JP2003524302A - Electronic support and method and apparatus for forming openings in electronic support - Google Patents

Abstract

SUMMARY OF THE INVENTION The present invention provides an electronic support comprising (A) a prepreg material layer (214) and (B) at least one layer (217), wherein (A) comprises (1) at least One reinforcement material (220); (2) including at least one substrate material (216), wherein the at least one substrate material (216) is in contact with at least a portion of the at least one reinforcement material (220). The at least one layer (217) is in contact with at least a portion (224) of at least one surface of the prepreg material layer (214) and the at least one layer (217) An inorganic filler (218) and up to 25 weight percent of an adhesive material based on the total weight of the at least one layer (217) based on total solids.

Description

Detailed Description of the Invention

REFERENCE TO PRIOR APPLICATION This application is related to US provisional application no.
of Making the Same ”), US Provisional Application No. 60/184
, 026 (Title filed on February 22, 2000, entitled "Methods and
Apparatus for Forming Apertures in E
electronic Supports and Electronic Su
ports Made There from "), and US Provisional Application No. 60.
/ 233,619 (Title “Electron filed on Sep. 18, 2000)
ic Supports and Methods and Apparatus
s for Forming Apertures in Electron
c Supports').

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates generally to electronic supports and methods of making electronic supports,
And, in detail, it relates to a prepreg material layer, a laminated board, a clad laminated board, a printed circuit board, and a method for producing these. The present invention further relates to methods and apparatus for forming openings in electronic supports made in accordance with the present invention, and more particularly to mechanically drilling openings in printed circuit boards.

2. Technical Considerations Electronic supports, and particularly printed circuit boards, commonly referred to as PCBs or printed wiring boards (PWBs), typically have two or more layers of polymer-impregnated reinforcing layer ( (Generally referred to as prepreg material), and one or more electrically conductive layers laminated together by the application of heat and pressure. The production of printed circuit boards is typically done in a circuit board to facilitate "in-board" electrical interconnection as well as interconnection between the printed circuit board and other electrical components mounted therein. Requires the formation of openings (called holes or vias). In-board interconnection includes, for example, connecting patterned circuits on different layers of a printed circuit board. Interconnects between the substrate and other electronic components include, for example, interconnections between printed circuit boards and embedded circuit devices mounted thereon. After forming the openings, which is typically accomplished by drilling, the walls of the holes are typically plated to form electrically conductive paths. The circuit is patterned on one or more electrically conductive layers by methods well known in the art (eg, photoimaging and etching).

As the electronics industry continues to increase the number of circuits and functionality that can be assembled on a single integrated circuit device, on printed circuit boards (both on internal boards and between the board and other components). The need for more connections must also increase to support the device. Increasing the size of the circuit board to accommodate the increased number of connections is considered both by size and weight limitations dictated by the final product in which the circuit board is incorporated, as well as product performance requirements.
It is impractical. Therefore, in order to accommodate the increased connectivity requirements, the number of feature layers of the printed circuit board can be increased while increasing the number of metal layers incorporated into the circuit board.
For example, the diameter of the holes and the width of the patterned lines) can be reduced.

The need to reduce feature size and the number of layers help to make the printed circuit board manufacturing process more complex and demanding. In particular, the formation of a large number of small openings has been found to significantly increase the manufacturing cost of printed circuit boards (
Joan Tourne, "Using New Interconnect
Technologies to Reduce Substrate Cos
t ”Proceedings of the European Joint
Conference VI: EIPC, (1997) pp. 167-174, which are specifically incorporated herein by reference). For example,
Mechanical drilling of holes with a diameter of less than 13 mils has been found to have a negative impact on yield, throughput, and cost of typical mechanical drilling processes. This is due in large part to the increased wear of the drilling tools associated with drilling small holes in the PCB. Drilling tool wear occurs during drilling when the drilling encounters a layer of glass fibers in the PCB. Glass fiber fabrics are typically P
Used to reinforce each layer of CB, providing both improved stiffness and strength to the substrate. However, glass fibers have a wear effect on the drilling tools and cause them to become dull. Dull or worn tools reduce the quality of the walls of the drilled holes, reduce the positional accuracy of the drilled holes, increase fiber fragmentation, and even clay, nailheads.
has been found to adversely affect the drilling process by increasing the occurrence of other drilling defects such as edging, wicking, and unevenness on the surface of the via (ie, holes). There is.

Moreover, as the performance requirements of embedded circuit devices increase, the power dissipation requirements of these devices also tend to increase. This results in increased heat flow at the surface of the device that must be controlled to prevent device failure.
For example, for every 10 ° C (18F) increase in device operating temperature, about 2
It is estimated that the failure rate increases by a factor of two (R. Tummala and E. Rym.
See Aszewski, Microelectronics Packaging Handbook, (1989) page 168, which is expressly incorporated herein by reference. By improving the thermal conductivity of the printed circuit board on which such a device is located (eg, by mounting the device directly on the PCB, or mounting a second level package containing the device on the PCB). Device performance and reliability can be improved.

Electronic supports in the form of both laminates and printed circuit boards that possess both good drilling properties and increased functionality, as well as can increase drilling life and reduce wear of drilling tools, An alternative apparatus and method for punching a printed circuit board that may improve the quality of the hole walls, reduce the punching cost, and be incorporated into an existing punching operation without the need for further processing steps The need for remains.

SUMMARY OF THE INVENTION The present invention provides an electronic support comprising: (A) (1) at least one reinforcing material; (2) contacted with at least a portion of at least one reinforcing material. A prepreg material layer comprising at least one matrix material; and (B) at least one layer in contact with at least a portion of at least one surface of the prepreg material. The at least one layer comprises at least one inorganic filler and no more than 25 weight percent adhesive material based on the total weight of the at least one layer based on total solids.

The present invention also provides a method of forming an electronic support including the steps of: (A) forming a prepreg material layer comprising at least one matrix material and at least one reinforcing material; (B) at least partially solidifying at least one matrix material; (C) at least partially solvating a portion of the at least partially solidified matrix material with at least one solvent; and ( D) Adhering at least one inorganic filler to at least a portion of the at least partially solvated matrix material.

The invention further provides a method of forming an electronic support comprising the steps of: (A) forming a prepreg material layer comprising at least one matrix material and at least one reinforcing material; (B) adhering at least one inorganic filler to at least a portion of at least one matrix material, wherein the at least one matrix material is tacky; and (C) at least one matrix material. At least partially solidifying.

The present invention also provides a laminate comprising: (A) a number of (laminated together)
a stack of) prepreg lumber layers; and (B) at least one layer comprising at least one lubricant located between at least portions of at least one combination of prepreg lumber layers adjacent to the stacked prepreg lumber layers.

The present invention also provides a method of forming an electronic support comprising at least one layer of an internal lubricant, the method comprising the steps of: (A) at least one lubricant Applying at least one lubricant to at least a portion of at least one surface of the first prepreg material layer to form a layer; (B) at least one layer of lubricant having a layer of internal lubricant. At least 1 so as to be located between the first layer of prepreg material and at least one further layer of prepreg material for forming.
Depositing one additional prepreg material layer and a first prepreg material layer; and (C) laminating the first prepreg material layer and at least one additional prepreg material layer together to form an electronic support.

DETAILED DESCRIPTION OF THE INVENTION Electronic supports and methods of forming electronic supports according to the present invention have good perforation properties, reduced processing costs, increased processing yields, good thermal conductivity, And in providing electronic supports in the form of laminates and printed circuit boards with increased functionality. Moreover, the method and apparatus of the present invention are particularly useful for forming openings in electronic supports, and more particularly in printed circuit boards.

As used herein, the term “electronic support” means a structure capable of mechanically supporting and / or electrically interconnecting elements, which is the electronic state of operation. Components, passive electronic components, printed circuits, embedded circuits, semiconductor devices and other hardware associated with such elements, including, but not limited to, connectors, sockets, securing clips and heat sinks. It is not limited to these.
Although not limited in the present invention, electronic supports may include, for example, prepreg material layers, laminates, clad laminates and printed circuit boards. As used herein, the term "laminate" means an electronic support formed from a polymer matrix material reinforced with a reinforcing material; and "clad laminate" or "panel" , A laminate having an electrically conductive material in contact with at least a portion of one or more surfaces thereof. Typically, the laminate is formed from two or more layers of prepreg material. As used herein, the term "prepreg material layer" or "prepreg material" refers to a reinforced polymer matrix material coated over at least a portion thereof, preferably by impregnation (but not limited to). Means a layer of material. As used herein, the terms "printed circuit board (PCB)", "electronic circuit board", and "printed wiring board (PWB)" refer to an electronic support formed from a polymer matrix material. Meaning, this may be reinforced with a reinforcing material and includes one or more printed circuits and / or openings.

Printed circuit boards are generally made by impregnating a polymeric matrix material with a reinforcing material, typically a glass fiber reinforced material. Generally, a woven fabric or a non-woven fabric (as a glass fiber reinforced material used for forming a printed circuit board,
(Including but not limited to unidirectional, biaxial, and triaxial fabrics)
, Knits, mats (both chopped and continuous strand mats), and multi-layered fabrics (ie, several layers for forming an overlay layer of a woven fabric by sewing or a three-dimensional fabric structure). Other materials) such as, but not limited to, textiles. In addition, coated fiber strands used as warp and weft strands (ie, fill strands) of the woven fabric are non-twisted ("untwisted" before the weaving process.
"wisted" or "zero twist") or twist, and the fabric may include various combinations of both twisted and untwisted warp and weft strands. But,
And, without limiting the invention, the glass fiber reinforced material is typically a woven fiber.

The present disclosure generally relates to electronic supports, particularly prepreg lumber layers formed from woven fiberglass fabrics, laminates, and electronic supports in the form of printed circuit boards. However, the present invention is not limited to electronic supports formed with woven reinforcement materials and may include any reinforcement material, including but not limited to the reinforcement materials discussed above. It will be understood by those skilled in the art. Furthermore, the present invention is not limited to reinforced laminates and printed circuit boards, but also includes electronic supports in the form of unreinforced printed circuit boards. As used herein, the term "non-reinforced printed circuit board" means a printed circuit board that does not include a reinforcing material. Further, the method of forming the openings of the present invention is directed to any electronic support, particularly printed circuit boards (unreinforced printed circuit boards and printed circuit boards formed using the reinforcing materials discussed above). It will be appreciated by those skilled in the art that it is useful to form openings in both (including both).

For the purposes of this specification, unless otherwise indicated in the examples dealt with or otherwise indicated, the amounts of components, all numbers representing reaction conditions and all numbers stated in the specification and claims. It is to be understood that is modified in all cases by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending on the desired properties sought to be obtained by the present invention. is there. At least, and not as an attempt to limit the application of the principle of equivalents to the claims, each numerical parameter considers the number of significant digits reported and by the application of conventional rounding techniques. At least it should be interpreted.

Although the numerical ranges and parameters set forth in the broad scope of the present invention are approximations, the numerical values set forth in particular examples are reported as accurately as possible. However, any numerical value inherently contains certain errors inherently arising from the standard deviation found in their respective testing measurements.

Referring to FIG. 1, an electronic support 1 according to one non-limiting embodiment of the present invention.
0 is shown. The electronic carrier 10 comprises at least one woven fiber reinforced material 2 having at least one matrix material 16 applied to at least a part thereof.
At least one prepreg material layer 14 is included. At least one matrix material 16 comprises at least one inorganic filler 18. Although not necessary, in one non-limiting embodiment of the present invention, at least one inorganic filler 1
8 is a particulate inorganic filler. As used herein, the term "particulate" means discrete non-fibrous particles. The at least one inorganic filler 18 is
It may have any particle size and shape suitable for the desired end product. In one particular embodiment of the invention, without limitation, the average particle size of the at least one inorganic filler is 0.01 microns (micrometers) in the major dimension.
To 1000 microns. The average particle size of the particles according to the invention can be measured according to known laser scattering techniques. In one non-limiting embodiment of the invention, the particle size is Beckman Coulter LS 23.
0 Laser Diffraction Particle Size Instrument (This instrument measures the size of a particle with a laser beam having a wavelength of 750 nm and assumes that the particle has a spherical shape (ie “particle size” refers to It refers to the smallest spherical shape that completely encloses a))). Examples of suitable particle shapes include, but are not limited to, cubic, faceted particles, spherical particles, platey particles, and acicular particles.

If desired, an additional layer of prepreg material (not shown) may be affixed to the layer of prepreg material 14 to form a laminate as shown in FIG. 3, for example, by a lamination process. This will be discussed in more detail later.

Without limitation herein, at least one matrix material 16 of the present invention.
Are commonly described in the sense of polymeric matrix materials. As used herein, the term "polymer matrix material" means a matrix material formed from macromolecules composed of long chains of atoms that are linked together and can be entrained in solution or solid state. (James Mark et al. Inorgan
ic Polymers, Prentice Hall Polymer Sc
ience and Engineering Series, (1992),
Page 1, which is incorporated herein by reference. However, it will be appreciated by those skilled in the art that other matrix materials, such as but not limited to ceramics and glass-ceramics, may be used as the at least one matrix material in some embodiments of the invention. It Polymer matrix molecules useful in the present invention include thermosetting and thermoplastic materials. Non-limiting examples of useful thermosetting polymer matrices include thermosetting polyesters, vinyl esters, epoxides (containing at least one epoxy or xylene group in the molecule, eg, polyglycidyl ethers of polyhydric alcohols or thiols. ), Phenolics, aminoplasts, thermoset polyurethanes, and their derivatives and mixtures. In one non-limiting embodiment of the invention, the polymer matrix material for forming a laminate for a printed circuit board is FR-4 epoxy resin, such as a difunctional brominated epoxy resin. Polyfunctional epoxy resins), polyimides, and liquid crystalline polymers, these compositions being well known to those skilled in the art. If further information about such compositions is needed, Electronic Materials Ha
ndbook ^™ , ASM International (1989), 534.
-Page 537, which is incorporated herein by reference in detail.

Non-limiting examples of useful thermoplastic polymer matrix materials include polyolefins, polyamides, thermoplastic polyurethanes, thermoplastic polyesters, vinyl polymers, and mixtures thereof. Further examples of useful thermoplastic materials include polyimides, polyether sulfones, polyphenyl sulfones, polyether ketones, polyphenylene oxides, polyphenylene sulfides, polyacetals, polyvinyl chloride, and polycarbonates.

A specific, non-limiting example of a polymer matrix material formulation useful in the present invention is EPON 1120-A80 epoxy resin (Shell Chemical).
Company, Houston, Texas), dicyandiamide, 2-methylimidazole, and DOWANOL PM glycol ether (The Dow Chemical Co., Midland, Mic.
(commercially available from Higan).

Other constituents that may be contained in the prepreg material layer 14 include coloring agents or pigments,
Lubricating oils or processing aids, ultraviolet light (UV) stabilizers, antioxidants, other fillers (eg, flame retardants) and extenders are included, but are not limited to.

In one non-limiting embodiment of the present invention, at least one matrix material 16 comprises at least one non-fluorinated treated polymeric material. In another non-limiting embodiment, at least one matrix material 16 does not include greater than 50 wt% fluorinated polymeric material, based on total solids. In another non-limiting embodiment, at least one matrix material 16 does not include greater than 30 wt% fluorinated polymeric material, based on total solids. In yet another non-limiting embodiment, at least one matrix material 16 does not include greater than 10% by weight fluorinated polymeric material, based on total solids. In one non-limiting embodiment of the present invention, at least one matrix material 16 is substantially free of fluorinated polymeric material. As used herein, the term "substantially free of fluorinated polymeric material" means that the polymer matrix material does not contain more than 5% by weight of fluorinated polymeric material, based on total solids, and preferably Means free of fluorinated polymeric material. While not meant to be limiting herein, a fluorinated polymer is defined as the addition of a fluorinated polymeric material to a polymer matrix material in some applications the overall performance of electronic supports made therefrom. It is not preferred for use in this embodiment as it can increase the dielectric constant of this polymer matrix material which can be detrimental to. Furthermore, fluorinated polymers tend to be expensive and can increase the cost of electronic supports.

Referring to FIG. 1, inorganic fillers 18 useful in the present invention include ceramic materials (eg, oxides, nitrides, carbides, borides), glass materials (eg, glass as described in detail below). Materials), metals, and inorganic materials such as, but not limited to, other minerals such as clay minerals. Although not limited herein, in order to minimize wear of the reinforcement material during laminate fabrication, in one non-limiting embodiment of the present invention, at least one inorganic filler 18 is provided between the reinforcement material 20. It has a hardness value that is not greater than the hardness value. The hardness values of the inorganic filler 18 and the reinforcing material 20 can be determined by any conventional hardness measurement method (eg, Vickers or Brinell hardness), but preferably are inherently indicative of the relative scratch resistance of the surface of the material. Is determined according to the Mohs hardness. Thus, for example, if the reinforcing material is formed from glass fibers having a Mohs hardness value of 6, in one non-limiting embodiment of the present invention, the Mohs hardness value of the at least one inorganic filler is:
In greater than 6 and in another non-limiting embodiment, the Mohs hardness is 0.
． It is in the range of 5 to 6. Mohs hardness values for some non-limiting examples of inorganic fillers suitable for use in the present invention are given in Table A below.

[0027]

[Table 1] ² K. Ludema, Friction, Wear, Lubrication,
(1996) 27 pp. (This document is hereby incorporated by ^reference) 3 R. West (ed), Handbook of Chemistry an
d Physics, CRC Press (1975) F-22 , page ⁴ R. Lewis, Sr. , Hawley's Condensed Chem
ical Dictionary, (12th Edition, 1993) 793 pp. (This document is hereby incorporated by ^reference) 5 R. Lewis, Sr. , Hawley's Condensed Chem
ical Dictionary, (12th Ed., 1993) 1113 pp. (This document is hereby incorporated by ^reference) 6 R. Lewis, Sr. , Hawley's Condensed Chem
edical Dictionary, (Twelfth Edition, 1993) page 784, which is hereby incorporated by reference. ⁷ Handbook of Chemistry and Physics, F.
-22 page ⁸ Handbook of Chemistry and Physics, F
-22, ⁹ Friction, Wear, Lubrication, 27, ¹⁰ Friction, Wear, Lubrication, 27, ¹¹ Friction, Wear, Lubrication, 27, ¹² Handbook of Chemistry, Physics,
CRC Press (71st edition, 1990) pp. 4-158 (This document is hereby incorporated by ^reference) 13 Friction, Wear, Lubrication, 27 pp. ¹⁴ Handbook of Chemistry and Physics,
F-22 p. ¹⁵ Handbook of Chemistry and Physics,
F-22 p. ¹⁶ Handbook of Chemistry and Physics,
F-22 p. ¹⁷ Handbook of Chemistry and Physics,
F-22 p. ¹⁸ Handbook of Chemistry and Physics,
F-22 p. ¹⁹ Handbook of Chemistry and Physics,
F-22 p. ²⁰ Handbook of Chemistry and Physics,
F-22 page.

As mentioned above, the Mohs hardness scale is related to the resistance of a material to scratching.
Accordingly, the present invention contemplates an inorganic filler having a hardness at its surface that is different from the hardness of the interior portion of the filler below its surface. More particularly, the surface of the particles is such that the hardness of the particles below the particles is higher than the hardness of the glass fibers, and the surface hardness of the particles is less than or equal to the hardness of the glass fibers. These include, but are not limited to, chemical changes in the surface properties of the particles using techniques known in the art.
It can be modified in any manner known in the art. As another alternative, the particles are coated with a first or more second materials, cladding, or encapsulated with a first first material.
Can be formed from the above materials to form a synthetic material having a softer surface. Alternatively, the particles may be formed from a first material that is coated, cladding, or encapsulated with a different form of the first material to form a composite material having a softer surface.

In one example, and without limiting the invention, inorganic particles formed from inorganic materials such as silicon carbide or aluminum nitride are provided with silica, carbonate, or nanoclay coatings to provide useful composites. Particles can be formed. In another non-limiting embodiment, the inorganic particles can be reacted with a coupling agent having a functional group capable of covalently bonding with the inorganic particles and a functional group capable of crosslinking with the film-forming material or the crosslinkable resin. Such coupling agents are described in US Pat.
, 853,809, column 7, line 20 to column 8, line 43, which is incorporated herein by reference. Useful silane coupling agents include glycidyl, isocyanate, amino or carbamyl functional silane coupling agents. In another non-limiting example, a silane coupling agent having an alkyl side chain is used to provide useful composite particles having a "softer" surface.
It can react with the surface of inorganic particles formed from inorganic oxides. Other examples include cladding, encapsulation, or coated particles formed from non-polymeric or polymeric materials and different non-polymeric or polymeric materials. A specific, non-limiting example of such a composite particle is DUALITE, which is available from Pierce and Stevens Corporation, Bu.
Synthetic polymer particles coated with calcium carbonate commercially available from Ffalo, NY.

In order to minimize water uptake in the electronic support of the present invention, one non-limiting example of the present invention
In one embodiment, the at least one inorganic filler 18 is non-hydratable (non-hydrated).
-Hydratable). As used herein, "non-hydratable"
By means that the inorganic filler does not react with water molecules to form hydrates and contains no water of hydration or water of crystallization. A "hydrate" is produced by the reaction of a molecule of water with a substance in which the H-OH bond is not broken. R. Lewis
, Sr. , Hawley's Condensed Chemical Dic
tionary (12th edition, 1993) 609-610, and T.W. Perr
os, Chemistry (1967), pp. 186-187, which are specifically incorporated herein by reference. In the hydrate formula, the addition of water molecules is conventionally indicated by a central dot (eg 3MgO.4Si).
O ₂ · H ₂ O (talc), Al ₂ O ₃ · 2SiO ₂ · 2H ₂ O (kaolinite)
). Structurally, hydratable inorganic substances contain at least one hydroxyl group within the layers of the crystal lattice (but on the surface plane of the unit structure or substance that adsorbs water on their surface plane or by capillary action). No hydroxyl group) in, for example, J. Mitchell, Fundamentals of Soil B
ehavior (1976) page 34, as shown in the structure of kaolinite given in FIG. van Olphen, Clay Col
loid Chemistry (2nd edition, 1977), FIGS. 18 and 1 on page 62.
As shown in the structure of the 1: 1 and 2: 1 layered minerals, respectively, shown in 9 (which are specifically incorporated herein by reference). A "layer" of a crystal lattice is a combination of sheets, which is a combination of atomic planes. Minerals in Oil Environments, S
oil Science Society of America (1977)
196-199, which is specifically incorporated herein by reference.
. The collection of materials (eg, cations) in the layers and interlayers is referred to as the unit structure.

A hydrate is (1) coordinated with the cations of the hydrated substance and cannot be removed without decomposition of the structure; and / or (2) voids in the structure. Occupies, and includes the water of structure, which adds electrostatic energy without disturbing the balance of charge. R. Evans, An Introduction to Crystal
See Chemistry, (1948) page 276, which is specifically incorporated herein by reference.

In one particular, non-limiting embodiment of the invention, the at least one inorganic filler 18 is as much as 80 weight percent hydratable, based on total solids.
ble) Contains filler. In another non-limiting embodiment, at least one inorganic filler 18 comprises as much as 30 weight percent hydratable filler, based on total solids. In yet another non-limiting embodiment of the present invention, at least one inorganic filler 1
8 is essentially free of hydratable filler. As used herein, the term "
"Essentially free of hydratable filler" means that at least one inorganic filler 18
It is meant to contain less than 5 weight percent, and more preferably less than 1 weight percent hydratable filler, based on total solids.

In another non-limiting embodiment of the present invention, which is discussed in more detail below, the at least one inorganic filler 18 is hydrated instead of or in addition to the non-hydratable inorganic materials described above. It may include at least one filler formed from an inorganic material or a hydrated inorganic material. Non-limiting examples of such hydratable inorganic materials include mica (eg,
Muscovite), talc, montmorillonite, kaolinite, smectite, and clay mineral phyllosilicates including gypsum.

In one embodiment, but not a limitation of the present invention, the at least one inorganic filler 18 is at least one inorganic solid lubricant. As used herein, the term "inorganic solid lubricant" means a solid inorganic material that acts to reduce the coefficient of friction between two surfaces, and the term "solid" means under mild pressure. Means a material that flows very little, has a certain ability to withstand the forces that try to deform it, and retains a certain shape and size under normal conditions. Webster
No New International Dictionary of the
English Language-Unbridged 3rd Edition (197)
1) See page 2169, which is specifically incorporated herein by reference. Solids include both crystalline and amorphous materials. For example, but not limiting of in the present invention, an inorganic solid lubricant may be used between the drill tool used to form the opening in the electronic support that encloses the filler 18 and the adjacent solid surface of the electronic support. Can produce an anti-friction lubrication effect between. As used herein, the term "friction" means the resistance of one solid to slide over another. F. Clauss, Solid Lubricants and Self-
Lubricating Solids (1972) page 1, which is specifically incorporated herein by reference.

Without wishing to be bound by any particular theory, it is formed therefrom by incorporating a layer of prepreg material 14 comprising at least one inorganic solid lubricant filler 18 into the electronic support 10 of the present invention. It is believed that the drilling characteristics of the printed circuit board that is made can be improved. More specifically, it is believed that the solid lubricant may act as a drilling aid (or drilling lubricant) during the drilling process, thereby reducing friction and tool wear. In addition, by incorporating a solid lubricant into the laminate itself (in the case of oil or other drilling lubricant) instead of externally applying it, the lubricant allows the immediate interface between the drill tool and the electronic support ( I.e. where the drill tool wear occurs).

Without limitation, the inorganic solid lubricants disclosed herein may have a characteristic crystal habit that causes them to shear into thin, flat plates, which easily lends themselves to each other. It slides, thus creating an anti-friction lubrication effect between the electronic support (more specifically, the glass fiber reinforcement) and the adjacent solid surface (at least one of which is in motion). R. Lewis, Sr. , Hawley's Condens
ed Chemical Dictionary "(12th edition, 1993) 71
See page 2, which is specifically incorporated herein by reference.
Although not required, in one non-limiting embodiment of the present invention, the inorganic solid lubricant has a layered structure. Inorganic solid lubricants with a layered structure consist of sheets or plates of atoms in a hexagonal system, have strong bonds within the sheets and weak van der Waals bonds between the sheets, and low shear forces between the sheets. provide. Fr
iction, Wear, Lubrication, page 125, Solid L
ubricants and Self-Lubricating Solid
s, 19-22, 42-54, 75-77, 80-81, 82, 90-102,
113-120 and 128 and W. Campbell "Solid L
ubricants ", Boundary Lubrication; An A
ppraisal of World Literature, ASME Re
search Committee on Lubrication (1969
) 202-203, which are specifically incorporated herein by reference.

Non-limiting examples of suitable inorganic solid lubricants useful in the present invention having a layered structure include boron nitride, graphite, metal dichalcogenides, mica, talc, kaolinite, cadmium iodide, boric acid, and These mixtures are mentioned. In one non-limiting embodiment of the invention, the inorganic solid lubricant is selected from boron nitride, graphite, metal dichalcogenides, and mixtures thereof. Non-limiting examples of suitable metal dichalcogenides include molybdenum disulphide, molybdenum diselenide, tantalum disulphide, tantalum diselenide, tungsten disulphide, tungsten diselenide and mixtures thereof.

Other inorganic solid lubricants having a layered structure that are considered useful in the present invention include, but are not limited to, organic cation intercalated natural and synthetic clays. As used herein, the phrase "organic cation intercalated" refers to a thin layer (or layer) of clay that is at least partially due to the introduction of the organic cation into the space between pairs of adjacent layers. Means to be separated into. Non-limiting examples of intercalated clays that are believed to have utility in the present invention are NANOMER® nanoclays (nanocla).
y), which is Arlington Heights, Illinois.
Nanocor Inc. Marketed by.

In one non-limiting embodiment of the present invention, the boron nitride particles having a hexagonal crystal structure are a layered solid lubricant used as the inorganic filler 18 in the present invention. A non-limiting example of hexagonal boron nitride particles suitable for use in the present invention is the Advanced Ceramics Cor, Lakewood, Ohio.
PolarTherm® 100 commercially available from poration
Series (PT120, PT140, PT160 and PT180), 300 series (PT350) and 600 series (PT620, PT630, PT6)
40 and PT670) boron nitride powder particles. "PolarTherm ^{T M} Thermally Conductive Fillers for P
"Olymical Materials" Lakewood, Ohio Adv
Technical Bulletin of advanced Ceramics Corporation (1996
), Which is specifically incorporated herein by reference.
These particles have a thermal conductivity of 250-300 watts / meter Kelvin (W / mK) at 25 ° C. (298K), a dielectric constant of 3.9, and a volume resistivity of 10 ¹⁵ Ω-cm. The 100 series powder particles have an average particle size in the range of 5 μm to 14 μm, the 300 series powder particles have an average particle size in the range of 100 μm to 150 μm, and the 600 series powder particles are from 16 μm to Two
It has an average particle size in the range of greater than 00 μm. Without limiting the invention, one particular grade of POLARTHERM particles useful as a filler in the present invention is POLARTHERM 160 particles, which, as reported by its source, have an average particle size of 6-12 μm. Size, less than micrometer ~
It has a particle size in the range of 70 μm and a particle size distribution as follows:

[0040]

[Table 2] According to this distribution, 10% of the measured POLARTHERM 160 boron nitride particles had an average particle size longer than 18.4 μm. As used herein, "average particle size" refers to the average particle size of the particles. The average particle size of the particles according to the invention can be measured according to known laser scattering techniques. In one non-limiting embodiment of the invention, the particle size is Beckman
Measured using a Coulter LS 230 laser diffractive particle size instrument, which measures 750 to determine the size of the particles as described earlier.
A laser beam with a wavelength of nm is used and it is assumed that the particles have a spherical shape. By independent analysis of the particle size of the POLARTHERM 160 boron nitride particle sample measured using a Beckman Coulter LS 230 particle size analyzer, the boron nitride particles have an average particle size of 11.9 μm and the particles are less than micrometer. It was found to have a range of .about.35 .mu.m and have the following particle size distribution:

[0041]

[Table 3] According to this distribution, 10% of the measured POLARTHERM 160 boron nitride particles had an average particle size greater than 20.6 μm.

Another non-limiting example of an inorganic filler that can act as an inorganic solid lubricant and is considered suitable for use in the present invention is an inorganic filler having a fullerene (“buckyball”) structure, And antimony oxide.

In one non-limiting embodiment of the present invention, at least one inorganic filler 18
Is formed from a non-hydratable layered inorganic solid lubricant.

At least one inorganic filler 1 in a matrix material which is also an inorganic solid lubricant 1
The reduction in friction between the drill tool and the laminate, in part due to the presence of the prepreg material layer 14 containing 8, reduces heat generation during drilling, thereby reducing the resin in the drilled hole. However, such resin smear is further reduced when the solid lubricant has a higher thermal conductivity than that of the polymeric matrix material 16 and the reinforcing material 20. It is thought to get. Although not meant to be bound by any particular theory, the use of solid lubricants with high thermal conductivity not only reduces the frictional heat generated during drilling, but also produced the lubricating properties. Any frictional heat is rapidly dissipated by the high thermal conductivity of the solid lubricant. In other words, heat is drawn from the drilling interface, thereby lowering the interface temperature and avoiding melting of the resin. In addition, the use of high thermal conductivity fillers may impart improved thermal spreading properties to the final printed circuit board made from it, as previously discussed, thereby bonding to this circuit board. Improve the performance and reliability of embedded circuit devices. As used herein, the term "high thermal conductivity" means at least 10 W / mK at 300K, preferably at least 20 W / mK at 300K.
And more preferably a material having a thermal conductivity of at least 30 W / mK at 300K.

Although one non-limiting embodiment of the present invention uses a high thermal conductive filler that is also a solid lubricant, the use of a high thermal conductive filler that is not necessarily a solid lubricant is also herein a present invention. Intended.

Non-limiting examples of high thermal conductivity materials suitable for use as the inorganic filler of the present invention include:
Provided in Table B.

[0047]

[Table 4] ²¹ G. Slack "Nonmetallic Crystals with
High Thermal Conductivity "J. Phys. Che
m. Solids (1973) Vol. 34, 322, which is hereby incorporated by reference. ²² R. Tumala (ed.) Microelectronics Packa
ging Handbook (1989) page 174, which is hereby incorporated by reference. ²³ Microelectronics Packing Handboo
k, p. 174. ^24, ibid., P. 37, which is hereby incorporated by reference. ²⁵ ibid., P. 174. ²⁶ Same as above. ²⁷ Same as above. ²⁸ Same as above. ²⁹ Same as above. ³⁰ Microelectronics Packaging Handsbo
k, p. 174. ³¹ G. Slack "Nonmetallic Crystals with
High Thermal Conductivity "J. Phys. Che
m. Solids (1973) Vol. 34, 322. ³² Id., P. 325, which is hereby incorporated by reference. ³³ Id., P. 333, which is hereby incorporated by reference. ³⁴ Id., P. 329, which is hereby incorporated by reference. ³⁵ ibid., 333 p. ³⁶ Id., P. 321 (which is hereby incorporated by reference). ³⁷ Microelectronics Packaging Handsbo
k, page 36, which is hereby incorporated by reference. ³⁸ Same as above. ³⁹ Id., P. 905, which is hereby incorporated by reference.

In one non-limiting embodiment of the present invention, the inorganic filler 18 has a high electrical resistivity. As used herein, the term "high electrical resistivity" refers to
By a material having an electrical resistivity of at least 1000 micro ohm centimeters (μΩ · cm). For example, and without limiting the invention, high electrical resistivity fillers can be used in conventional electronic circuit board applications to prevent loss of electronic signals due to conduction of electrons through the filler. Special applications (eg,
For microwave applications, high frequency interference applications and circuit boards for electromagnetic interference applications) high electrical resistivity is not required. Without limiting the invention, the electrical resistivity of selected materials having a high electrical resistivity useful as inorganic filler 18 in the present invention is provided in Table C below.

[0049]

[Table 5] ⁴⁰ ESK Engineered Ceramics, Titanium D
_{iboride Powder Datasheet TiB 2/03/} 95 (
Wacker Chemicals (USA), Inc. , ESK Divi
sion, Norwalk, CT) ⁴¹ A. Weimer (Ed.), Carbide, Nitride and
Boride Materials Synthesis and Proce
ssing, (1997) page 654, which is incorporated herein by reference. ⁴² A. Weimer (Ed.), Carbide, Nitride and
Boride Materials Synthesis and Proce
ssing, (1997) page 654, which is incorporated herein by reference. ⁴³ A. Weimer (Ed.), Carbide, Nitride and
Boride Materials Synthesis and Proce
Ssina, (1997), page 653, which is incorporated herein by reference. ⁴⁴ Handbook of Chemistry and Physics,
CRC Press (71st Ed. 1990), pages 12-63, which is incorporated herein by reference. ⁴⁵ Handbook of Chemistry and Physics,
CRC Press (71 st Ed. 1990), pages 12-63, which is incorporated herein by reference. ⁴⁶ A. Weimer (Ed.), Carbide. Nitride and
Boride Materials Synthesis and Proce
Ssinq, (1997), page 654, which is incorporated herein by reference.

In one non-limiting embodiment of the invention, at least one inorganic filler 1
8 is at least one solid lubricant having high thermal conductivity and high electrical resistivity. A non-limiting example of an inorganic filler that is a solid lubricant and has both high thermal conductivity and high electrical resistivity is hexagonal boron nitride.

In another non-limiting embodiment of the invention, at least one inorganic filler 18
Has a low thermal expansion. As used herein, the term “low thermal expansion” means a material that has a lower coefficient of thermal expansion (CTE) than the polymer matrix material 16. A material having a low coefficient of thermal expansion, which is not required, is the CT of the stiffener 20.
E also has a low CTE. In one non-limiting embodiment of the present invention, the inorganic filler 18 has a negative CTE. That is, the organic filler 18 contracts when heated. For example, and without limitation herein, the polymer matrix material 16 comprises 600-800 per ° C over a temperature range of 0 ° C to 200 ° C.
In one embodiment, which is an epoxy material having a CTE in the range of 10 ⁻⁷ , the inorganic filler 18 has a smaller CTE than that of the polymer matrix material over the same temperature range, particularly 600-800 × over the same temperature range. 10 ^-7 /
It has a CTE of less than ° C. In another non-limiting embodiment, the inorganic filler 18 has a C of less than 100 × 10 ⁻⁷ / ° C. over a temperature range of 0 ° C. to 200 ° C.
Has TE. In yet another non-limiting embodiment, the inorganic filler 18 is 0 ° C.
Have a CTE of less than 50 x ^10-7 / C over a temperature range of -200C. Without wishing to be bound by any particular theory, the incorporation of a low thermal expansion filler in the prepreg layer 14 may reduce the z-axis thermal expansion of the electronic support 10 made therefrom. As used herein, the term "z-axis thermal expansion" refers to
It refers to the thermal expansion of the electron support in a direction substantially parallel to the thickness of the electron support and substantially perpendicular to the major surface of the electron support. As used herein, the term "
The "major surface" is approximately perpendicular to the thickness of the electronic support, and the major dimension of the reinforcing material (
That is, it means the surface of the electron support which is substantially parallel to the (xy dimension). The reduction of the z-axis thermal expansion of the electronic support is made therefrom, in particular by reducing the incompatibility between the CTE of the polymer matrix material and the plating on the walls of the openings formed therein. The reliability of the printed circuit board can be improved. Reducing the thermal expansion mismatch between the polymer matrix material and the plating can reduce the phenomenon of plating cracking (often referred to as barrel cracking) on the opening walls in printed circuit boards. Non-limiting examples of low thermal expansion materials that are considered useful in the present invention include those listed in Table D below.

[0052]

[Table 6] ⁴⁷ R. Tummala (Ed.), Microelectronics P
acking Handbook, (1989), page 637, which is incorporated herein by reference. ⁴⁸ Tummala, p. 637. ⁴⁹ ld. ⁵⁰ Id. ⁵¹ lnvar is an iron-nickel alloy. ⁵² ld. ⁵³ Id. ⁵⁴ ld. ⁵⁵ Hlavac, J .; The Technology of Glass & The Technology of Glass &
Ceramics: An Induction, (1983), 232.
Page, which is incorporated herein by reference. ⁵⁶ ld, 278, which is hereby incorporated by reference. ⁵⁷ Hiavac, p. ⁵⁸ Tummala, p. 637. ⁵⁹ Hivac, p.

Other suitable inorganic fillers 18 having a low CTE include, but are not limited to, aluminum titanate and aluminum nitride.

In another non-limiting embodiment of the invention, at least one inorganic filler 18
Is a material that inhibits the formation of conductive anode fragments (CAF) in the PCB, which in turn reduces electrical shorts in the PCB that result from the filament.
Conductive anode filaments are electrically conductive filaments that are formed on a circuit board due to the electrochemical migration of metal ions, most commonly copper ions. Generally, these filaments contain a glass fiber reinforcement and P
Form along the interface between the polymer matrix material used to form the CB (typically an epoxy). It is believed that CAF is formed when the interface between the glass fiber reinforcement and the epoxy is compromised in some fashion (eg, by delamination or hydrolysis), and the PCB is Subjected to humidity and high bias conditions. When these conditions exist, the electrochemical corrosion cell
It can be established between oppositely charged features. For example, and without limitation, CAF has been observed to occur in oppositely charged lines, holes, and between lines. In general, CAF occurs when water penetrates the glass toughener and the interface between the epoxy between the positively charged features (ie, anode) and the negatively charged features (ie, cathode). Conceivable. Ions that may be present as epoxy themselves or as contaminants (eg, free chloride ions) dissolve in water to form an electrolyte and create an electrochemical corrosion cell. Corrosion of the anode can then occur by dissolution of metal ions, especially copper ions from the anode, and transport through the electrolyte to the cathode. As metal ions precipitate as halide salts or are plated from solution, the insulation resistance of the space between the anode and cathode tends to reduce and leak currents that can occur between these features. It is in. If an electrical conduction path or CAF is formed between the two features, an electrical short can occur. In other cases, a portion of the anode may be electrically depleted due to metal depletion. The growth of these conductive filaments can be inhibited by trapping, binding or reacting with metal ions in such a way as to prevent the ions from forming unwanted filaments. In one non-limiting embodiment of the invention, the at least one inorganic filler 18 has a high affinity for metal ions. As used herein, the term "high affinity for metal ions" means that the filler material is complexed with the metal ions and adsorbs the metal ions on its surface and / or edges.
It is meant to trap or encapsulate metal ions in its lattice structure and / or to have a tendency to undergo ion exchange. Although not meant to be limited to the application of the present invention, the use of inorganic fillers having a high affinity for metal ions, especially copper ions, has been described above due to the formation of conductive anode filaments. It is considered to be advantageous in reducing or preventing a physical short circuit. By placing the inorganic filler 18 having a high affinity for metal ions in the path of the moving metal ions, for example, the inorganic filler 1 in the polymer matrix material 16
By dispersing 8, metal ions migrating through the polymer matrix material 16 can be stopped or trapped by the inorganic filler 18, thereby inhibiting the growth of electrically conductive filaments and the resulting electrical shorts. To do. Therefore, in one non-limiting embodiment of the present invention, the matrix material 16
Includes an amount of inorganic filler 18 having a high affinity for metal ions, sufficient to prevent electrical shorting due to conductive anode filament formation.

In one non-limiting embodiment of the invention, the inorganic filler 18, which has a high affinity for metal ions, has at least 20 milliequivalents (meq / 100g) of cation exchange per 100 grams of dry filler. It is a clay material with a capacity. As used herein, the term "cation exchange capacity" or "CEC" is the adsorbed amount required to balance the layer charge deficiency in the material resulting from the isomorphous substitution of ions of the layer structure. By the amount of exchangeable cations, both interstitial and intercalation. D. Hillel, Fundamentals of Soil P
hysics, (1980), pp. 71-74 and J. Mitchell, Fu
ndamentals of Soil Behavior, (1976), 3
See page 2, which are specifically incorporated herein by reference. C
EC, which is often referred to as total exchange capacity, reference exchange capacity, or cation adsorption capacity, is generally measured by techniques well known to those skilled in the art, and further description thereof is necessary in light of the present disclosure. I can't think of that. If more information is needed, Rich, Removal of excess sal
t in CEC determinations, Soil Science
, Vol. 93 (1962), pp. 87-94, Rich, Ca ⁺ 2deter.
magnetization for CEC determinations, Soil
Science, vol. 92 (1961), pp. 226-231, and h.
ttp: // bluehen. ags. udel. edu / deces / pro
d-agric / chap9-95. htm (January 31, 2001
) (These are specifically incorporated herein by reference).

Examples of clay materials having a cation exchange capacity of at least 20 meq / 100 g include montmorillonite, nontronite, saponite, illite (hydrated mica), vermiculite, chlorite, sepiolite, attapulgite, bentonite, hectorite, Examples include, but are not limited to, synthetic fluoromica (described below), and any of the above blends. Hillell et al., Pp. 44-45 (this is
Incorporated herein by reference).

In another non-limiting embodiment of the present invention, the filler 18 having a high affinity for metal ions has a cation exchange capacity of at least 80 meq / 100g. Examples of clay minerals having a CEC of at least 80 meq / 100 g include montmorillonite, nontronite, saponite, vermiculite, bentonite, hectorite, illite, synthetic fluoromica (discussed below), and any of the foregoing. Examples include but are not limited to:

In another non-limiting embodiment of the present invention, the inorganic filler 18 having a high affinity for metal ions, especially copper ions, is an expandable clay mineral. As used herein, the term "expandable clay" means a swellable clay. In general, expandable clay minerals can provide a cation exchange capacity of at least 80 meq / 100 g due to their large surface area and exchangeable intercalating cations. Non-limiting examples of expandable clay minerals useful in the present invention include montmorillonite, vermiculite, saponite, illite, bentonite, hectorite, expandable synthetic fluoromica, and any of the foregoing. Generally, although not required, expandable clay minerals have a negative layer charge (X) in the range of 0.1-0.9, balanced by the presence of exchangeable intercalation cations. Be done. Minerals having a layer charge of less than 0.1 (eg, kaolinite and talc) are free of intralayer cations; therefore, minerals having one charge per formula unit greater than 0.9 (eg, mica) are , Containing only non-exchangeable intra-layer cations and, in their non-weathered form, generally do not expand. J. B. Dix
on et al. (Eds.), Minerals in the Oil Envir.
onment, (1977), 200, 221-232, and Mitch.
ell, p. 32, which are specifically incorporated herein by reference.

In another non-limiting embodiment of the present invention, the swelling clay mineral having a high affinity for metal ions, especially copper ions, has been isomorphically replaced (substituted) by lithium cations, It is selected from fluorophlogopite having at least one portion of those potassium cations, and fluorophlogopite having at least one portion of those potassium cations isomorphically replaced by sodium cations. Sodium phlogopite is a synthetic fluoromica where at least a portion of the intercalated potassium cations is isomorphously replaced by sodium cations. Such sodium phlogopite is expandable, but typical non-weathered mica is not expandable (discussed below). Kirk-Othmer En
cyclopedia of Chemical Technology, Vo
l. 13 ⁽² nd Ed., 1967), pp. 412-413 (which is herein particularly, incorporated by reference).

In yet another non-limiting embodiment of the present invention, the inorganic filler 18 can be any of the inorganic fillers discussed above, which have a high affinity for metal ions. Surface treated or coated with material. For example, without limitation herein, boron nitride particles may be treated with an organometallic ion complexing agent to form an inorganic filler having a surface that has a high affinity for metal ions.
Non-limiting examples of suitable organometallic ion complexing agents include porphyrins and amines such as ethylenediamine, triethylenetetraamine, ethylenediaminetetraacetic acid (EDTA), polyvinylpyridine, and 2-aminopyrimidine. As used herein, the term "porphyrin" is derived from living material and contains four interconnected rings, each ring containing four carbon atoms and one nitrogen atom. A complex compound having a basic structure consisting of Non-limiting examples of porphyrins include red hemoglobin and green chlorophyll. J. Hunt, Petroleum Geochemis
try and Geology, (1979), page 551, and G. et al. Haw
ley, Hawley's Condensed Chemical Dic
Ionary, (10th edition, 1981), page 843, which are specifically incorporated herein by reference. In another non-limiting example, the inorganic filler particles (eg, boron nitride and aluminum nitride) are at least 20 meq.
/ 100 g coated with nanoclay particles having a cation exchange capacity,
Filler particles can be formed that have a surface that has a high affinity for metal ions.

In addition to the clay materials discussed above, other silicate materials that have a high affinity for metal ions, especially copper ions, can be used as the filler 18. For example, without limiting the invention, porous silicates, especially organofunctional porous silicates, can be used as fillers. In one non-limiting embodiment of the present invention, the porous silicate having a high affinity for metal ions has a CEC of at least 20 meq / 100g. In another non-limiting embodiment,
Porous silicates with high affinity for metal ions should be at least 80 m
It has a CEC of eq / 100 g.

In another non-limiting embodiment of the present invention, the packing material 18, which has a high affinity for metal ions, is characterized by its ability to remove, ie, uptake, cations from aqueous solution. This capability is quantified by replacing the distribution coefficient K _d, the distribution coefficient _the K _d is defined as the ratio of the amount of cations adsorbed to the solid 1 g relative to the amount of cations remaining in solution per 1 ml, ml / g It is represented by. Materials that remove selected metal ions, particularly copper ions, from aqueous solutions are also expected to reduce CAF when incorporated into a matrix as discussed herein. The partition coefficient, K _d, is determined by Komaneni et al., Material Re.
search Laboratory, The Pennsylvania S
Tate University, University Park, PA can be measured according to the method developed. For more information on K _d , see Sridhar, Komanneni, Naofumi Kozai and Rustum Roy, “Novell function for anion.
ic plays: selective transition metal
“Cation uptake by diadochy”, Journal o
f Material Chemistry, 8 (6) (1998), 1329.
Pp. 1331; Sridhar Komanneni, William J. et al. P
aulus and Rustum Roy, "Novell swelling m
ica: synthesis, characterisation and c
ation exchange ”, New Developments in
Ion Exchange: Materials, Fundamentals
and Applications, Proceedings of the
International Conference on Ion Exch
age, Tokyo (1991), 51-56; Masamichi Ts.
uji and Sridhar Komanneni, “An extended
method for analytical evaluation of
distribution coefficients on select
live organic exchanges ", Separa
motion science and technology, 27 (6) (19)
92), 813-821; and Masamichi Tsuji and S.
ridhar Komanneni, "selective exchange
of different transition metal ions in
cryptomelane-type manganic acid wit
h tunnel structure ", Journal of Mater
See ears Research, 8 (3) (1993), pages 611-616.

To determine the K _d using the method developed by Komarneni,
An aqueous 0.5 N NaCl solution containing 0.0001 N M ⁺ was prepared at room temperature, where M ⁺ is the cation being studied. The solution sample was sealed in a glass vial for 24 hours and then analyzed using techniques well known in the art (eg, direct current plasma method) to determine the exact amount of M ⁺ in solution (in parts per million). 1 unit (ppm
)) Is determined. This analysis provides a reference point in determining how much M ⁺ is removed during the test. A 20 mg sample of the material to be tested is equilibrated in a sealed glass vial with 25 ml of solution for 24 hours. After equilibration, the solid and liquid phases are separated and the solution is analyzed to determine M ⁺ uptake and reported as K _d (M ⁺ ).

In one non-limiting embodiment of the present invention, when the cation is Cu ²⁺ , the filler having a high affinity for metal ions is at least 600 ml.
Clay minerals or other silicates with a K _d (Cu ²⁺ ) of / g. In another non-limiting embodiment of the invention, the particles having a high affinity for metal ions are clay minerals or other silicates with a K _d (Cu ²⁺ ) of at least 1500 ml / g. In yet another non-limiting embodiment of the invention,
Particles with high affinity for metal ions should be at least 15,000 ml /
Clay minerals or other silicates with K _d (Cu ²⁺ ) of g. In another non-limiting embodiment of the invention, the particles having a high affinity for metal ions are clay minerals or other silicates with a K _d (Cu ²⁺ ) of at least 40,000 ml / g.

Non-limiting examples of clay minerals and other silicates with acceptable K _d (Cu ²⁺ ) values include bentonite, hectorite and porous silicates, especially porous organofunctional silicates. .

In addition to the materials discussed above with respect to reducing CAF, other chelating agents and polymers can be used as filler materials with high affinity for metal ions to reduce CAF. Conceivable. While not limiting in the present invention, the chelating material preferably comprises a nitrogen atom containing organic functional group such as, but not limited to, amines and imines. Other non-limiting chelating agents or polymers that can serve this purpose can have sulfur-containing organic functional groups, oxygen-containing organic functional groups, phosphorus-containing organic functional groups, or combinations of these chelating functional groups. Non-limiting examples of additional chelating agents that can be used to reduce CAF include SILQUEST A1387 silane, which is available from Crompto.
n Corporation of Greenwich, Connectic
It is a silylated polyazamide commercially available from ut)
And Emery 6717 (partially amidated polyethyleneimine), and Versamid 140 (polyamide), both of which are Cogni.
s Corporation of Cincinnati, Ohio).

Referring again to FIG. 1, the inorganic filler 18 incorporated into the prepreg material layer 14
Type and amount depends in part on the desired function of the inorganic filler. In a non-limiting embodiment of the invention, the inorganic filler 18 is in an amount sufficient to form an essentially continuous or interconnected phase 30 (see FIG. 1) via the PCB. Exists. Without limitation in the present invention, the volume fraction of the inorganic filler 18 present in the polymer matrix material 16 may be greater than or equal to the permeation threshold (or permeation limit) of the filler 18. As used herein, the term "permeation threshold" means the volume fraction of filler required to form an essentially interconnected path of filler through the matrix material. Tummala (1989) pp. 576-577 (this is
), Which is specifically incorporated herein by reference. In another non-limiting embodiment, the filler 18 can be present as an essentially continuous layer in an electronic support (as described in more discussion below).

Nonetheless, polymer matrix materials 16 containing a volume fraction of the filler 18 that is less than the permeation threshold of the filler 18 are desirable for electronic supports made from them (eg, thermal conductivity, It will be appreciated by those skilled in the art that they can effectively provide (including but not limited to electrical resistance, CAF resistance, lubricity and CTE). Furthermore, since it can be difficult to add a large amount of inorganic filler to the polymer matrix material, in one non-limiting embodiment of the invention, the polymer matrix material is present in an amount that does not exceed the permeation threshold of the filler. Including inorganic filler material. It will also be understood by those skilled in the art that, for a given volume fraction (or percent) of the inorganic filler used, the exact weight percent of this inorganic filler will depend on the density of the particulate inorganic filler and the polymeric matrix material. .

In one embodiment of the invention, including but not limited to the at least one inorganic filler 18 being an inorganic solid lubricant, the amount of the at least one inorganic filler 18 is based on total solids. Thus, the total weight of the polymer matrix material 16 and the at least one inorganic filler 18 is in the range of 0.03% to 70% by weight. In another non-limiting embodiment, the amount of the at least one inorganic filler 18 is 0 based on the total solids of the combined weight of the polymer matrix material 16 and the at least one inorganic filler 18. It is in the range of 0.03% by weight to 50% by weight. In yet another non-limiting embodiment, the amount of the at least one inorganic filler 18 is based on total solids and is the total weight of the polymer matrix material 16 and the at least one inorganic filler 18. Is 0.03% by weight to 35% by weight.

At least one inorganic filler 18 is at least 30 W / m at 300K
In one non-limiting embodiment of the present invention having a thermal conductivity of K, the amount of the at least one inorganic filler 18 is based on total solids and the polymer matrix material 16 and the at least one inorganic filler. 0.3 of the total weight including the material 18
It is in the range of 70% by weight to 70% by weight. In another non-limiting embodiment, the amount of the at least one inorganic filler 18 is based on total solids of the total weight of the polymer matrix material 16 and the at least one inorganic filler 18 combined. 10
It is in the range of 70% by weight to 70% by weight. In yet another non-limiting embodiment, the amount of the at least one inorganic filler 18 is based on total solids and is the total weight of the polymer matrix material 16 and the at least one inorganic filler 18. In the range of 35% to 70% by weight.

In one non-limiting embodiment of the present invention, wherein at least one inorganic filler 18 has a low coefficient of thermal expansion, the amount of at least one inorganic filler 18 is based on total solids. It ranges from 5% to 80% by weight of the total combined weight of the polymer matrix material 16 and the at least one inorganic filler 18. In another non-limiting embodiment, the amount of the at least one inorganic filler 18 is based on total solids of the total weight of the polymer matrix material 16 and the at least one inorganic filler 18 combined. It is in the range of 20% by weight to 75% by weight. In yet another non-limiting embodiment, the amount of the at least one inorganic filler 18 is based on total solids and is the total weight of the polymer matrix material 16 and the at least one inorganic filler 18. In the range of 25% to 60% by weight.

In one non-limiting embodiment of the present invention, wherein the at least one inorganic filler 18 has a high affinity for metal ions, the at least one inorganic filler 1
The amount of 8 ranges from 0.03% to 80% by weight of the total combined weight of the polymer matrix material 16 and the at least one inorganic filler 18, based on total solids. In another non-limiting embodiment, the amount of the at least one inorganic filler 18 is based on total solids of the total weight of the polymer matrix material 16 and the at least one inorganic filler 18 combined. It is in the range of 10% by weight to 80% by weight. In yet another non-limiting embodiment, the amount of the at least one inorganic filler 18 is based on total solids and is the total weight of the polymer matrix material 16 and the at least one inorganic filler 18. In the range of 35% to 80% by weight.

Referring again to FIG. 1, as mentioned above, the reinforcing material 20 may be present in the form of, for example, woven and non-woven fabrics, mats, knits and multilayer fabrics as described above. In one embodiment, but not a limitation of the present invention, the reinforcing material 20 is a woven fabric. In another non-limiting embodiment, the reinforcing material 20 is
As shown in FIG. 1, it is a woven fabric containing glass fibers.

The glass fibers useful in the present invention include “E-glass”, “A-glass”, and “C”.
-Glass, prepared from fiberizable glass compositions such as, but not limited to, "glass", "D-glass", "R-glass", "S-glass" and E-glass derivatives. Not done. As used herein, the term "fiberizable" means a material that can be formed into a nearly continuous fiber, strand or yarn. As used herein, the term "strand" means a plurality of individual fibers; the term "fiber" means an individual filler material; and the term "yarn".
Means twisted strands. As used herein, the term "E glass derivative" means a glass composition containing small amounts of fluorine and / or boron, which is preferably free of fluorine and / or free of boron. .
Further, as used herein, "minor amount of fluorine" means less than 0.5 wt% fluorine, preferably less than 0.1 wt% fluorine, and "minor amount of boron". Means less than 5% by weight boron, preferably less than 2% by weight boron. In one non-limiting embodiment of the present invention, the glass fibers are formed from E-glass or E-glass derivatives. Such compositions and methods of making glass filler materials from the compositions are well known to those of skill in the art and further discussion of these is considered unnecessary in light of the present disclosure. If further information is needed, such glass compositions and fiberizing methods are described in K.K. Loewen
Stein, "The Manufacturing Technology
"Continuous of Glass Fibers" (3rd edition, 1993)
30-44, 47-60, 115-122, and 126-135, and U.S. Pat. Nos. 4,542,106 and 5,789,329, which are specifically The specification is incorporated by reference.

Without limitation in the present invention, the reinforcing material 20 may include at least one glass fiber, and if one non-limiting embodiment is a woven glass fiber fabric, the reinforcing material 20 may be of ordinary skill in the art. Can be formed from any type of fibrable material known in the art, including, but not limited to, fibrable non-glass inorganic materials, fibrable organic materials, and mixtures and combinations thereof.
The inorganic and organic materials can be either artificial or naturally occurring materials. Those skilled in the art will understand that the fibrous inorganic and organic materials can also be polymeric materials. Examples of non-glass inorganic fibers suitable for use in the present invention include, but are not limited to, silicon carbide, carbon, graphite, mullite, aluminum oxide and ceramic fibers formed from piezoelectric ceramic materials. Non-limiting examples of suitable animal-derived and plant-derived natural fibers include cotton, cellulose, natural rubber, flax, columbine, hemp, sisal, and wool. Suitable polymer fibers include polyamides (eg nylon and aramid), thermoplastic polymers (eg polyethylene terephthalate and polybutylene terephthalate), acrylics (eg polyacrylonitrile), polyolefins, polyurethanes and vinyl polymers (eg polyvinyl. Examples thereof include, but are not limited to, fibers formed from alcohol). Non-glass fibers that are considered useful in the present invention include "En
cyclopedia of Polymer Science and Te
Chnology, Vol. 6 (1967), pp. 505-712, which is specifically incorporated herein by reference. It is understood that, if desired, blends or copolymers of any of the above materials and combinations of fibers formed from any of the above materials can be used in the present invention.

As discussed above, various glass compositions can be used to form the toughening agent of the present invention, and in one non-limiting embodiment of the present invention, the glass toughening agent comprises: At least 1 having an iron content of 11% by weight or less of the total weight of the glass composition
Includes seed glass fiber. In another non-limiting embodiment, the glass reinforcement is
It comprises at least one glass fiber having an iron content of not more than 5% by weight of the total weight of the glass composition. For example, but not limited to basalt fibers typically having a FeO content of 11 wt% and a Fe ₂ O ₃ content of 2 wt% based on the total glass composition,
Glass fibers with an iron content of less than 11% by weight are not used for some applications due to their dark color. As used herein, the term "basalt fiber" means a fiber formed from inorganic rocks having a low silica gel content, dark color, and a suitable abundance of iron and magnesium. F. Wallenber
ger et al. (eds.), Advanced Inorganic Fibers, Pr.
processes-Structures-Properties-Applic
ations (2000), page 335, which is specifically incorporated herein by reference. Therefore, in one non-limiting embodiment of the present invention, the woven fiber reinforced material is made from at least one fiber that is free of basalt fibers. For non-limiting examples of specific basalt compositions, see R.S. V. Sub
ramanian, "Basalt Fibers", Handbook of
Reinforcements for Plastics, J. Am. Milew
ski and H.M. Katz (1987), pp. 287-295 (this is
See, in particular, incorporated herein by reference). In another non-limiting embodiment of the present invention, the woven fiber reinforcement is essentially free of basalt fibers. As used herein, the term "essentially free of basalt fibers" comprises less than 1% by weight of basalt, and more preferably, based on the total weight of woven fiber reinforcement. It means that it contains no basalt fiber at all.

In another limiting embodiment of the present invention, preferably the woven fiber reinforcement comprises at least one E glass fiber (discussed above).

The following discussion briefly discusses a method of forming glass fibers suitable for use in the present invention, and means one possible method of forming glass fibers that may be used in accordance with the present invention, It is not meant to limit the invention in any way. In a typical glass fiber forming operation, molten glass is tapered through a plurality of openings in the bottom wall of a bushing or spinner to form a plurality of fibers. Almost immediately after formation, the fibers are coated with a sizing composition to protect the surface from abrasion and provide the fibers with the required process properties. As used herein, the term "size" or "sizing" refers to any coating composition applied to the fibers after formation. The fiber is then collected into strands and braided on the package for further processing. Such methods of forming glass fibers are well known in the art, and further disclosure of such methods is not considered necessary in view of the present invention. However, if more information on the fiber forming operation is desired, Loewenstein (115-115)
235), which is specifically incorporated herein by reference.

Typically, sizing compositions applied to glass fibers to be used in forming woven glass fibers are described by Loewenstein (pp. 238-244), which is specifically incorporated herein by reference. Have been disclosed). In addition, the slashing composition may include a wrapping or beaming to protect the wrap yarn from abrasion during the weaving operation when the fill yarn is inserted between the wrap yarns. A) is typically applied to sized glass fibers between. Such slashing compositions typically include ingredients such as polyvinyl alcohol and are well known to those skilled in the art. Such sizing and slashing compositions are generally effective in providing good weave of glass fiber strands and yarns made therefrom, and these compositions typically provide an electronic support. It is not compatible with the polymer matrix material used to form it. Thus, by subjecting the formed fiberglass fabric to high temperatures (eg, heating the fabric at 380 ° C. for 60-80 hours),
It is common practice in the industry to remove such non-resin compatible compositions from the surface of glass fibers prior to incorporation into the polymer matrix material by polishing the fabric and / or the fabric. These types of operations are typically referred to as heat cleaning, deoiling, or degreasing and are referred to hereafter as "degreasing (d
e-greasing) ". The fabric is then recoated with finish sizing. The finish size may typically include saline coupling agent and water and is applied to the fabric to improve compatibility between the fabric and the polymeric matrix material in which it is incorporated. However, the sizing removal process damages the fabric and can be both costly. Thus, in one non-limiting embodiment of the present invention, the reinforcing material 20 comprises a non-defatted woven glass fiber reinforced material, which is a glass fiber coated with a resin compatible sizing composition. including. As used herein, the term "resin compatible" or "polymer matrix material compatible" means that the glass fiber compatible coating composition is compatible with the polymer matrix material. However, the material incorporates glass fibers and, as a result, the coating composition (or selected coating composition) achieves at least one of the following properties: removal prior to incorporation into the matrix material (eg, , No degreasing or deoiling), good penetration of matrix material through the fibers of individual bundles of mats or fibers incorporating yarns, and good matrix material through the mat or fibers during conventional processing. A final product with properties that facilitate rapid penetration, as well as the desired physical properties and hydrolytic stability. Characteristics that. The resin-compatible sizing composition is used immediately after formation or often thereafter (eg, after weaving).
Either of them can be applied to glass fiber. As used herein, a "non-defatted" material or fabric is one that does not withstand conventional processing to remove non-resin compatible sizing constructs from the material or fabric.

Without limiting the invention, one embodiment of the resin compatible sizing composition provides one or more lattice spaces when applied to fibers attached to the fibers and between adjacent glass fibers. In this case, it comprises one or more, preferably a plurality of particles. Non-limiting examples of particles include hexagonal boron nitride and hollow styrene acrylic acid polymer particles.

In addition to the particles, non-limiting embodiments of the resin compatible sizing composition preferably include one or more film forming materials (eg, organic, inorganic and polymeric materials). Non-limiting examples of film forming materials include, but are not limited to, vinyl polymers such as polyvinylpyrrolidone, polystyrene, polyamides, polyurethanes, and combinations thereof.

In addition to or in place of the film-forming materials described above, non-limiting embodiments of the resin compatible sizing composition include one or more glass fiber coupling agents (eg,
Organosilane coupling agents, transition metal coupling agents, phosphonate coupling agents, aluminum coupling agents, amino-containing Wetner coupling agents and mixtures thereof).

Non-limiting embodiments of the resin compatible sizing composition may further include one or more emollients or surfactants. Non-limiting examples of emollients include amine salts of fatty acids, alkyl imidazole derivatives, acid solubilized fatty acid amides, condensates of fatty acids with polyethyleneimine, and amide substituted polyethyleneimines.

Non-limiting embodiments of the resin compatible sizing composition may further include one or more lubricants chemically different from the polymeric agent and the softeners described above, which may be desired on the fiber strands during weaving. Gives the treatment characteristics of. Non-limiting examples of such fatty acid esters useful in the present invention include cetyl palmitate, cetyl myristate, cetyl laurate, octadecyl laurate, octadecyl myristate, octadecyl palmitate and octadecyl stearate. Other useful fatty acid esters (lubricants) include trimethylolpropane triperalgonate, natural whale wax and triglyceride oils (eg, soybean oil, linseed oil, epoxidized soybean oil, and epoxidized linseed oil). However, it is not limited to these. Lubricants also include, but are not limited to, non-polar petroleum waxes and water-soluble polyol materials (polyalkylene polymers and polyoxyalkylene polyols).

Non-limiting examples of resin compatible sizing compositions may further include a resin reactive diluent to further improve lubrication of the coated fiber strands. As used herein, "resin-reactive diluent" means that the diluent comprises a functional group that can chemically react with the same resin that is compatible with the coating composition. To do. The diluent can be any lubricant that has one or more functional groups that react with the resin system, preferably functional groups that react with the epoxy resin system. Non-limiting examples of suitable lubricants include amine groups (eg modified polyethylene amines), alcohol groups (eg polyethylene glycol), anhydride groups, acid groups (eg fatty acids) or epoxy groups (eg epoxidation). Lubricants with soybean oil and epoxidized linseed oil).

Non-limiting embodiments of resin compatible sizing compositions include coating compositions (
For example, one or more emulsifiers are further included to suspend or disperse the components of the particles and / or the lubricant). Non-limiting examples of suitable emulsifiers or surfactants include polyoxyalkylene block copolymers, ethoxylated alkylphenols, polyoxyethylene octylphenyl glycol ethers, ethylene oxide derivatives of sorbitol esters, polyoxyethylated vegetable oils, ethoxylated alkylphenols. And nonylphenol surfactants.

Other additives may include non-limiting embodiments of resin compatible sizing compositions such as crosslinkers, plasticizers, silicones, fungicides, fungicides and antifoams. Sufficient organic and / or inorganic acids or bases to provide a coating composition of pH 2-10 can also be included in the resin compatible sizing composition.

A non-limiting example of a resin compatible sizing composition is shown in Table E, where the values in this table are all on a solids basis and are in weight percent of particular components of the total coating composition. is there.

[0089]

[Table 7] ⁶⁰ PVP K-30 Polyvinylpyrrolidone (this is Wayne, New
Commercially available from ISP Chemicals, Jersey) ⁶¹ STEPANTE 653 (this is Maywood, New Jersey)
commercially available from Stepan Company, Inc. ⁶² A-187 γ-glycidoxypropyltrimethoxysilane, which is Gr
commercially available from Crompton Corporation of eenwich, CT. ⁶³ A-174 γ-methacryloxypropyltrimethoxysilane, which is
⁶⁴ commercially available from Crompton Corporation, Greenwich, CT ⁶⁴ EMERY® 6717 partially amidated polyethyleneimine, which is Cognis Corporation of Cincinnati, Ohio.
n commercially available) ⁶⁵ MACOL OP-10 ethoxylated alkylphenol (this material is
MA, except OP-10SP accepts a post-treatment to remove the catalyst.
Similar to COL OP-10SP; MACOL OP-10 is no longer commercially available) ⁶⁶ TMAZ-81 Ethylene oxide derivative of sorbitol ester (commercially available from BASF Corp., Parsippany, New Jersey) ⁶⁷ MAZU DF-136 anti-foaming agent (this is available from Parsippany, Ne.
commercially available from BASF of Jersey) ⁶⁸ ROPAQUE® OP-96 0.55 micron particle dispersant (available from Rohm man of Philadelphia, Pennsylvania).
d commercially available from Hass Company) ⁶⁹ ORPAC BORON NITRIDE RELEASECOAT-CO
NC25 Boron Nitride Dispersant (available from Oak Ridge, Tennes
commercially available from ZYP Coatings of See) ⁷⁰ POLARTHERM® PT160 Boron Nitride powder (this is available from Advanced Ceramics Co of Lakewood, Ohio).
⁷¹ SAG10 anti-foaming agent (available from Greenwish, Connectic).
commercially available from Crompton Corporation of Ut.) ⁷² RD-847A polyester resin, which is available from Columbus, Ohio.
Commercially available from Borden Chemicals, Inc.) ⁷³ DESMOPHEN 2000 polyethylene adipate diol, which is
(Commercially available from Bayer Corp, Pittsburgh, Pennsylvania).

[0090]

[Table 8] ⁷⁴ PLURONIC ^™ F-108 polyoxypropylene-polyoxyethylene copolymer (this is BA of Parsippany, New Jersey)
Commercially available from SF Corporation) ⁷⁵ ALKAMULS EL-719 polyoxyethylated vegetable oil (this is P
Rinetone, New Jersey Rhone-Poulenc / Rh
⁷⁶ ICONOL NP-6 alkoxylated nonylphenol (which is commercially available from Odia).
BASF Corporation of Rsippany, New Jersey
⁷⁷ POLYOX WSR301 poly (ethylene oxide) (available from Dan
commercially available from Union Carbide Corp, Bury, Connecticut) ⁷⁸ DYNAKOLL Si 100 resin (this is Eka Chemica).
ls AB, commercially available from Sweden) ⁷⁹ SERMULL EN668 ethoxylated nonylphenol, which is CO
N BEA, commercially available from Benelux) ⁸⁰ SYNPERONIC F-108 polyoxypropylene-polyoxyethylene copolymer (this is the Europ for PLURONIC F-108).
⁸¹ EUREDUR 140 is a polyamide resin (which is Ciba G).
(commercially available from Eigy, Belgium) ⁸² VERSAMID 140 polyamide resin (which is Cincinnat)
i, Ohio Cognis Corp. ⁸³ FLEXOL EPO epoxidized soybean oil is available from Union Carbid.
e of Danbyry, Connecticut.

A further non-limiting example of a glass fiber yarn having a resin compatible sizing composition is the title “Impregnating Glass Fiber Strands” of US Application No. 09 / 620,526, filed November 3, 2000.
and Products Inclusion the Same ", which is specifically incorporated herein by reference.

With reference to FIG. 1, although not limiting the invention, this enhancer 20 is
0 wt% to 70 wt% prepreg material layer 14 (including the weight of inorganic filler 18) may be included. In one non-limiting embodiment, the enhancer 20 is 48% by weight.
Includes ~ 66 wt% prepreg material layer 14 (including the weight of inorganic filler 18).

In one non-limiting embodiment of electronic support 10 according to the present invention, electronic support 10 is at least one woven fiber reinforcement formed from at least one fiber that is free of basalt glass. At least one prepreg material layer 14 comprising a material 20 and at least one matrix material 16 in contact with at least a portion of the at least one reinforcement material 20, the at least one matrix material 16 comprising at least one non-fluorine. Polymer and at least one inorganic filler 18, wherein the at least one inorganic filler 18 comprises at least one non-hydratable layered inorganic solid lubricant having high electrical resistance and is all solid. At least 6% by weight, based on the matrix material 16 and at least one inorganic charge. Including the combined total weight of fillers 18. Moreover, although not required,
The at least one inorganic filler 18 may have one or more of the following properties: Mohs hardness of 6 or less, thermal conductivity of 30 W / mK or less, low coefficient of thermal expansion, and high affinity for metal ions. In one non-limiting embodiment of the invention of electronic support 10 discussed above, the at least one particulate inorganic filler 18 is hexagonal boron nitride.

In another non-limiting embodiment of the electronic support 10 according to the present invention, the electronic support 10 comprises at least one prepreg material layer 14 comprising at least one braided fiber reinforced material 20, and At least one matrix material 16 in contact with at least a portion of the at least one reinforcing material 20;
One matrix material 16 comprises at least one non-fluorinated polymer and at least one inorganic filler 18, where the at least one inorganic filler 1
8 includes at least one non-hydratable layered inorganic solid lubricant having a high electrical resistance, and a combined total of at least 10% by weight, based on total solids, of matrix material 16 and at least one inorganic filler 18. Including weight. Moreover, although not required, the at least one inorganic filler 18 may have one or more of the following properties: Mohs hardness of 6 or less, thermal conductivity of 30 W / mK or less, low coefficient of thermal expansion, and metal. High affinity for ions. In one non-limiting embodiment of the invention of electronic support 10 discussed above, the at least one particulate inorganic filler 18 is hexagonal boron nitride.

In another non-limiting embodiment of the electronic support 10 according to the present invention, the electronic support 10 is formed of at least one fiber that is free of basalt glass, at least one woven fiber reinforcement. At least one prepreg material layer 14 comprising a material 20 and at least one matrix material 16 in contact with at least a portion of the at least one reinforcing material 20, the at least one matrix material 16 comprising at least one non-fluorine. Polymer and at least one inorganic filler 18, wherein the at least one inorganic filler 18 comprises at least one inorganic solid lubricant having high thermal conductivity and high electrical resistance, and on an all solids basis. At least 6% by weight of matrix material 16 and at least one inorganic filler. Including the combined total weight of fillers 18. Moreover, although not required,
The at least one inorganic filler may have one or more of the following properties: Mohs hardness of 6 or less, thermal conductivity of 30 W / mK or less, low coefficient of thermal expansion, good lubrication properties (ie, inorganic solid lubrication). Agent), and a layered structure. Electronic support 10 discussed above
In a non-limiting embodiment of, the at least one particle inorganic filler is hexagonal boron nitride.

In another non-limiting embodiment of the electronic support 10 according to the present invention, the electronic support 10 comprises at least one prepreg material layer 14 comprising at least one braided fiber reinforced material 20, and At least one matrix material 16 in contact with at least a portion of the at least one reinforcing material 20;
One matrix material 16 comprises at least one non-fluorinated polymer and at least one inorganic filler 18, where the at least one inorganic filler 1
8 includes at least one inorganic solid lubricant having high thermal conductivity and high electrical resistance, and a combined total weight of matrix material 16 and at least one inorganic filler 18 of at least 10% by weight, based on total solids. including. further,
Although not required, the at least one inorganic filler may have one or more of the following properties: Mohs hardness of 6 or less, thermal conductivity of 30 W / mK or less, low coefficient of thermal expansion,
Good lubrication properties (ie inorganic solid lubricant), and layered structure. In one non-limiting embodiment of electronic support 10 discussed above, the at least one particulate inorganic filler is hexagonal boron nitride.

In yet another non-limiting embodiment of the electronic support 10 according to the present invention, the electronic support 10 comprises at least one prepreg material layer 14 comprising at least one fiber reinforced material 20, and at least this. There is at least one matrix material 16 in contact with at least a portion of one reinforcing material 20, the at least one matrix material 16 inhibiting conductive anode filament formation and reducing electrical shorts within the electronic support. At least one inorganic filler 18 in an amount sufficient to do so. In one particular, non-limiting embodiment, the at least one fiber reinforcement is a woven glass fiber reinforcement. In another non-limiting embodiment, the filler has a high affinity for metal ions. Although not required, fillers with high affinity for metal ions should be at least 20 meq / 100.
g CEC, and in another embodiment, at least 80 meq / 10
Having 0 g. In another non-limiting embodiment, the filler having a high affinity for metal ions has a Kd (Cu ²⁺ ) of at least 600 ml / g, and in another non-limiting embodiment, at least 1500 ml. / G and in another non-limiting embodiment at least 15,000 ml / g, and in another non-limiting embodiment at least 40,000 ml / g. Moreover, although not required, the at least one inorganic filler 18 may further have one or more of the following properties: Mohs hardness of 6 or less, low coefficient of thermal expansion, good lubricating properties, high thermal conductivity. , And high electrical resistance. Non-limiting examples of fillers with high affinity for metal ions include, but are not limited to, montmorillonite, vermiculite, saponite, bentonite, hectorite, illite, nontronite, chlorite, attapulgite, porous. Includes sex silicates, synthetic fluoromicas, and mixtures thereof. One non-limiting embodiment of the expandable synthetic fluoromica is sodium fluorophlogopite. One non-limiting embodiment of a porous silicate is an organofunctionalized porous silicate.

In one non-limiting embodiment of the electronic support 10 according to the present invention, the electronic support 10 comprises at least one woven fiber reinforced material 20.
One prepreg material layer 14 and at least one matrix material 16 in contact with at least a portion of the at least one reinforcing material 20, the at least one matrix material 16 comprising at least one non-fluorinated polymer and at least one. An inorganic filler 18 is included, wherein the at least one inorganic filler 18 has a high affinity for metal ions and comprises at least 10% by weight, based on total solids, of the matrix material 16 and the at least one inorganic filler. Including the combined total weight of material 18. In another non-limiting embodiment of electronic support 10, at least one woven fiber-reinforced material 20 is formed from at least one fiber that is free of basalt glass, and at least one inorganic filler 18 is ,
High affinity for metal ions and at least 6% by weight based on total solids
Of the combined total of the matrix material 16 and the at least one inorganic filler 18.

In another non-limiting embodiment of the electronic support 10 according to the present invention, the electronic support 10 comprises at least one prepreg material layer 14 comprising at least one braided fiber reinforced material 20, and It comprises at least one matrix material 16 in contact with at least one reinforcing material 20 and at least part of at least one inorganic filler, wherein the at least one inorganic filler 18 has a high affinity for metal ions. And including a combined total weight of matrix material 16 and at least one inorganic filler 18 of up to 5% by weight based on total solids. In another embodiment of electronic support 10, the at least one inorganic filler 18
Has a high combined affinity for metal ions and comprises up to 10% by weight, based on total solids, of a combined total weight of matrix material 16 and at least one inorganic filler 18. In yet another non-limiting embodiment of electronic support 10, the at least one inorganic filler 18 has a high affinity for metal ions,
And up to 15% by weight, based on total solids, of matrix material 16 and at least 1
Including the combined total weight of the two inorganic fillers 18.

In another non-limiting embodiment of the electronic support 10 according to the present invention, the electronic support 10 comprises at least one prepreg material layer 14 comprising at least one braided fiber reinforced material 20, and At least one matrix material 16 is in contact with at least a portion of the at least one reinforcing material 20, the matrix material 16 including at least one inorganic filler 18, where the at least one
One inorganic filler 18 is a chelating agent selected from materials having nitrogen-containing organic functional groups, sulfur-containing organic functional groups, oxygen-containing organic functional groups, phosphorus-containing organic functional groups, and mixtures thereof. In a non-limiting embodiment, the chelating agent comprises a combined total weight of matrix material 16 and at least one inorganic filler 18 of up to 5% by weight, based on total solids. In another non-limiting embodiment of electronic support 10, the chelating agent comprises a combined total weight of matrix material 16 and at least one inorganic filler 18 of up to 10% by weight, based on total solids. In yet another non-limiting embodiment of electronic support 10, the chelating agent is 1 on an all solids basis.
Includes a combined total weight of matrix material 16 and at least one inorganic filler 18 of up to 5% by weight.

The filler 18 may include a number of different materials such that together the filler material
It should also be appreciated that a combination of properties may be provided.

If not required, but desired, any of the foregoing embodiments of the electronic support 10 according to the present invention may further comprise at least a portion of at least one surface of at least one of the one or more prepreg material layers 14. It may include a contacting electrically conductive material (not shown). Without limitation herein, at least one surface can be an outer major surface. As used herein, the term "outer major surface" means the exposed major surface. Further, the electrically conductive material may include at least one circuit. As used herein, the term "circuit" means any feature formed in or by an electrically conductive material, and as defined herein, for example. No line, pad, land (l
and) and other features normally formed on printed circuit boards to provide the necessary electrical and / or thermal interconnections. Electronic support 10 may also include at least one opening that at least partially extends the electronic support, as described further below. Continuing with reference to FIG. 1, a non-limiting method of forming an electronic support 10 according to one embodiment of the present invention is generally discussed. The method includes combining at least one filler material 18 and at least one matrix material 16. This combining step can be accomplished by any method known in the art for combining fillers with polymeric materials. For example, without limiting the invention, if at least one matrix material 16 comprises a curable polymer, a solvent solution of the polymer is formed and then at least one inorganic filler 18 is mixed into the solution.
However, at least one matrix material 16 comprises a thermoplastic polymer, which may first be melted and then at least one inorganic filler 18
Can be mixed with the molten polymer. Alternatively, a powder mixture of a thermoplastic polymer and at least one inorganic filler 18 may be formed and then heated to melt the polymer or the powder mixture is mixed and passed through an extruder to obtain intimate contact. An intimate mixture can be formed, and the resulting mixture can be calendered into flat sheets.

The inorganic filler 18 is a binder or other compatibilizer.
It will be appreciated by those skilled in the art that it may be pre-treated with a gagent) to improve the wettability of the matrix material 16 on the inorganic filler 18. Moreover, although not required in the present invention, a binder may be added to the matrix material prior to the addition of the inorganic filler material to improve wettability. The treatment of inorganic fillers for use in polymeric materials is well known to those skilled in the art, and further disclosure of methods of treating particles can be found in
Not considered necessary. However, if more information is desired, Hand
book of Fillers for Plastics, H.M. Katz
and J. See Milewski, eds. (1987), pages 65-115, which are specifically incorporated herein by reference.

In one non-limiting embodiment of the present invention, at least one inorganic filler 1
8 is pretreated with at least one solvent that is compatible with the polymer matrix material 16, formed into a paste and then dispersed in the polymer matrix material 16. As used herein, the phrase "at least one solvent compatible with the polymeric matrix material" may allow at least one solvent to at least partially solvate or swell the polymeric matrix material. Means that. In one embodiment of the invention where the polymeric matrix material is an epoxy material, but not limited to this, the inorganic material 18 is acetone, dimethylformamide (DM).
It is pretreated with at least one solvent selected from F), methylene chloride, glycol ether, methyl ethyl ketone (MEK), and mixtures thereof.

After combining or dispersing at least one inorganic filler 18 in the polymeric matrix material 16, the polymeric matrix material 16 is then
It is applied to the reinforcing material 20 by any method known to form prepreg materials. For example, without limiting the invention, when the reinforcement 20 is in the form of a woven glass fiber fabric, the reinforcement 20 is immersed in a bath containing a polymeric matrix material 16 containing at least one inorganic filler 18. Obtained and subsequently squeezed between a set of metering rolls, leaving a measured amount of matrix material 16 therein. Alternatively, the polymeric matrix material 16 comprising at least one inorganic filler 18 may be sprayed onto the reinforcement 20 by any method known to those skilled in the art. Polymeric matrix material 1 with inorganic filler 18, such as electrostatic coating and electrostatic coating
Other ways of applying 6 are also contemplated by the present invention.

After forming the prepreg material 14, the polymeric matrix material 16 is typically at least partially cured, for example by passing the prepreg material through a dryer. As used herein, the phrase "at least partially cured" refers to at least partially dried, cooled, and / or cured polymeric matrix material. The prepreg lumber material can then be cut to the required size and, if necessary, combined with one or more additional prepreg lumber layers. Generally, but not limiting the invention, in a conventional layering operation, the prepreg material is cut (or punched) to a desired size and two or more cut prepreg material layers are stacked together. Layered and cured, for example, by compressing the stack between steel plates that have been polished at elevated temperature and pressure for a predetermined length of time to cure the polymeric material and laminate of the desired thickness. 310 (shown in FIG. 3)
To form the electronic support. The method of forming the laminate according to the present invention is discussed in further detail below.

In one non-limiting example of the method according to the present invention, the filler 18 comprises particulate boron nitride, which is pretreated with acetone to form a paste. Then
This paste is dispersed in an epoxy resin containing 45-65 wt% solids (before the addition of boron nitride paste) to form an epoxy resin containing 13 wt% -17 wt% boron nitride, based on total solids. To do. This epoxy resin with particulate boron nitride dispersed therein is then applied to the woven glass fiber reinforcement to form a prepreg material layer. Then, the epoxy resin of the prepreg material layer is at least partially solidified. It was observed that by pretreating the boron nitride in this manner, the boron nitride could be more easily dispersed in the epoxy resin.

Referring now to FIG. 2, another non-limiting embodiment of an electronic support 210 according to the present invention is shown. The electronic support 210 comprises at least one layer of prepreg material 214, which layer comprises at least one reinforcement 220 and at least one matrix material 216, which matrix material comprises:
It is in contact with at least a portion of at least one reinforcement 220. At least 1
At least one layer 217 including two inorganic fillers 218 is prepreg material layer 21.
4 at least in part 224 of at least one surface (eg, major surface 226 of the prepreg material). Although not necessary, but desired, at least one layer 217 is located on one or more selected portions of at least one surface 226 of the prepreg material layer 214, as discussed in further detail below. To provide at least a partial layer or to be located substantially entirely over at least one surface 226 of the prepreg material layer 214 to form an essentially continuous layer or surface of the filler 218. obtain.

The at least one reinforcement 220 may include any of the reinforcements 20 discussed above for use in the electronic supports of the present invention. In one non-limiting embodiment, the reinforcement 220 is a glass fiber reinforcement. In another non-limiting embodiment, the reinforcement 220 is a woven glass fiber reinforcement. In yet another non-limiting embodiment, the reinforcement 220 is a non-defatted, resin-compatible, woven glass fiber reinforcement.

Further, the matrix material 216 can be any of the matrix materials 16 discussed above, and can contain any of the inorganic fillers 18 discussed above. For example, without limitation herein, at least one reinforcement 220.
Can be a non-defatted resin compatible woven fiberglass fabric, and the matrix material 216 can be up to 40% by weight based on the combined total weight of epoxy resin and boron nitride based on total solids. It can be an epoxy material, including hexagonal boron nitride.

Layer 217 may include one or more inorganic fillers discussed above. In one non-limiting embodiment of the invention, the at least one inorganic filler 218 comprises an inorganic solid lubricant, a high thermal conductivity material, a low thermal expansion material, a material having a high affinity for metal ions, a high It is selected from electrically resistive materials (all of which are discussed above) and combinations and mixtures of these.

In one non-limiting embodiment of the present invention, wherein the at least one inorganic filler 218 is at least one inorganic solid lubricant, the inorganic solid lubricant is hexagonal boron nitride, metal dichalcogenide, It is selected from boric acid, antimony oxide, talc, and mixtures thereof. In another non-limiting embodiment, the inorganic solid lubricant is a non-hydratable inorganic solid lubricant having a laminated structure (discussed above). In yet another non-limiting embodiment, the non-hydratable inorganic solid lubricant having this layered structure is hexagonal boron nitride.

In another non-limiting embodiment of the present invention, wherein at least one inorganic filler 218 is a high thermal conductivity material, the high thermal conductivity material is hexagonal boron nitride, aluminum nitride, graphite, and the like. Selected from a mixture of. In another non-limiting embodiment, the high thermal conductivity material has a thermal conductivity of at least 30 W / mK. In yet another non-limiting embodiment of the present invention, at least 30
This high thermal conductivity material with a thermal conductivity of W / mK is hexagonal boron nitride.

In another non-limiting embodiment of the present invention, wherein the at least one inorganic filler 218 is a low thermal expansion material, the low thermal expansion material is hexagonal boron nitride, yugite, aluminum titanate, And mixtures thereof. In another non-limiting embodiment, the low thermal expansion material has a coefficient of thermal expansion of 100 × 10 ⁻⁷ / ° C. or less over a temperature range of 0 ° C. to 200 ° C. In yet another non-limiting embodiment, the low thermal expansion material has a coefficient of thermal expansion of 50 × 10 ⁻⁷ / ° C. or less over a temperature range of 0 ° C. to 200 ° C. In one non-limiting embodiment of the present invention, the low thermal expansion material is hexagonal boron nitride.

In one non-limiting embodiment of the invention, wherein at least one inorganic filler 218 is a material having a high affinity for metal ions, the material has a CEC of at least 200 meq / 100 g. And in another non-limiting embodiment, has a CEC of at least 80 meq / 100 g. In another non-limiting embodiment, the filler having a high affinity for this metal ion has a K _d (Cu ²⁺ ) of at least 600 ml / g, and in another non-limiting embodiment, Is at least 1500 ml / g, and in another non-limiting embodiment, at least 15,000 ml / g, and in another non-limiting embodiment, at least 40,000 ml / g K _d (Cu ^2+). ) Has. Non-limiting examples of fillers with high affinity for metal ions include montmorillonite, vermiculite, saponite, bentonite, hectorite, illite, nontronite, chlorite, attapulgite, porous silicates, synthetics. Included, but not limited to, fluoromica, and mixtures thereof. In one non-limiting embodiment, the expandable synthetic fluoromica is sodium fluorophlogopite. In one non-limiting embodiment, the porous silicate is an organofunctionalized porous silicate.

In another non-limiting embodiment of the present invention, at least one inorganic filler 21.
8 is a chelating agent selected from a material having a nitrogen-containing organic functional group, a material having a sulfur-containing organic functional group, a material having an oxygen-containing organic functional group, a material having a phosphorus-containing organic functional group, or a combination thereof. Is.

In one non-limiting embodiment of the present invention, wherein at least one inorganic filler 218 is a high electrical resistivity material, the high electrical resistivity material is boron nitride, talc, mica, And mixtures thereof. In one non-limiting embodiment, the high electrical resistivity material is at least 1000 μΩ · cm.
It has an electric resistivity of. In one embodiment, but not limited to the present invention, the high electrical resistivity material having an electrical resistivity of at least 1000 μΩ · cm is hexagonal boron nitride.

In yet another non-limiting embodiment of the present invention, the at least one inorganic filler 218 has a Mohs hardness value that is less than or equal to the Mohs hardness value of the at least one reinforcement 220. In another non-limiting embodiment, at least one inorganic filler 218
Has a Mohs hardness value of 6 or less. In one embodiment, but not limited to the present invention, the inorganic filler 218 having a Mohs hardness value of 6 or less is hexagonal boron nitride.

At least one of, but not limited to, at least one layer 217 herein.
One inorganic filler 218 may comprise 5 wt% to 35 wt% of the combined total weight of matrix material 216 and at least one layer 217, based on total solids. In one non-limiting embodiment, at least one inorganic filler 218 is
10% to 30% by weight of the matrix material 216 and at least one layer 217, based on total solids. In yet another non-limiting embodiment, the at least one inorganic filler 218 is based on an all solids matrix material 21.
12 to 28% by weight of the total combined weight of 6 and at least one layer 217.
Make up.

Layer 217 may further include other materials in addition to the inorganic fillers discussed above. For example, without limitation in the present invention, layer 217 may be an organic lubricant (eg, polytetrafluoroethylene and stearate (eg, zinc stearate)).
Particulate organic fillers (eg, rubber particles); and adhesives (discussed below)
Can be included.

In one embodiment of the invention, without limitation herein, the at least one layer 217 comprises no more than 25% by weight of adhesion, based on the total weight of the at least one layer 217 based on total solids. Including agents. In another non-limiting embodiment, at least one layer 217 comprises 10 wt% or less adhesive, based on the total weight of the at least one layer 217 based on total solids. In another non-limiting embodiment, at least one layer 217 comprises no more than 5 wt% adhesive, based on the total weight of the at least one layer 217 based on total solids. As used herein, the term "adhesive" refers to layer 217 to support adhesion between layer 217 and other materials (eg, other prepreg material layers or conductive layers). Means a polymeric material added to. The adhesive may have the same chemical composition as the matrix material 216, or the adhesive may have a different chemical composition.

Incorporation of an adhesive into layer 217 allows for the entire resin of prepreg material layer 214 (compared to a prepreg material layer comprising layer 217 that is essentially free of such adhesive).
It will be appreciated by those skilled in the art that the polymer) content can be increased. Such an increase in overall resin content can be detrimental to the properties of the electronic support incorporating the prepreg material layer. As a result, including but not limited to herein, when an adhesive is incorporated into layer 217, the adhesive and polymer matrix material 21
The amount of 6 results in a total resin content of the prepreg material layer 214 (based on the combined total weight of reinforcement 220, polymer matrix material 216, and layer 217 based on total solids) of 25 to 45 weight percent. Can be adjusted. In one non-limiting embodiment, the amounts of adhesive and polymer matrix material 216 are adjusted so that the total resin content of prepreg material layer 214 is in the range of 28-42% by weight.

In another non-limiting embodiment of the invention, layer 217 is essentially free of adhesive. As used herein, the phrase "essentially free of adhesive" means that layer 217 is at least 0.1% by weight, based on the total weight of layer 217 based on total solids. It is meant to include an adhesive, and preferably to include no adhesive.

As discussed in further detail below, the prepreg material layer 214 of the electronic support 210 can be a first prepreg material layer and the electronic support 210 can be a first prepreg material layer.
May further comprise at least one additional prepreg material layer (not shown in FIG. 2 but shown in FIG. 3) laminated to at least a portion of the prepreg material layer 214 of FIG. In one non-limiting embodiment of the invention, at least one layer 217 is located between at least one additional prepreg material layer and the first prepreg material layer 214 to form a laminate. In another non-limiting embodiment, the first layer and prepreg material layer are combined in such a manner that layer 217 is at least partially exposed.

If not necessary, but desired, a conductive material (not shown in FIG. 2) may also be located on at least one outer surface of electronic support 210, and in more detail below. As discussed, at least one circuit can be formed in the conductive material.

In one embodiment, but not limited to herein, the at least one layer 217 overlies at least a portion of the first surface 226 of the prepreg material layer 214 and the conductive material is , The second opposite surface 2 of the prepreg material layer 214
Located on at least a portion of 28.

If desired, but not required, electronic support 210 further comprises at least one opening extending at least partially through the electronic support, as discussed below. obtain.

Non-limiting methods of forming the electronic support 210 are generally discussed herein.
Referring again to FIG. 2, a prepreg material layer 214 comprising at least one matrix material 216 and at least one reinforcement 220 is formed in a conventional manner and at least one matrix material 216 is at least partially solidified. It Thereafter, at least a portion of the at least partially solidified matrix material 216 is at least partially solvated and at least one inorganic filler 218 is at least a portion of the at least partially solvated polymeric matrix material 226. Bonded to a portion to form at least one layer 217.
If desired, a further layer of matrix material and / or inorganic filler 218 (not shown) can then be applied over layer 217 to add, and at least partially, as discussed above. Can be solidified into. This prepreg material can then be further processed into a laminate, as discussed below.

In one non-limiting embodiment of the present invention, after the prepreg material layer 214 has been at least partially solidified, at least one layer 217 comprising at least one inorganic filler 218 is at least one inorganic filler. Material 218 and propellant,
And, if desired, by spraying an aerosol containing a solvent compatible with the at least one polymer matrix material, the prepreg material layer 21
4 may be adhered to at least a portion 224 of at least one surface 226. A non-limiting example of an inorganic filler in aerosol form suitable for use in the present invention is Boron Nit containing boron nitride, acetone, and propellant.
Ride Aerosol Lubricant, which is Oak Ri
Dge, Tennessee's ZYP Coatings, Inc. Is commercially available from.

Alternatively, without limitation in the present invention, at least one inorganic filler 218.
At least one layer 217 comprising at least one solvent and at least one layer
It may be applied to at least a portion 224 of at least one surface 226 of the prepreg material layer 214 by dip coating the prepreg material layer 214 in a solvent bath containing one inorganic filler 218. For example, without limitation, prepreg material layer 214 is at least partially immersed in a solvent bath comprising at least one solvent compatible with at least one polymer matrix material 216 and at least one inorganic filler 218, the bath Removed from the prepreg material layer 2 and then dried
A prepreg material layer 214 may be formed that includes at least one partial layer 217 overlying at least a portion 224 of at least one surface 226 of the fourteen.

Preferred solvents for use in the aforementioned methods of forming layer 217 include:
A solvent compatible with at least one polymer matrix material 216 used to form the prepreg material layer 214 may be included, but is not limited to. While not meant to be bound by any particular theory, the use of such a solvent ensures that the surface of the prepreg material is at least one polymer matrix material 216 when the prepreg material is contacted with the solvent. It becomes tacky due to partial solvation, which facilitates adhesion of the at least one inorganic filter to the surface of the prepreg material. Moreover, making the surface of the prepreg lumber layers tacky in this manner is intended to facilitate the lamination of the prepreg lumber layers by reducing slippage between the prepreg lumber layers when stacked. To be done. One of skill in the art will recognize that the choice of solvent will depend on several factors, including but not limited to, the polymeric matrix material 216 used to form the prepreg material and the desired amount of solvation. To be done. Non-limiting examples of solvents for use in prepreg materials that include epoxy-containing polymeric matrix materials include acetone, dimethylformamide (DMF), methylene chloride, glycol ethers (eg, methoxyisopropanol), other ketones ( For example, methyl ethyl ketone (MEK)) and mixtures thereof. Although not required, the solvent bath may further include, for example, polymeric matrix materials (epoxys), adhesives, particulate organic fillers, and other processing aids (eg, dispersants for at least one inorganic filler 218). . It will be appreciated by those skilled in the art that the type and amount of solvent can be controlled to produce the desired level of solvation for a given polymeric matrix material 216.

Although not necessary, if desired, a portion of the surface of the prepreg material 214 may be coated with any of those known in the art prior to coating to prevent adhesion of the at least one inorganic filler 218 in the masked area. Can be masked in this manner. For example, without limiting the invention, the selection of surface 226 of prepreg material 214 prior to application of inorganic filler 218 to prevent adhesion of inorganic filler 218 of layer 217 to selected portions of the prepreg material surface. A masking tape may be applied to the formed portion. Further, any or all surfaces of the prepreg material layer 214 may be at least partially or entirely coated with at least one inorganic filler 218 to form a continuous flat surface or layer 217.

In another non-limiting method for forming electronic support 210 in accordance with the present invention, at least one polymeric matrix material 216 can be applied to at least one reinforcing material 220, and then at least one. At least one layer 217 comprising one inorganic filler 218 may be applied to at least one portion 224 of at least one surface 226 of the prepreg material layer 214 (although the polymer is still tacky) (ie, previously Prior to at least partially setting at least one polymer matrix material 216). For example,
The inorganic filler 218 may be applied by spraying or spraying the filler 218 on a portion 224 of the surface 226, or by electrostatically depositing the filler 218 on the location 224 of the surface 226 ( However, the polymer matrix material 216 is at least partially tacky). If desired, a further layer of polymer matrix material and / or inorganic filler 218 (not shown) is then added to layer 2
17 and can be at least partially set. The prepreg material can then be further processed into laminates as described below.

Referring now to FIG. 3, an electronic support 310 with a laminate 312 is shown. The laminated plate 312 includes a first prepreg material layer 314, a second prepreg material layer 315 adjacent to a surface 326 of the first prepreg material layer 314, the first prepreg material layer 314, and the second prepreg material layer 314. A material layer 315 and at least one layer 317 including at least one inorganic filler 318. In one non-limiting embodiment of the invention, and as previously discussed, at least one layer 317 is 25 based on the total weight of the at least one partial layer on the layer solid substrate.
Contains less than or equal to wt% adhesive material. In one non-limiting embodiment, at least 1
The two layers 317 are essentially free of adhesive material.

As shown in FIG. 3, but not limited to the present invention, the first prepreg material layer 314 of the laminate 312 comprises at least one reinforcing material 320, at least a portion of the at least one reinforcing material 320. At least one comprising at least one polymeric material 316 in contact with the prepreg material layer 314 and at least one inorganic filler 318 disposed on at least a portion 324 of the surface 326 of the prepreg material layer 314.
The second prepreg material layer 315 includes at least one reinforcing material 321 and at least one polymeric matrix material 336 in contact with at least a portion of the at least one reinforcing material 321. Although not required, in one non-limiting embodiment of the invention, the reinforcing materials 320 and 321 are the same and the polymeric matrix materials 316 and 336 are the same.

If desired, but not required, the prepreg material layer 315 also includes a layer similar to the layer 317 of prepreg material 314 (FIG. 3) applied to at least one portion of at least one surface of the prepreg material layer 315. (Not shown). Laminate 312 is 1
One or more additional prepreg lumber layers (not shown) may further be included, and the one or more additional prepreg lumber layers may further comprise one or more layers similar to layer 317, if desired. As will be appreciated by those skilled in the art.

In one non-limiting embodiment of an electronic support in the form of a laminate according to the invention, the laminate comprises a plurality of layers of prepreg material laminated together, so that
At least one layer comprising at least one inorganic filler is disposed between at least part of at least one pair of adjacent prepreg material layers. In another non-limiting embodiment, the laminate comprises a plurality of layers of prepreg material laminated together such that at least one layer comprising at least one inorganic filler comprises each of the adjacent layers of prepreg material. Located between at least some of the pairs.

With reference to FIG. 3, in one non-limiting embodiment of the present invention, as described above,
The laminate includes a plurality of prepreg materials, where one or more prepreg material layers 314.
Is at least one layer 317 (at least one surface 32 of this prepreg material).
6 of at least one inorganic filler 318) and / or one or more layers of prepreg material 315 (comprising at least one reinforcing material 321 and at least one polymeric matrix material 336). The polymeric matrix material 336 includes at least one inorganic filler 319 in contact with at least a portion of the reinforcing material 321. In another non-limiting embodiment, the laminate comprises at least one layer of prepreg material, the layer being at least one in contact with at least a portion of at least one surface of the prepreg material.
At least one layer comprising two inorganic fillers, and at least one reinforcing material;
And at least one polymeric matrix material (including at least one inorganic filler in contact with at least a portion of the reinforcing material). In yet another embodiment, the laminate comprises one or more layers of prepreg material, the prepreg material layer being essentially free of inorganic filler in addition to the prepreg material layers discussed above.

Referring now to FIGS. 2 and 3, prepreg material 214 and laminate 312.
The above-described method of forming the electronic supports 210, 310 in the form of: a high dose fraction of the inorganic filler, prior to impregnation with the reinforcing materials 220, 320, into a polymeric matrix material 216, 316. Advantageously, it allows at least one layer 217, 317 (including at least one inorganic filler 218, 318) to be incorporated into the electronic support 210, 310 without direct mixing therein. It is believed that there is. Furthermore, the placement and distribution of layers 217, 317 on surfaces 226, 326 of prepreg material layers 214, 314 may be more carefully controlled by these methods, which allows for inorganic packing within electronic supports 210, 310 themselves. Material 2
18, 318 specified distributions are possible.

Further, as shown in FIG. 3, when at least one layer 317 is desired, it may be incorporated into laminate 312 to form an essentially continuous inner layer or plane within laminate 312. obtain. Therefore, the inorganic filler material 31 is required to have specific properties.
By choosing 8, for example, but not limited to herein, high temperature conduction, good lubrication properties, low temperature expansion, low electrical conduction, and / or high affinity for metal ions, and electronic support 310. Functionality and ability may be improved. This is particularly advantageous when the electronic support 310 is used to form a PCB. For example, without limitation herein, if the at least one inorganic filler 318 is selected to have high temperature conduction, the continuous inner layer formed by the layer 317 containing the inorganic filler 318 may be in a PCB. Heat spreader (heat)
It can act as a spreader (heat spreader) and improve the ability of the active device to be mounted on the PCB. In addition, such an inner layer reduces or eliminates the differential thermal expansion and distortion of the PCB by spreading or spreading the heat from soldering and other bonding processes that are evenly spread over the PCB during assembly. By doing so, the yield in the assembly process can be enhanced.

In another non-limiting example, the continuous layer 317 of the electronic support 310 can comprise at least one inorganic filler 318 that has a low thermal expansion. This filler, as discussed previously, is barr at the plateed openings formed in the PCB.
el) can reduce cracking.

In another non-limiting example, the continuous layer 317 can include at least one inorganic filler 318 that has a high affinity for metal ions. This filler can prevent electrical shorts due to conductive anode filament formation within the PCB, as discussed previously.

In another non-limiting example of an electronic support that is particularly desirable for use in mechanical drilling operations, layer 317 can include a lubricant. More specifically, electronic support 310 may include laminate 312 (comprising a stack of prepreg material layers 314, 315 laminated together); and layer 317 (comprising a lubricant). As discussed earlier, layer 317 includes at least one of the adjacent prepreg lumber layers of the prepreg lumber layer.
It may be placed between two pairs or along one of the outer large surfaces of the support. As used herein, the term "stack" refers to at least two items, such as layers of prepreg material, laminates, electronic supports, and the like.
It is meant to be aligned in a stacked relationship to form a stack of such items. In one embodiment, without limitation herein, layer 31
7 includes a lubricant and further comprises less than 25 weight percent adhesive material based on the total amount of layers on the total solid substrate. Lubricants include, but are not limited to, inorganic solid lubricants and organic lubricants. Inorganic solid lubricants include, but are not limited to, hexagonal boron nitride, boric acid, molybdenum disulfide, graphite, and mixtures thereof. Organic lubricants include, but are not limited to, polytetrafluoroethylene, zinc stearate, and mixtures thereof.

Non-limiting methods of forming electronic supports that are particularly desirable for use in mechanical drilling operations are generally described herein. The method comprises applying a lubricating material to at least a portion of at least one large surface of the first prepreg lumber layer, stacking the first prepreg lumber layer with one or more additional prepreg lumber layers. A step (so that this lubricating layer is disposed between the first prepreg material layer and at least one of the one or more further prepreg material layers to form an internal lubricating layer), as well as the first prepreg material layer And overlaying one or more additional layers of prepreg material together to form an electronic support. If desired, but not necessarily, at least one of the one or more additional prepreg material layers may further include a lubricating layer disposed on at least a portion of at least one surface thereof.

In another non-limiting embodiment of the method of forming an electronic support in the formation of a laminate according to the present invention, an inorganic filler can be first applied to the desired portion of the reinforcing material, then A polymeric matrix material can be applied thereon. For example, without limitation, the inorganic filler may be electrostatically placed on top of the reinforcing material, or the reinforcing material may be immersed in a slurry of inorganic filler and solvent (preferably water). After coating the reinforcing material, the polymeric matrix material may be applied to the reinforcing material over the inorganic filler, for example by spraying or dip coating. The polymer matrix material can then be partially solidified. If desired, but not necessarily, an additional layer of inorganic filler may be applied to the polymeric material before or after drying, particularly as described above. Thereafter, the polymeric material may be at least partially solidified and / or additional layers of polymeric matrix material and / or inorganic filler may be built upon the reinforcing material, if desired. The prepreg lumber material may then be cut and laminated as described above to form an electronic support in the form of a laminate.

In another non-limiting embodiment of the invention, the reinforcing material is wet laid (we).
t-laid) paper making process. Here, at least one inorganic filler is applied thereto during the formation of the paper reinforcement material.
For example, but not a limitation of the present invention, the glass fiber paper reinforcement material may be formed by dipping the chopped glass fiber strands in a white aqueous solution with an inorganic filler material. As used herein, the term “white water solution” refers to, for example, a dispersant,
An aqueous solution that may include thickeners, softeners, and hardeners, and dispersing or emulsifying polymers. Such white solution (white turbid aqueous solution) is well known to those skilled in the art. If further information is needed, US Pat. No. 5,393,379
Incorporated herein by reference in detail). The dispersant or slurry can then be deposited during the headbox and subsequent casting (ie, deposited on a moving wire screen to form a glass fiber sheet). The sheet is then at least partially dried by a suction or vacuum (vacuum) device to form a filled glass fiber paper reinforcement material (ie, a glass fiber paper reinforcement material incorporated into the filler material). The polymer matrix material is then applied to the paper reinforcement material, as discussed in detail above, to form the prepreg material layer according to the present invention. If desired, the inorganic filler may be incorporated into a polymer matrix material applied to the paper-reinforced material, as discussed previously, and / or the layer comprising one or more inorganic fillers may be prepreg material. It can be applied to layers. Two or more layers of prepreg material may then be stacked and laminated as discussed above.

In another non-limiting example of a wetride paper process that can be used to form a filled glass fiber paper reinforcement material according to the present invention, chopped glass fibers and one or more inorganic fillers are included. Disperse in water with one or more blowing agents. A suitable blowing agent for use in the present invention is ethoxylated octylphenol, which is a Union carbide Corporation of Dan.
TRITON X10, commercially available from bury, Connecticut
It is 0. The dispersion is then stirred to form a foamy slurry. It is then cast onto a web and the foam is aspirated and at least partially dried to form a filled glass fiber paper reinforcement material. The polymer matrix material can then be applied to the paper-reinforced material, in particular as discussed above, to form the prepreg material layer according to the present invention. If desired, the inorganic filler may be incorporated into a polymer matrix material applied to the paper-reinforced material as previously discussed, and / or the layer containing one or more inorganic filler materials may be the prepreg material. It can be applied to layers. The two or more layers of prepreg material are then
It can be stacked and stacked as discussed above.

The present invention further contemplates electronic supports in the form of coated laminates and printed circuit boards made from layers and laminates of prepreg material as described in detail above. Referring back to FIG. 3, an electronic support 310 according to the present invention may include an electrically conductive layer 322 comprising an electrically conductive material, which is at least a portion of at least one surface 327 of the laminate 312. 325 in contact with the coated laminate 3
13 is formed.

The layer 322 of electrically conductive material may be formed by any method known to one of ordinary skill in the art. For example, without limiting the invention, the electrically conductive layer 322 may comprise a thin sheet or foil of electrically conductive material, such as, but not limited to, metallic materials, semi-cured or cured prepreg. Formed by laminating the material 315 or at least a portion 325 of the surface 327 of the laminate 312. Alternatively, the electrically conductive layer 322 may be formed from a layer of electrically conductive material using a well-known technique including, but not limited to, electroplating, electroless plating or sputtering, a semi-cured or cured prepreg. It may be formed by depositing material 315 or at least a portion 325 of surface 327 of laminate 312.

Suitable electrically conductive materials for use as the electrically conductive layer 322 include copper,
Included, but not limited to, silver, aluminum, gold, tin, tin-lead alloys, palladium, and combinations and alloys thereof.

With continued reference to FIG. 3, a non-limiting method of forming a coated laminate 313 according to the present invention will now be discussed generally. This method includes two or more prepreg material layers 3
14, 315, at least one of which is made according to one of the methods discussed above for making the prepreg material according to the present invention, and the electrically conductive material 32.
Stacking one or more layers 322 of 3 together, as well as its prepreg material 3
14, 315 and the electrically conductive layer 322 are laminated together to form a coated laminate 313. In one embodiment, but not limited to herein, at least one layer of the one or more layers of electrically conductive material 323 is disposed on at least one outer large surface 327 of the coated laminate 313. To exist
Positioned.

Those skilled in the art will appreciate that the prepreg materials, laminates and coated laminates of the present invention are useful in forming multilayer printed circuit boards well known in the art. As used herein, the term "multilayer printed circuit board" means a printed circuit board having at least one inner layer of electrically conductive material. The inner layer may be present as a substantially continuous plane (ie, a power or ground plane), or the inner layer may be patterned with one or more circuits, as discussed below.

A non-limiting method of forming a printed circuit board according to the present invention will now be described generally. The method comprises the steps of forming a coated laminate according to the present invention as discussed above, and one or more circuits in any manner well known in the art to at least one electrically conductive layer of the coated laminate. Patterning on at least a portion of the layer. For example, but not meant to be limiting herein, a photoresist is applied to this electrically conductive layer, photo-imaged and developed according to procedures well known in the art. . The exposed electrically conductive material can then be etched to form circuits on the surface of the electronic support. Such methods are well known in the art, and the examples given above are meant to be merely illustrative of one suitable method of patterning a circuit and are not meant to be limiting in the present invention. In addition to or instead of forming one or more circuits on at least one surface of the laminate, one or more openings or vias extending at least partially through the electronic support are provided in the art. Can be drilled or drilled into its electronic support to form a circuit board in accordance with the invention by any method known in, for example, but not limited to mechanical or laser drilling.

Non-limiting methods of forming openings in an electronic support, and in particular in a printed circuit board according to the present invention, will now be discussed generally.

[0155] Typically, the openings are formed in the electronic support, most commonly by drilling the electronic support by a mechanical drilling process,
It enables electronic interconnection between circuits that are patterned on opposite surfaces of the electronic support. After formation of the opening, a layer of electrically conductive material is deposited on the wall of the opening and / or the opening is filled with the electrically conductive material,
Facilitates required electronic interconnections and / or heat dissipation. As discussed above, the drilling process is an important step in determining the overall production yield and cost as well as the quality of the printed circuit board to be manufactured. If the drilled holes are not correctly positioned, or if the hole walls are rough, the resin will be disturbed (sm
or otherwise, the defective panel may have to be scrapped. Moreover, if drilling defects occur after circuitry patterning, the cost of scrapping the panel is significantly increased. It has been observed that aperture forming devices used to form apertures in printed circuit boards or electronic supports are consumed during drilling, which
The quality and position accuracy of the drilled holes and the overall quality of the substrate are reduced. As a result, the production yield is reduced, which causes an increase in production costs.

The method of forming openings according to the present invention provides for these to potentially increase drill life, reduce drill tool wear, improve hole wall quality and hole location accuracy, and drilling costs. It is particularly advantageous in forming openings in electronic supports during the production of printed circuit boards in that it is believed that they can provide a reduction in Further, the method and apparatus of the present invention can be incorporated into existing drilling operations without requiring significant equipment modifications or additional processing steps. Other printed circuit board processing operations (eg, router machining, edging, dicing and finishing)
It is further contemplated that may benefit from the methods disclosed herein.

A non-limiting method of forming an opening in an electronic support according to the present invention is described herein.
Discuss in general. With reference to FIG. 4, the method involves positioning the electronic support 410 in register with the aperture forming device 412. Without being meant to be limiting, the electronic support 410 is an electronic support formed in a manner as discussed in detail above, and a matrix material and / or as disclosed herein. Alternatively, it may include a layer incorporating a filler material. Nevertheless, the method of the present invention is also suitable for use with conventional electronic supports, which are readily commercially available from various manufacturers. As used herein, "aperture forming device" means any device capable of mechanically forming an opening in an electronic support. In the embodiment shown in FIG. 4, but not limited to the present invention, the aperture forming device 412 uses a drill bit 413 to form the aperture 414. Examples of commercially available aperture forming devices 412 suitable for use with the present invention include Hitachi-H Mark 10D 5 heads (
Spindle machine, Uniline 2000 single head machine, and Pl
Examples include, but are not limited to, uritec single-spindle multi-station drilling machines.

After positioning the electronic support 410 in place using the aperture forming device 412, the opening 414 extending at least partially through the thickness 416 of the electronic support 410 is opened. The forming device 412 is formed by placing the forming device 412 in contact with at least a portion 417 of the electronic support 410 and penetrating the portion 417. In one non-limiting embodiment of the present invention, solid lubricant 42
2 and carrier 423, a fluid flow 420 is provided proximate opening formation device 412 during at least a portion of the opening formation operation, such that as the drill bit advances through electronic support 410. The solid lubricant 422 contacts at least a portion 424 of the interface 426 between the drill bit 413 of the aperture forming device 412 and the electronic support 410. It is understood that the methods discussed above can be used to form openings in laminates incorporating filler material as disclosed herein, and in conventional laminates. Should be.

In one non-limiting embodiment of the present invention, solid lubricant 422 is preferably an inorganic solid lubricant. Any of the inorganic solid lubricants discussed above for use as the inorganic filler material 18 (shown in FIG. 1) can be used as the inorganic solid lubricant 422 according to the method of forming an opening in accordance with the present invention. In one non-limiting embodiment, the inorganic solid lubricant 422 is an inorganic solid lubricant material having a layered structure. For example, without limitation herein, suitable inorganic solid lubricant particles having a layered structure include boron nitride, boric acid, graphite, metal dichalcogenides, mica, talc, kaolinite, cadmium iodide, and the like. A mixture of Suitable metal dichalcogenides include, but are not limited to, molybdenum disulfide, molybdenum diselenide, tantalum disulfide, tantalum diselenide, tungsten disulfide, tungsten diselenide, and mixtures thereof. In one non-limiting embodiment of the present invention, an inorganic solid lubricant for use in fluid stream 420.

Non-limiting examples of boron nitride particles suitable for use in the present invention include the POLARTHERM hexagonal boron nitride particles discussed above.

The carrier 423 of the fluid stream 420 can be either a liquid or a gas. If the carrier 423 is a liquid, the solid lubricant 422 can be present as a dispersion, suspension or emulsion in the liquid. Non-limiting examples of suitable liquid carriers are water; oils (eg mineral oil or petroleum-based oils); alcohols;
And other organic solvents (eg, acetone, methyl ethyl ketone (MEK), methylene chloride, toluene); and mixtures thereof. A non-limiting example of a dispersion is ORPAC BORON NITRIDE RELEASECOAT-
CONC 25, which is a dispersion of 25 wt% hexagonal boron nitride particles in water, which is available from ZYP Coatings, Inc. of Oa
k Ridge, Tennessee. For example, "ORPAC
BORON NITRIDE RELEASE COAT-CONC ", ZYP
Coating, Inc. , Which is specifically incorporated herein by reference. According to the supplier, the hexagonal boron nitride particles of this product have an average particle size of less than 3 μm. The dispersion also contains 1% magnesium-aluminum silicate, which according to the supplier acts as a suspending agent to prevent the precipitation of boron nitride and is hexagonal to the substrate to which the dispersion is applied. It may aid in the bonding of the crystalline boron nitride particles. Beckman Coulter
ORPAC BORON NITR using LS 230 particle size analyzer
Independent testing of a sample of IDE RELEASE COAT-CONC 25 boron nitride found an average particle size of 6.3 [mu] m with particles of ~ 35 [mu] m or less.
m range and has the following particle distribution:

[0162]

[Table 9] According to this distribution, the measured ORPAC BORON NITRIDE RE
10% of LEASECOAT-CONC 25 boron nitride particles are 10.2 μm.
Had a larger average particle size.

ZYP Coatings, Inc. of Oak Ridge, Tenne
Other useful products available from ssee include BORON NITRIDE
LUBRICOAT® paint, BRAZE STOP and WELD RELEASE products. Non-limiting examples of gas carriers that are considered useful in the present invention include compressed air, nitrogen, argon, and also propellants (such as butane or propane), which are their flammability. (Not necessarily preferred due to the above).

While not meant to be bound by any particular theory, the fluid flow 420 containing the solid lubricant 422 is dispersed in proximity to the aperture forming device 412 so that the solid lubricant 422 causes the interface 426. By contacting a portion 424 of the drill bit, abrasive wear of the drill bit 413 during drilling is reduced, thereby increasing drill life. In addition, the heat generated during drilling reduces friction between the aperture forming device 412 and the electronic support 410, thereby reducing resin turbulence in the drilled aperture 414. , Will be reduced. This reduction in generated heat is increased by using solid lubricants having high thermal conductivity, such as, but not limited to, hexagonal boron nitride, to remove heat from interface 426. It is further envisioned that the escape can thereby reduce the occurrence of resin turbulence. Solid lubricants with high thermal conductivity suitable for use in the fluid stream 420 include the lubricants disclosed above for use as the inorganic filler 18, 218 (shown in Figures 1 and 2). , But not limited to these.

The fluid stream 420 may be dispersed by any method known in the art. For example, the fluid stream 420 can be sprayed through a nozzle or atomizer (not shown). In one non-limiting embodiment of the invention, a flow of fluid, including a solid lubricant and a liquid carrier, extends through at least a portion of the inner portion of the drill bit 413 of the aperture forming device 412 (shown). Provided). A fluid flow 420 passes between the drill bit and the electronic support by passing the fluid flow through the hollow channel to at least one hole extending from the outer surface of the drill bit into the hollow channel. Are dispersed at the interface.
Another way to disperse the fluid stream 420 including the solid lubricant 422 and the liquid carrier 423 is to coat and dip the electronic support 410 just prior to drilling to coat the electronic support with the solid lubricant 422. However, the present invention is not limited to these.

The size and number of openings 414 formed in electronic support 410 can vary as desired. For example, without limitation, 0.025 millimeters (0.0
An opening 414 having a diameter in the range of 01 inch) to 12.7 millimeters (0.50 inch) can be formed in the electronic support 410 according to the method of the present invention.

The openings 414 formed in the electronic support 410 may extend partially through the thickness of the electronic support 416 (eg, blind bias (vi).
as) or embedded bias), or they may extend completely through the thickness 416 of the electronic support 410, as shown in FIG. 4 (eg, through holes). Further, if desired, the electronic support 410 may include openings 414 of each type described above.
, And one or more of different diameter openings. Further, if desired, this opening 414 can be filled with an electrically conductive material such as solder.

In another non-limiting embodiment of a method of forming an opening in an electronic support in accordance with the present invention, the electronic support is provided with a registry (re).
The fluid stream, located in the gistry and containing the solid lubricant, impinges on the opening forming device. The opening forming device is then contacted with at least a portion of the electronic support and an opening is formed that extends at least partially through the thickness of the electronic support. This fluid stream may be provided on an intermittent basis, i.e., supplied during at least a portion of the opening formation operation, or it may be continuously provided on the opening formation device during the opening formation step. Can collide.

Referring now to FIGS. 5-7, in another non-limiting embodiment of a method of forming an opening in an electronic support according to the present invention, electronic support 510 is The surface 518 of the support 510 is located in the registry with the aperture forming device 512 such that it is in close proximity to the aperture forming device 512. The layer 520 including the inorganic solid lubricant material 522 is located along at least a portion of the top surface 518 of the electronic support 510 between the top surface 518 of the electronic support 510 and the aperture forming device 512. Then the thickness 516 of this electronic support 510
An opening 514 extending at least partially through the opening forming device 51.
It is formed by two drill bits 513. By doing so, the drill bit 51
3 also forms an opening 524 that extends completely through the thickness 526 of layer 520. If desired, a second layer 530 containing an inorganic solid lubricant 532 can be located along the opposing surface 528 of the electronic support 510, as shown in FIG.

In one non-limiting embodiment, this layer 520 is a single layer. As used herein, the term “single layer” with reference to layer 520 means that this layer 520 is unsupported on the second support substrate. Layer 520 can be a single layer applied directly to surface 518 of this electronic support 510, or it can be a self-supporting layer that is inserted between surface 518 and aperture-forming device 512 prior to perforation. Can be.

In another non-limiting embodiment, layer 520 is located on surface 518 such that solid lubricant 522 is in direct contact with surface 518 of electronic support 510. In this particular embodiment, layer 520 may be a single layer, as discussed above, or it may include multiple layers. For example, in the present invention, without limitation, layer 5
20 is laminated to or otherwise adhered to a second carrier substrate (not shown), surface 518 of electronic carrier 510 and aperture forming device 51.
Support for layer 520 may be provided prior to placing layer 520 between the two.

In another non-limiting example according to the present invention, the inorganic solid lubricant is hexagonal boron nitride and the layer of hexagonal boron nitride is a phenol-paper entry plate.
It can be applied directly to the outer surface of the board by spraying or painting a dispersion of boron nitride (as discussed above) on the surface. Such inlet plate materials are well known in the art and are "thick pa.
As "per core phenolic back up EB-95",
Commercially available from Centerline of Baltimore, Maryland. The layer of hexagonal boron nitride also forms on the surface 518 of the electronic support 510.
, Spraying or painting the dispersion of boron nitride in an amount sufficient to provide the desired drilling properties when the drill bit first penetrates the boron nitride prior to forming the openings 514 on the upper surface. Can be applied directly to the electronic support 510.

While not wishing to be bound by any particular theory, when the drill bit 513 of the aperture-forming device 512 cuts through the lubrication layer 520, a portion of the inorganic solid lubricant 522 causes a portion of the drill bit 513. It is believed that it adheres to and / or is drawn into the opening and provides lubrication during perforation. Additionally (as discussed above), if the inorganic solid lubricant 522 is considered to have high thermal conductivity, the temperature of the drill 513 may be reduced as it drills through the layer 520 by thermal conduction.

This layer 520 may include one or more of the solid lubricant materials discussed above. In one non-limiting embodiment of the present invention, layer 520 preferably comprises hexagonal boron nitride. Layer 520 may further include other materials such as polymers and waxes, if desired. In another non-limiting embodiment of the invention, layer 52
0 is at least 1 for binding together the individual particles of the solid lubricant material 522.
Including two bonding materials. However, solid lubricant material 522, which solidifies without the use of a bonding material to form layer 520, can also be used in accordance with the present invention. Non-limiting examples of binding materials that are considered useful in the present invention are polymers such as polyvinyl alcohol, polyvinyl pyrrolidone; polyurethanes, polyvinyl acetates, polyacrylates, polyesters, fatty acid esters, polyethers, polyglycidal methacrylates; And waxes such as paraffin. In addition to the binding material and the inorganic solid lubricant, layer 520 may include organic lubricating materials such as zinc stearate, polytetrafluoroethylene, paraffin wax, fatty acids, fatty acid esters, and polyethylene glycol.

Layer 520 can have any thickness 526 required to provide the desired perforation properties. In one non-limiting embodiment, this layer 520 is as thin as possible while providing the necessary perforation and handling properties.

It is contemplated that multiple electronic supports can be stacked and perforated in a single opening formation operation using the teachings of the present invention. More specifically, and with reference to FIG. 6, in one non-limiting embodiment of the present invention, the first electronic support 610 and the second electronic support 611 are one top of the other. The first electronic support 61
The bottom surface 628 of 0 can be stacked adjacent to the top surface 618 of the second electronic support 611. The layer 620 including the inorganic solid lubricant 622 is formed on the adjacent upper surface of the first electronic support 610 prior to forming the opening 614 in the electronic support 610, 611 using the opening forming device 612. 619. Although 610 and 611 are shown in FIG. 6 as single layer electronic supports, those skilled in the art will recognize that they are any known in the art including, but not limited to, multi-layer laminates and printed circuit boards. It will be appreciated that it can be any type of electronic support.

It is further contemplated that the lubricious layer may be placed between selected adjacent electronic supports during the opening formation operation. More specifically, and as shown in FIG. 7, the layer 740 including the inorganic solid lubricant 742 may be formed on the lower surface 728 of the first electronic support 710 and the second electronic support prior to forming the opening. It may be located between the upper surface 718 of the body 711. It is also contemplated that multiple lubricating layers may be used in the opening formation operation. For example, and as discussed above, FIG. 5 illustrates an electronic support with two lubricating layers 520 and 530 disposed along opposing major surfaces 518 and 528 of electronic support 510, respectively. 510 is shown. As shown in FIG. 7, in another non-limiting embodiment of the invention, a plurality of electronic supports 710, 711 is provided.
And a layer 740 containing an inorganic solid lubricant 742 is disposed between the first electronic support 710 and the second electronic support 711, and optionally an inorganic solid lubricant 722. 720 may be disposed adjacent to the top surface 719 of the electronic support 710 prior to forming the openings 714 in the electronic supports 710, 711 with the aperture forming device 712.

In one non-limiting embodiment of the present invention, a plurality of electronic supports are stacked together, and a layer containing an inorganic solid lubricant is added to each adjacent electronic support of the plurality of electronic supports. It is placed between the bodies. Further, if desired, the lubricious layer can be disposed adjacent to either or both exposed major opposing surfaces of the stacked electronic supports.

In another non-limiting embodiment of the method of forming an opening in an electronic support according to the present invention, the at least one electronic support comprises a top surface of the at least one electronic support. Positioned in the registry with the aperture-forming device adjacent to the aperture-forming device. A layer comprising hexagonal boron nitride is disposed between the upper surface of the at least one electronic support and the aperture forming device,
An opening is then formed at least partially through the thickness of the at least one electronic support using the opening forming device.

In any of the methods of forming the openings described above, the layer containing the inorganic solid lubricant is perforated with an opening forming device prior to positioning the electronic support (s) in the registry. It will be appreciated by those skilled in the art that it may be disposed along at least a portion of the electronic support (s) that is (are) provided.

In another non-limiting embodiment of the invention, the solid lubricant material can be incorporated into an aperture forming device. More specifically, and with reference to FIG. 8, the aperture forming device 812 includes a drill bit 813 having an outer surface 848, and the outer surface 8.
A coating material 850 including a layered solid lubricant 852 disposed on at least a portion 854 of 48. In one non-limiting embodiment of the invention, the lubricating oil 853 is hexagonal boron nitride. In one embodiment, but not a limitation of the present invention, the coating material 850 may include a drill bit 813.
Disposed on at least a portion of the outer cutting surface of the.

The coating material 850 disposed on at least a portion 854 of the outer surface 848 of the drill bit 813 can be applied by any method known in the art for applying such coatings. For example, the coating 850, and in particular the coating comprising hexagonal boron nitride, can be applied by spraying, painting, sputtering, CVD (chemical vapor deposition), plasma deposition or pulsed laser deposition. Alternatively, the coating containing the solid lubricant 852 can be formed by chemical methods. For example, and without limiting the invention, applying a coating comprising hexagonal boron nitride provides the reaction product formed by reacting boric acid and melamine to the outer surface of the drill bit, and The drill bit may be exposed to temperatures above 800 ° C. for 60 minutes to form a layer of hexagonal boron nitride.

In another non-limiting example of an alternative method of forming the aperture-forming device 812 according to the invention, without limitation, an inorganic solid lubricant 852, such as powdered hexagonal boron nitride, The drill bit 813 may be formed therefrom in combination with one or more powdered metals and / or carbides and aided by sintering, and by powder metallurgical techniques well known in the art. For more information,
"Cement Carbide Using Self-Lubricating Boron Nitride", Japanese N
ew Materials High-Performance Cerami
c, Newmedia International Japan, September 2, 1991.

The aperture-forming device 812 described above can be used in combination with any method of forming apertures in an electronic support discussed above, or it can be used in a conventional aperture-forming process. It will be appreciated by those skilled in the art that it can be used. More specifically, when the aperture-forming device 812 is used to form an opening in an electronic support, the electronic support is (1) at least partially coated with a coating material including hexagonal boron nitride. Positioned in a registry with an aperture-forming device that includes a drill bit having an outer surface coated on; (2) the aperture-forming device contacting at least a portion of a first side of the electronic support; and ( 3) An opening extending at least partially through the electronic support is formed through at least a first side surface of the electronic support.

The present invention further contemplates electronic supports and printed circuit boards made using the aperture-forming methods discussed in detail above.

[0186]   Non-limiting embodiments of the present invention are now described in the Examples below.

Example A laminate incorporating a series of electrical grade prepregs and features of the present invention was prepared as follows: Laminate A: Nelco Inter of California, Anaheim.
National Corporation uses commercially available prepregizing equipment and techniques to form prepreg materials and impregnates heat-cleaned and silanized electrical grade 7628 style E-glass fabric and B-stage cure (ie, partial cure). Let Impregnated resin has Tg of 140 ℃
Is a FR-4 epoxy resin and has been designated by Nelco as 4000-2 epoxy resin. Eight prepreg materials were laminated with a laminating press (lami
nating press) plate between 1 oz. Copper foil was placed on top and bottom of the stack and stacked. The press plates of the laminate press were preheated to a temperature of 93 ° C (200 ° F) and the stack was pressed at a pressure of 0.1 megapascals (MPa) (16 psi) for 4 minutes. The temperature is then increased from 4.4 ° C to 6.6 ° C (8 ° C) until the plate temperature reaches 177 ° C (350 ° F).
° F to 12 ° F). Next, the laminating pressure is set to 2.3 Mpa (
350 psi) and held for 60 minutes. The temperature of the laminate was reduced by first circulating water through the press plate for 25 minutes and then air through the press plate for 25 minutes while maintaining the laminating pressure throughout. The pressure was then released and the laminate was removed from the laminating press. Next, this laminated plate was trimmed to form a laminated plate A. The glass content of each laminate accounts for 60-65% by weight. The dimensions of the laminate A are 45.7.
It was cm × 61.0 cm (18 in. × 24 in.).

Laminate B: Laminate B was coated with a layer of boron nitride between each set of prepreg material (ie, the laminate comprises 8 layers of prepreg material and 7 layers of boron nitride). Except that it was prepared in the same manner and using the same materials as laminate A.
More specifically, each of the boron nitride layers was manually applied to the major surface of the seven prepreg materials by spraying a boron nitride aerosol lubricant until visual inspection showed uniform coverage. Boron Nitride Aerosol Lubricant is available from Oak Ridge, Te
Nnessee's ZYP Coatings, Inc. Marketed by and includes boron nitride, acetone, and propellants. The total amount of boron nitride contained in the seven layers varies between 50 and 70 g. Boron nitride was not applied to the surface of the prepreg material that was the outer major surface of the laminate. Since this spray coating was applied manually, the amount of boron nitride varied between layers and between laminates. However, each layer was expected to contain boron nitride in the range of 2.56 to 3.58 mg / cm ² of prepreg. The glass content of each laminate was in the range of 70-75% by weight.

Laminate C: 50.8 cm × 68.6 cm (20 in. × 27 in.) 7628
Style E-glass fabric was hand coated with 120 g of Nelco 4000-2 FR-4 epoxy resin (using a brush to coat and evenly spread the resin solution over the fabric). The coated fabric is then treated for 3-5 minutes at 154 ° C (310 ° F) in an air circulation oven to form a prepreg material.
B stage cured. This fabric is from Bedford, Lynchburg, VA
Heat-cleaned and silanized electrical grade 7628 style fabric for epoxy resin, commercially available from d Weaving. Then
Laminates were formed by stacking and pressing eight prepreg materials and two copper foil layers in the same manner as described above for laminate A. The glass content of each laminate was in the range of 70-75% by weight.

Laminate D: Laminate D was prepared in the same manner and material as Laminate C, except that the FR-4 epoxy resin contained boron nitride particles. More specifically, 9g POL
25 g of ARTHERM 160 hexagonal boron nitride powder (discussed previously)
Acetone (Fisher Scientific of Pittsburgh, PA)
(commercially available from C.) to wet the boron nitride and form a paste that is 26% by weight boron nitride. This paste is then added to 120 g of N
Elco 4000-02 Epoxy resin, 11% based on total solids
Forming an epoxy resin containing weight percent boron nitride. The glass content of each laminate was in the range of 70-75% by weight.

Test 1 Laminates A, B, and D were placed in air at a temperature of 300 K (70 ° F.) according to ASTM method C-177, which is specifically incorporated herein by reference. Inside,
The thermal conductivity and heat resistance were evaluated. For laminate B specifically tested, this laminate contained a total of 55 g of boron nitride. The values for thermal conductivity measured for each laminate are shown in Table 1 below.

[0192]

[Table 10] Referring to Table 1, the measured thermal conductivity of Laminate B and Laminate D (both of which incorporate boron nitride) is higher than the measured thermal conductivity A of Laminate A. It was More specifically, laminate B, which incorporates features of the present invention.
The measured thermal conductivity of laminate A is 50% higher than that of laminate A, and the measured thermal conductivity of laminate D, which incorporates features of the invention, is It was 45% higher than the measured thermal conductivity of Plate A.

Based on the above data, in one non-limiting embodiment of the present invention, a first prepreg material layer; a second prepreg material layer disposed adjacent to a major surface of the first prepreg material layer; And the thermal conductivity of the electronic support in the form of a laminate comprising at least one layer comprising hexagonal boron nitride powder disposed between the first prepreg material layer and the second prepreg material layer is at least It is 0.27 W / mK. The at least one layer comprises up to 25% by weight of adhesive, based on total solids and based on the total weight of the at least one partial layer. In one non-limiting embodiment, the thermal conductivity of the electronic support is at least 0.29 W / mK. In another non-limiting embodiment, the electronic support has a thermal conductivity of at least 0.31 W / mK.

In another non-limiting embodiment of the invention, the thermal conductivity of an electronic support comprising a laminate comprising two or more layers of prepreg material is at least 0.27 W / mK. At least one of the two or more prepreg layers is (1) at least one woven glass fiber reinforced material formed from at least one fiber free of basaltic glass; and (2) at least one reinforced material. At least one matrix material in contact with at least a portion of (i) at least one non-fluorinated polymer, (ii) epoxy resin, and (iii) at least one inorganic filler comprising hexagonal boron nitride powder , At least one matrix material, and the at least one inorganic filler, based on total solids,
It comprises at least 6% by weight of the total combined weight of at least one inorganic filler and at least one matrix material. In another non-limiting embodiment, the electronic support has a thermal conductivity of at least 0.29 W / mK. In another non-limiting embodiment, the electronic carrier has a thermal conductivity of at least 0.31 K / mK.

Test 2 Laminates A, B, C and D were drill tip wear (drill tip w).
It was tested to evaluate the ear). With reference to FIG. 9, as used herein, the term “drill tip wear” means a reduction in the width 970 of the main cutting edge of the drill 974 as measured at the peripheral edge of the drill tip.

A drill was used with a three-height stack of laminate with a 0.0105 inch (0.2667 mm) thick aluminum entry and a 0.082 inch (2.083 mm) thick paper core phenolic resin coated backup. went. Drilling three laminates at a time is generally standard practice in the industry. Drill tip wear was determined for a 0.018 inch (0.4572 mm) diameter drill. The drill is Schwendi-Horenhausen
, Solid Carbide Microdrill supplied by HAM, Germany. The tip load during the drill was held constant at 0.00125 during the drill. As used herein, "tip load" means the ratio of drill insertion speed measured in inches per minute to axial speed measured in revolutions per minute (rpm). The shaft speed was 100,000 rpm and the insertion speed was 125 inches (317.5 cm) per minute. Retention rate is 1000 per minute
It was inch (25.4 m). Drill the Pluro from Burolo, Italy
Pluritec single spindle, multi-station drilling machine, commercially available from Ritec spa.
It was performed using a multi-stage drilling machine).

For each laminate type, 4 stacks of 3 laminates were drilled. 1000
1 hole for each laminate type is drilled into the stack of the 1st laminate using a single drill and 2000 holes for each laminate type are used for the 2nd laminate using a single drill Drill into a stack of plates, drill 3000 holes into a third stack of stacks using a single drill for each laminate mold, and 4
000 holes were drilled into the fourth stack of laminates using a single drill for each laminate type. The drill tip wear was measured after drilling each stack.

To compare the drill tip wear, based on the total number of holes drilled and taking into account both the total thickness drilled by each drill and the variation in laminate thickness, the drill wear factor for each drill It was determined. As used herein, "
"Drill wear factor" and "" means the amount of drill tip wear per distance drilled and is calculated using the following formula:

[0199]

[Equation 1] For example, if the drill tip wear was 6 meters after drilling 3000 holes through a stack of three laminates, each 1524 m (0.06 inch) thick, the drill wear factor would be 0.437 m. / Meter (ie 0.437 m of drill tip wear per meter of wide range of drilled thickness). In addition, the drill wear factors for each set of drilled laminates averaged to
As discussed above, give the average drill wear coefficient, _ave , based on 10,000 drilled holes.

Table 2 shows and _ave for the four sets of laminates.

[0201]

[Table 11] When comparing Laminates A and B (both of which include commercial treated prepreg material), the drill wear factor for boron nitride containing laminate B is the drill wear for laminate A without boron nitride. It was less than the coefficient. Similarly, laminates C and D
When compared to (both of which include hand-prepared prepreg material), the drill wear factor for the boron nitride-containing laminate D was less than the drill wear factor for the boron nitride-free laminate C. . These test results showed that the addition of boron nitride to the laminate, either contained within the epoxy resin or as a layer between prepreg materials, tended to reduce drill tip wear. .

It will be appreciated by those skilled in the art that the above-described embodiments may be modified without departing from its broad inventive concept. Accordingly, the invention is not limited to the particular embodiments disclosed, as defined by the appended claims, but is intended to include modifications that fall within the spirit and scope of the invention. It is understood that there is.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of one non-limiting embodiment of an electronic support incorporating features of the present invention.

FIG. 2 is a cross-sectional view of another non-limiting embodiment of an electronic support incorporating features of the present invention.

FIG. 3 is a cross-sectional view of another non-limiting embodiment of an electronic support incorporating features of the present invention.

FIG. 4 is a cross-sectional view of an electronic support having an opening formed therein and incorporating features of the present invention.

FIG. 5 is a cross-sectional view of an alternative embodiment similar to FIG. 4 of an electronic support having an opening formed therein and incorporating features of the present invention.

FIG. 6 is a cross-sectional view of an alternative embodiment similar to FIG. 4 of an electronic support having openings formed therein and incorporating features of the present invention.

FIG. 7 is a cross-sectional view of an alternative embodiment similar to FIG. 4 of an electronic support having an opening formed therein and incorporating features of the present invention.

[Figure 8]   FIG. 8 is a schematic diagram of an aperture forming device incorporating features of the present invention.

[Figure 9]   FIG. 9 is an end view of a perforation illustrating the major cutting edges of the perforation tip.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B32B 27/18 B32B 27/18 Z (31) Priority claim number 60/233, 619 (32) Priority date Heisei September 18, 2012 (September 18, 2000) (33) Priority claiming country United States (US) (31) Priority claim number 09 / 783,537 (32) Priority date February 15, 2001 (2001) 2.15) (33) Priority claiming country United States (US) (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE, TR), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, MZ SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, BZ, CA, CH, CN, CR, CU, CZ, DE, DK, DM, DZ, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU. , ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MA, MD, MG, MG, MN, MW, MX, MZ, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, TZ, UA, UG, UZ, VN, YU, ZA, ZW (72) Inventor Ramon-Hilinski, Kami United States Pennsylvania 15212, Ttsubagu, Montorei stream door 1218 F-term (reference) 4F100 AA09B AA09H AA31B AA31H AC03B AC03H AC05B AC05H AC10B AC10H AD06B AD06H AD11B AD11H AG00A AH03B AH03H AH08B AH08H AK18B AK18H AK53A AR00C AS00B BA01 BA02 BA03 BA07 BA10A BA10B BA10C CA23B DG01A DH01A GB43 JA02 JG01C JG04 JJ01 JK12B JK12H YY00B YY00H

Claims (50)

[Claims] 1. An electronic support comprising: A. A prepreg material layer; and B. At least one layer in contact with at least a portion of at least one surface of the prepreg material layer, the prepreg material layer comprising: 1. at least one reinforcing material; and At least one matrix material in contact with at least a portion of the at least one reinforcing material, the at least one layer comprising at least one inorganic filler and the at least one layer based on total solids. An electronic support comprising less than 25 weight percent adhesive material, based on total weight. 2. The electronic support according to claim 1, wherein the at least one
The electronic support, wherein the two reinforcing materials are glass fiber reinforced materials. 3. The electronic support of claim 2, wherein the glass fiber reinforced material is a woven glass fiber reinforced material. 4. The electronic support according to claim 3, wherein the glass fiber reinforced material is a non-defatted woven glass fiber reinforced material. 5. The electronic support of claim 1, wherein the at least one
An electronic support in which two partial layers form an essentially continuous surface on at least one surface of the prepreg material layer. 6. The electronic support according to claim 1, wherein the at least one
An electronic support, wherein the two inorganic fillers are selected from inorganic solid lubricants, high thermal conductivity materials, high electrical resistance materials, low thermal expansion materials, and materials with high affinity for metal ions. 7. The electronic support according to claim 6, wherein the at least one
An electronic support wherein the one inorganic filler is at least one inorganic solid lubricant selected from boron nitride, molybdenum disulfide, talc, boric acid, antimony oxide, and mixtures of any of these. 8. The electronic support according to claim 7, wherein the at least one
One inorganic filler is at least one inorganic solid lubricant having a layered structure,
Electronic support. 9. The electronic support according to claim 8, wherein the inorganic solid lubricant having the layered structure is hexagonal boron nitride. 10. The electronic support as claimed in claim 6, wherein the at least one inorganic filler is boron nitride, graphite, yugite, ammonium nitride, ammonium titanate, and mixtures thereof. An electronic support selected from. 11. The electronic support of claim 6, wherein the at least one inorganic filler has a thermal conductivity of at least 30 W / mk.
An electronic support, which is two high thermal conductivity materials. 12. The electronic support according to claim 6, wherein the at least one inorganic filler is 100 × 10 ⁻⁷ / in a temperature range of 0 ° C. to 200 ° C.
An electronic support, which is at least one low thermal expansion material having a coefficient of thermal expansion of less than or equal to ° C. 13. The electronic support according to claim 6, wherein the at least one inorganic filler is at least one material having a high affinity for metal ions. Has an cation exchange capacity of at least 20 meq / 100 g. 14. The electronic support according to claim 6, wherein the at least one inorganic filler is at least one material having a high affinity for metal ions. An electronic support having a distribution coefficient K _d (Cu ²⁺ ) of at least 600 mg / l. 15. The electronic support according to claim 6, wherein the at least one inorganic filler is montmorillonite, nontronite, saponite, illite (hydrated mica), vermiculite, chlorite, sepiolite. An electronic support that is a clay mineral selected from, attapulgite, bentonite, hectorite, synthetic synthetic fluoromica, and mixtures thereof. 16. The electronic support according to claim 6, wherein the at least one inorganic filler has a nitrogen-containing organic functional group-containing metal, a sulfur-containing organic functional group-containing metal, and an oxygen-containing organic functional group. An electronic support that is a chelating agent selected from a metal having a group, a metal having a phosphorus-containing organic functional group, and a mixture thereof. 17. The electronic support of claim 1, wherein the at least one inorganic filler has a Mohs hardness of 6 or less. 18. The electronic support of claim 1, wherein the at least one inorganic filler is based on total solids, the combined total of the at least one matrix material and the at least one layer. An electronic support comprising 5 to 35 weight percent of the weight. 19. The electronic support of claim 18, wherein the at least one inorganic filler is based on total solids, the combined total of the at least one matrix material and the at least one layer. An electronic support comprising 10 to 30 weight percent of the weight. 20. The electronic support of claim 1, wherein the at least one sublayer comprises no more than 10 weight percent adhesive material, based on the total weight of the at least one sublayer based on total solids. Including an electronic support. 21. The electronic support of claim 20, wherein the at least one sublayer is less than or equal to 5 weight percent based on the total weight of the at least one sublayer based on total solids. Including an electronic support. 22. The electronic support according to claim 21, wherein the at least one sublayer is essentially free of adhesive material. 23. The electronic support of claim 1, wherein the prepreg material layer is a first prepreg material layer, and the electronic support is the at least partial layer of at least one additional layer. An electronic support comprising at least one further prepreg material layer laminated to at least a portion of the first prepreg material layer such that it is located between the prepreg material layer and the first prepreg material layer. . 24. The electronic support of claim 23, further comprising at least one electrically conductive material located along at least a portion of at least one surface of the electronic support. Electronic support. 25. The electronic support of claim 24, wherein the at least one electrically conductive material comprises at least one circuit. 26. The electronic support of claim 1, wherein the at least one layer is located along at least a portion of a first surface of the prepreg material layer and at least one electrical layer. A conductive material is provided on a second side of the prepreg material layer opposite the second layer.
An electronic support located along at least a portion of the surface of the. 27. The electronic support of claim 26, wherein the at least one electrically conductive material comprises at least one circuit. 28. The electronic support of claim 1, further comprising at least one opening extending at least partially through the electronic support. 29. A method of forming an electronic support comprising: A. B. forming a prepreg material layer comprising at least one matrix material and at least one reinforcing material; B. At least partially solidifying the at least one matrix material; C. At least 1 part of the at least partially solidified matrix material;
At least partially solvating with one solvent; and D. Adhering at least one inorganic filler to at least a portion of the at least partially solvated matrix material. 30. The method of claim 29, wherein the at least one matrix material is an epoxy material. 31. The method of claim 29, wherein the at least one solvent is selected from acetone, dimethylformamide, methylene chloride, glycol ethers, methyl ethyl ketone, and mixtures of any of these. 32. The method of claim 31, wherein the bonding step comprises
A method comprising spraying the at least one inorganic filler onto at least a portion of the at least partially solvated matrix material. 33. The method of claim 29, wherein the at least one inorganic filler is positioned between the prepreg material layer and the at least one additional prepreg material layer to form a laminate. And at least one layer of the prepreg material
The method further comprising laminating together with two additional layers of prepreg material. 34. The method of claim 33, comprising disposing at least one electrically conductive material on at least a portion of at least one surface of the laminate. 35. The method of claim 29, further comprising disposing an electrically conductive material on at least a portion of at least one surface of the electronic support. 36. A method of forming an electronic support, the method comprising: A. B. forming a prepreg material layer comprising at least one matrix material and at least one reinforcing material; B. Adhering at least one inorganic filler to at least a portion of the at least one matrix material, wherein the at least one matrix material is tacky; and C. At least partially solidifying the at least one matrix material,
Including the method. 37. The method of claim 36, wherein the at least one inorganic filler is positioned between the prepreg material layer and the at least one additional prepreg material layer to form a laminate. And at least one layer of the prepreg material
Laminating together with two additional layers of prepreg material. 38. The method of claim 37, comprising disposing at least one electrically conductive material on at least a portion of at least one surface of the laminate. 39. The method of claim 36, further comprising disposing an electrically conductive material on at least a portion of at least one surface of the electronic support. 40. A laminated board, comprising: A. Multiple layers of prepreg material laminated together; and B. At least one layer comprising at least one lubricant located between at least a portion of at least one pair of adjacent prepreg material layers of the multiple prepreg material layers. 41. The laminate of claim 40, wherein the at least one layer comprises no more than 25 weight percent adhesive material based on the total weight of the at least one layer based on total solids. Board. 42. The laminate of claim 40, wherein the at least one lubricant is selected from inorganic solid lubricants, organic lubricants, and mixtures thereof. 43. The laminate of claim 42, wherein the at least one lubricant is selected from hexagonal boron nitride, boric acid, molybdenum disulfide, graphite, and mixtures of any of these. A laminate, which is at least one inorganic solid lubricant. 44. The laminate of claim 43, wherein the at least one inorganic solid lubricant is hexagonal boron nitride. 45. The laminate of claim 42, wherein the at least one lubricant is at least one organic lubricant selected from polytetrafluoroethylene, zinc stearate, and mixtures thereof. , Laminated boards. 46. The laminate of claim 40, further comprising an electrically conductive material in contact with at least a portion of at least one surface of the laminate. 47. The laminate of claim 40, wherein the at least one lubricant comprises (a) high thermal conductivity, (b) high electrical resistance, (c) low thermal expansion, (d).
) A laminate having a high affinity for metal ions and (e) at least one additional property selected from Mohs hardness of 6 or less. 48. A method of forming an electronic support comprising at least one internal lubricant layer, the method comprising: A. Applying at least one lubricant to at least a portion of at least one surface of the first prepreg material layer to form at least one lubricant layer; B. So that the at least one lubricant layer is located between the first prepreg material layer and the at least one further prepreg material layer to form an internal lubricant layer,
Depositing the first layer of prepreg material with at least one additional layer of prepreg material; and C. Laminating the first prepreg material layer and the at least one further prepreg material layer together to form an electronic support. 49. The method of claim 48, wherein the at least one further prepreg material layer comprises at least one lubricant layer, the at least one lubricant layer comprising the at least one lubricant layer. At least one in contact with the surface of
A method involving one lubricant. 50. The method of claim 48, wherein before the laminating step,
The method further comprising disposing at least one electrically conductive layer on at least one surface of at least one of the prepreg material layers.