alcohols such as 2-methyl-1-butanol, 4-methyl-2-pentanol, and methyliso butylmethanol); esters such as ethyl lactate, propylene glycol methyl ether acetate, dimethylacetamide, methyl 2-hydroxyisobutyrate, methyl 3-methoxypropionate, n-butyl acetate and 3-methoxy-1-butyl acetate; lactones such as gamma-butyrolactone; lactamides such as N-methylpyrrolidone; ethers such as propylene glycol methyl ether and dipropylene glycol dimethyl ether isomers , such as PROGLYDE ^™ DMM (The Dow Chemical Company, Midland, MI); ketones such as 2-butanone, cyclopentanone, cyclohexanone, and methylcyclohexyl Ketones; and mixtures thereof.

Appropriate additives may be added to the liquid composition or liquid solution as necessary. Examples of additives may include, but are not limited to, one or more of each of the following: curing agents, crosslinking agents, surfactants, inorganic fillers, organic fillers, plasticizers, metal passivation materials, inhibitors, flame retardants, and A combination of any of the foregoing. Suitable surfactants are well known to those skilled in the art and are preferably nonionic surfactants. Such surfactants may be present in amounts of 0 to 10 g/L, or 0 to 5 g/L.

Any suitable inorganic filler may be optionally used in the compositions of the present invention and is well known to those skilled in the art. Exemplary inorganic fillers may include, but are not limited to, silica, silicon carbide, silicon nitride, alumina, aluminum carbide, aluminum nitride, zirconia, and mixtures thereof. Inorganic fillers may be in the form of powders, rods, spheres or any other suitable shape. Such inorganic fillers may be of any suitable size. The inorganic filler may be used as a solid in an amount of 0 to 80 wt.%, or 40 wt.% to 80 wt.%, based on the total weight of the composition. In some embodiments, no inorganic filler is present.

The metal passivating material may be a copper passivating agent. Suitable copper deactivators are well known in the art and include imidazole, benzotriazole, ethylenediamine or a salt or acid ester thereof, and iminodiacetic acid or a salt thereof.

A liquid composition or liquid solution as described above may be coated or deposited on the surface of a substrate to form a film using any known technique and heated to remove the solvent. In one embodiment, the liquid composition may be soft baked at a suitable temperature (such as 90°C to 140°C) for a suitable time (such as 1 to 30 minutes) to remove any solvent. After this, an additional heating step may be performed to cure the film. Suitable methods for coating or disposing the liquid compositions of the present disclosure on the surface of a substrate may include, but are not limited to, spin-coating, curtain coating, spray coating, roller coating, among others. Roller coating, dip coating, vapor deposition, slot-die coating, gravure printing, and lamination, such as vacuum lamination (vacuum lamination) and other methods.

Any substrate known in the art can be used in the present disclosure. Examples of substrates may include, but are not limited to, silicon, copper, silver, indium tin oxide, silicon dioxide, glass, silicon nitride, aluminum, gold, polyimide, and epoxy mold compounds, Polyester sheets such as polyethylene terephthalate (PET) sheets, polyimide sheets such as KAPTON ^™ polyimide (DuPont, Wilmington, Delaware), or combination. The film formed on the substrate can be used directly, or can be peeled off as a self-supporting film and used on a different substrate in an electronic device. The self-supporting film can be laminated to the substrate surface using roll lamination or vacuum lamination with or without an adhesive layer. The lamination temperature may be 100°C to 400°C, or 140°C to 400°C, or 140°C to 300°C.

The dielectric films of the present disclosure have good tensile strength, tensile elongation, good adhesion to desired substrates such as copper, and low dielectric loss at high frequencies. At high frequencies such as 10 GHz, or 20 GHz, or 30 GHz, the dielectric film may have a _Dk value of less than 3.0, or less than 2.5, or less than 2.2; and a _Df value of less than 0.004, or less than 0.003, or less than 0.0025.

(BT)樹脂(日本東京三菱瓦斯化學株式會社(MGC))。 The present disclosure also relates to electronic devices comprising at least one layer of the dielectric film of the present disclosure on an electronic device substrate. The electronic device substrate can be any substrate used to make any electronic device. Exemplary electronic device substrates include, but are not limited to, semiconductor wafers, glass, sapphire, silicate materials, silicon nitride materials, silicon carbide materials, display device substrates, epoxy molding wafers, circuit board substrates materials, and thermally stable polymers. As used herein, the term "semiconductor wafer" is intended to encompass semiconductor substrates, semiconductor devices, and various packages for various levels of interconnection, including single-die wafers, multi-die wafers, packages for various levels , substrates for light-emitting diodes (LEDs), or other components requiring solder connections. Semiconductor wafers, such as silicon wafers, gallium arsenide wafers, and silicon germanium wafers, may be patterned or unpatterned. As used herein, the term "semiconductor substrate" includes any substrate having one or more semiconductor layers or structures comprising an active or operable portion of a semiconductor device. The term "semiconductor substrate" is defined to mean any construction, such as a semiconductor device, comprising a semiconductor material. Semiconductor device means a semiconductor substrate on which at least one microelectronic device has been fabricated or is being fabricated. Thermally stable polymers include, but are not limited to, any polymer that is stable at the temperature used to cure arylcyclobutene materials, such as polyimides, such as KAPTON ^™ polyimide (DuPont Co., Wilmington, Del. ), liquid crystal polymers such as VECSTAR ^TM LCP film (Kuraray, Tokyo, Japan) and bismaleimide-three

(BT) resin (Mitsubishi Gas Chemical Corporation (MGC), Tokyo, Japan).

example

The concepts described herein will be further described in the following examples, which do not limit the scope of the disclosure described in the claims. Unless otherwise stated, all temperature units are room temperature (20°C-25°C), and all pressure units are standard pressure or 101 kPa.

Material

(1) filler

PFA-1: perfluoroalkoxyalkane powder (MJX-10000, average particle size 4.5 μm, commercially available from Chemours-Mitsui Fluoroproducts Co., Ltd., Tokyo, Japan)

PFA-2: Perfluoroalkoxyalkane powder (532G-9420 PFA POWDER CLEAR, average particle size 7 μm, commercially available from Chemours Company FC, LLC, Wilmington, DE)

FEP: Fluorinated ethylene propylene powder (3M ^™ Dyneon ^™ Fluoroplastic Powder FEP 6322PZ, average particle size 6.4 μm, commercially available from 3M Company, St. Paul, MN)

_Al2O3 : aluminum _oxide (AEROXIDE® Alu 65, primary particle size 20 nm, commercially available from Evonik Industries AG, Essen, Germany)

_TiO2 : titanium dioxide (AEROXIDE® _TiO2 P 25, primary particle size 30 nm, commercially available from Evonik Industries, Essen, Germany)

(2) Organic matter:

SEBS: polystyrene-block-poly(ethylene-random-butylene)-block-polystyrene-graft-maleic anhydride, melt index is about 21g/10min (230°C/5.0kg);

ODA: 4,4'-diaminodiphenyl ether;

PMDA: pyromellitic dianhydride;

NMP: N-methyl-2-pyrrolidone;

All organics were purchased from Sigma Aldrich.

(3) Substrate:

Copper foil: CF-TGFB-THE with an average thickness of 18 μm, commercially available from Suzhou Fukuda Metal Co., Ltd., Suzhou, China.

PI film: Kapton ^® EN with an average thickness of 50 μm, commercially available from DuPont-Toray Co., LTD, Tokyo, Japan.

Processing Fluoropolymer Powders

PFA-1, PFA-2 and FEP were further processed in a Nobilta ^™ NOB Mini (commercially available from Hosokawa Micron Corporation, Osaka, Japan) at 7,000 rpm for 9 minutes. The process is controlled at a temperature below 70°C with cooling water. The processed fluoropolymer powders were named m-PFA-1, m-PFA-2 and m-FEP, respectively.

Membrane preparation

Film 1 - 4 g of SEBS was dissolved in 10 g of toluene with stirring overnight to form a SEBS/toluene solution. The SEBS/toluene solution was cast on a glass substrate by an automatic casting machine, and then dried in an oven at 130° C. for 5 min to form Film 1 . The formed film 1 was peeled off from the glass substrate to form a self-supporting film with a thickness of 25 μm.

Film 2 - 4 g of SEBS was dissolved in 10 g of toluene with stirring overnight to form a solution. 6 g of PFA-1 was added to the solution and mixed with the solution using a planetary centrifugal mixer "THINKY MIXER" ARE-310 (commercially available from Thinky USA Inc., Laguna Hills, California), Mixing was performed at 2000 rpm for 1 min ("Thinky Process"). This rebasing process was repeated 3 times. Afterwards, the mixture was degassed at 2400 rpm for 1 min to form a PFA-1/SEBS/toluene mixture. The PFA-1/SEBS/toluene mixture was cast on a glass substrate by an automatic casting machine, and then dried in an oven at 130° C. for 5 min to form Film 2 . The formed film 2 was peeled off from the glass substrate to form a self-supporting film with a thickness of 25 μm.

Membrane 3 - Membrane 3 was prepared using the same procedure as Membrane 2, except that m-PFA-1 was used instead of PFA-1.

Membrane 4 - 28g of m-PFA- ₁ and 0.57g of _Al2O3 were added to the Nobilta NOB Mini. The machine was run at 3000 rpm for 1 minute and then increased to 7000 rpm for 9 minutes. The process is performed at temperatures below 70°C using cooling water to form _{Al2O3 -} coated fluoropolymer powder. Finally, after opening all air valves, the coated powder was collected as fluoropolymer composite particles. Membrane 4 was prepared using the same procedure as Membrane 2, except that PFA-1 was replaced with fluoropolymer composite particles prepared as above.

Membranes 5 and 6 - Membranes 5 and 6 were prepared using the same procedure as Membrane 4, except that 1.14 g of Al ₂ O ₃ was used in the fluoropolymer composite particles for Membrane 5, and the fluoropolymer composite particles for Membrane 6 1.71 g of Al ₂ O ₃ were used in .

Membranes 7 and 8—Membranes 7 and 8 were prepared using the same procedure as Membranes 2 and 3, except that PFA-1 and m-PFA-1 were replaced by FEP and m-FEP, respectively.

Membrane 9 - Membrane 9 was prepared using the same procedure as Membrane 4, except that m-FEP was used instead of m-PFA-1; and 0.51 g of _TiO2 and 0.37 g of _Al2O3 were used instead of 0.57 _g of _Al2 O ₃ .

Membrane 10 - Dissolve 31 g of ODA in 214 g of NMP at 30 °C with stirring under _N2 . Then, 33 g of PMDA was gradually added to form a PMDA-ODA solution. The solution was kept under a continuous flow of _N2 overnight. The solution was cast on a glass substrate by means of an automatic casting machine, and then dried in an oven at 110° C. in air for 30 min. The dried coated glass substrate was placed in a glove box at 350 °C under N for ₁ h to form a polyimide film. The formed polyimide film was then peeled off from the glass substrate to form a self-supporting film with a thickness of 25 μm.

Membrane 11 - The PMDA-ODA solution was prepared using the same procedure as described for Membrane 10. Based on the total amount of PFA-2 and PMDA-ODA, 60 wt% of PFA-2 was added to the PMDA-ODA solution and mixed with the PMDA-ODA solution. Mixing was carried out at 2000 rpm for 1 min using a planetary centrifugal mixer "Celtech Mixer" ARE-310 ("Celtech Process"). This rebasing process was repeated 3 times. Afterwards, the mixture was degassed at 2400 rpm for 1 min. The mixture was then cast on a glass substrate by means of an automatic casting machine and then dried in an oven at 110° C. in air for 30 min. The dried coated glass substrate was placed in a glove box at 350 °C for 1 h under N flow to form a polyimide film containing PFA- ₂ . The formed polyimide film containing PFA-2 was then peeled off from the glass substrate to form a self-supporting film with a thickness of 25 μm.

Membrane 12 - Membrane 12 was prepared using the same procedure as Membrane 11 except that m-PFA-2 was used instead of PFA-2.

Membrane 13 - Membrane 13 was prepared using the same procedure as Membrane 11, except that PFA-2 was replaced with fluoropolymer composite particles made by adding 28 g of m-PFA-2 to the Nobilta NOB Mini, and then adding _N2 gas was filled into the chamber to purge the air. The machine runs at 7000rpm. After 9 min, 0.86 g of _TiO2 was then added to the chamber and filled with _N2 to purge the air. The machine was run at 3000 rpm for 1 min and then increased to 7000 rpm for 9 min. After 9 min, 0.57 g of _TiO2 was then added to the chamber and filled with _N2 to purge the air. The machine was run at 3000 rpm for 1 min and then the speed was increased to 7000 rpm for another 9 min. The whole process is controlled at a temperature below 70°C with cooling water. Finally, after opening all air valves, the coated powder was collected as fluoropolymer composite particles.

measurement and testing

1. Adhesion (ADH) test

The films prepared as described above were sandwiched between copper foil and PI film. The sandwich structure was then laminated on a vacuum laminator at a pressure of 19 kgf/ ^cm2 at 180 °C for 5 min under vacuum. The laminate was then cut into 1 cm wide strips. Adhesion is tested on 01/LFLS/LXA/CN Lloyd material tester. The 90° peel was performed at a speed of 2 inches/min.

2. Electrical test

The dielectric constant (D _k ) and dissipation factor (D _f ) of the films were measured by the cavity method at 20 GHz on a N5224B-20 VPN network analyzer. The prepared films were thermally dried at 120 °C for 4 hours before measurement.

3. Viscosity measurement:

The viscosity of the PMDA-ODA solution was measured with a Brookfield DV3T rheometer with a CP-52 spindle at a shear rate of 2/s and a speed of 1 rpm.

4. Hygroscopicity measurement:

The hygroscopicity (wt %) of the films was measured on a TGA Q5000SA analyzer. The films were dried at 60°C and 0% room humidity. The films were then stabilized and measured at 25°C and 50% room humidity.

5. Measurement of elongation at break:

The polyimide film was cut into 1 cm wide strips. Measurements were made on an Instron 5566Q8442 with an effective test length of 2 inches and a speed of 0.2 inches/min.

result

Table 1 lists the composition and test results of the SEBS films prepared as described above.

Table 1 shows that the addition of fluoropolymer particles or fluoropolymer composite particles to SEBS films maintains low dielectric constant (D _k ) and low dissipation factor (D _f ) of the film. Due to the poor compatibility of fluoropolymers with SEBS, the adhesion of SEBS films containing fluoropolymer particles to copper foil and PI films was lower than that of SEBS films without fillers. However, Table 1 shows that the membranes containing fluoropolymer composite particles had higher adhesion strength than the membranes containing fluoropolymer particles. For fluoropolymer composite particles containing only Al ₂ O ₃ , the adhesion strength of the film increases with the addition of more Al ₂ O ₃ . However, adding a small amount of _TiO2 significantly increases the adhesion strength. The film adhesion strength of the fluoropolymer composite particles is close to that of the film without any filler.

As shown in Figures 1 to 3, fluoropolymer composite particles showed improved UV cutability in SEBS films compared to fluoropolymer particles. The tests were performed on a bilayer film comprising SEBS film and copper foil. The bilayer films were laminated on a vacuum laminator at 180 °C for 5 min at a pressure of 19 kgf/ ^cm2 to form SEBS/Cu laminates. A 100 μm wide line was cut from the SEBS film side of the SEBS/Cu laminate using a 355 nm UV laser. Figure 1 shows the Membrane 2 side of the diced Membrane 2/Cu laminate. The line indicated by the arrow in Figure 1 shows the absence of Cu, which indicates that the fluoropolymer particle-filled SEBS was not removed by the UV laser, and that the film 2 residue completely covered the copper foil. Figure 2 shows the Membrane 3 side of the diced Membrane 3/Cu laminate. Similar to Fig. 1, no Cu was observed, indicating poor UV laser cuttability. Figure 3 shows the Membrane 5 side of the diced Membrane 5/Cu laminate. After UV laser cutting, a large area of copper foil can be seen from Figure 3. Thus, the film 5 comprising fluoropolymer composite particles significantly improved the UV cutability of the material compared to the film comprising fluoropolymer particles.

Table 2 shows the composition and test results of the polyimide membranes prepared as described above.

Table 2 shows that both _Dk and _Df decrease significantly with the addition of fluoropolymer and fluoropolymer composite particles as fillers to polyimide membranes. The elongation at break decreased and the decrease in m-PFA-2 was greater compared to the polyimide film without filler. However, the membranes containing fluoropolymer composite particles had a higher fracture point compared to the membrane containing m-PFA-2, and was close to that of the polyimide membrane without any filler. Table 2 also shows that the addition of fluoropolymer particles and fluoropolymer composite particles has greatly reduced hygroscopicity. In addition, the polymer solution containing fluoropolymer composite particles has a much lower viscosity than the polymer solution containing fluoropolymer particles (PFA-2 and m-PFA-2). FIG. 4 shows cracks at the interface between the fluoropolymer particles and the polyimide on the membrane 11 . As shown in FIG. 5 , no cracks were observed at the interface between the fluoropolymer composite particles and polyimide on the membrane 13 . Therefore, the inorganic nanoparticles of the fluoropolymer composite microparticles improve the compatibility between the fluoropolymer and polyimide.

Claims (18)

A composite particulate material comprising: Fluoropolymer particles; and Inorganic nanoparticles having an average particle size of less than 200 nm, Wherein, the composite particulate material basically does not contain silane or hydroxyl functional groups. The composite particulate material as claimed in claim 1, wherein the fluoropolymer particles are coated by the inorganic nanoparticles as cores. The composite particulate material according to claim 1 or 2, wherein the fluoropolymer particles have an average particle size of 1 to 20 μm. The composite particulate material according to any one of claims 1 to 3, wherein the average particle size of the inorganic nanoparticles is in the range of 5 to 175 nm. The composite particulate material according to any one of claims 1 to 4, wherein the fluoropolymer particles comprise a fluoropolymer selected from the group consisting of tetrafluoroethylene perfluoroalkyl vinyl ether copolymer ( PFA), chlorotrifluoroethylene polymer (CTFE), tetrafluoroethylene chlorotrifluoroethylene copolymer (TFE/CTFE), ethylene chlorotrifluoroethylene copolymer (ECTFE), polyvinylidene fluoride (PVDF), poly( Tetrafluoroethylene-co-hexafluoropropylene) (FEP), polytetrafluoroethylene (PTFE) and poly(ethylene-co-tetrafluoroethylene) (ETFE). The composite particulate material according to any one of claims 1 to 5, wherein the inorganic nanoparticles comprise inorganic compounds selected from the group consisting of alumina, silica, zirconia, titania and combinations thereof . The composite particulate material according to any one of claims 1 to 6, wherein the ratio of the average particle size of the fluoropolymer particles to the average particle size of the inorganic nanoparticles is at least 20. A method of manufacturing a composite particulate material, the method comprising the steps of: (a) providing fluoropolymer particles and inorganic nanoparticles having an average particle size of less than 200 nm; and (b) mechanically mixing the fluoropolymer particles and the inorganic nanoparticles at a speed of 100 to 10,000 rpm and at a temperature below 200°C for no more than 30 minutes. The method of claim 8, wherein the fluoropolymer particles and the inorganic nanoparticles are mixed at a temperature lower than 150°C. A dielectric film comprising a polymer and the composite particulate material according to any one of claims 1 to 7. The dielectric film as claimed in claim 10, wherein the polymer is selected from the group consisting of polyimide (PI), polystyrene-block-poly(ethylene-random-butylene)- Block-polystyrene-graft-maleic anhydride (SEBS), epoxy resin, hydrocarbon resin, polyester resin, urea resin, silicone resin, polyphenylene ether resin, modified polyphenylene ether resin, liquid crystal polymer Resins and combinations thereof. The dielectric film as claimed in claim 11, wherein the polymer is polyimide and the polyimide is derived at least in part by contacting one or more dianhydride components with one or more diamine components produced polyamic acid. The dielectric film according to claim 12, wherein the dianhydride component is selected from the group consisting of: pyromellitic dianhydride (PMDA); 3,3',4,4'-biphenyl tetra Formic dianhydride (BPDA); 3,3',4,4'-benzophenone tetracarboxylic dianhydride; 3,3',4,4'-diphenylene tetracarboxylic dianhydride; 4,4'-( Hexafluoroisopropylidene) diphthalic anhydride (6FDA); cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA); cyclopentanetetracarboxylic dianhydride (CPDA); and combination. The dielectric film according to claim 12 or 13, wherein the diamine component is selected from the group consisting of: 3,4'-diaminodiphenyl ether; 4,4'-diaminodiphenyl ether (ODA); 1,4-diaminobenzene; 1,3- Diaminobenzene; 4,4'-diaminobiphenyl; 2,2'-bis(trifluoromethyl)-1,1'-biphenyl-4,4'-diamine (TFDB); and its combination. The dielectric film according to any one of claims 10 to 14, wherein the film has a thickness of 10 to 2000 μm. The dielectric film according to any one of claims 10 to 15, further comprising: a substrate selected from the group consisting of copper, silicon, silicon nitride, aluminum, gold, silver, poly Imide and epoxy moldings. The dielectric film according to any one of claims 10 to 16, wherein the film has a D _k at 20 GHz

3 with D _f

0.004. An electronic device having a layer comprising at least one dielectric film according to any one of claims 10 to 17.