KR20020077917A - Electronic supports and methods and apparatus for forming apertures in electronic supports - Google Patents

Abstract

The present invention provides an electronic support 210 comprising a prepreg layer 214 and at least one layer 217. The prepreg layer 214 includes at least one reinforcing member 220 and at least one matrix member 216 in contact with at least a portion of the at least one reinforcing member 220. The at least one layer 217 is in contact with at least a portion 224 of at least one surface of the prepreg layer 214 and includes at least one inorganic filler 218. The at least one layer 217 has an adhesive member in an amount of no greater than 25% by weight, based on the total load of the at least one layer 217 located on a total solid basis.

Description

ELECTRONIC SUPPORTS AND METHODS AND APPARATUS FOR FORMING APERTURES IN ELECTRONIC SUPPORTS

Typically, electronic supports, in particular printed circuit boards (generally referred to as PCBs or printed wiring boards), are laminated plastics composed of two or more reinforcing layers infused with a polymer and generally referred to as resin impregnated workpieces. And one or more conductive layers laminated by applying heat and pressure. In the manufacture of printed circuit boards, holes (so-called holes) are typically formed in the circuit board to facilitate the electrical interconnection between the " intraboard " and the interconnection between the printed circuit board and the electronic components attached thereto. Or vias. The interconnection method between the plates is, for example, a method of connecting circuits engraved on several layers of a printed circuit board. An interconnection method between a circuit board and an electronic component is, for example, a connection between a printed circuit board and an integrated circuit device mounted thereon. Typically, after drilling to form a hole, the wall of the hole is usually plated to form an electrically conductive passage. Circuitry is inscribed in one or more electrically conductive layers by methods well known in the art, such as photoimaging and etching.

As the number and functionality of circuits that can be assembled on a single integrated circuit device in the electronics industry continues to grow, better connection between the board and the components, both on the printed circuit board, to support the device, and between components The need for) is also increasing. Increasing the size of the circuit board to accommodate the increased number of connections results in impractical restrictions on the size and weight of the finished product incorporating the printed circuit board and the performance requirements of the product. Thus, to accommodate the increased wiring requirements, the size of the features of the printed circuit board (eg, the diameter of the holes and the width of the pattern lines) is reduced while increasing the number of metal layers incorporated in the circuit board.

The need for reduced size features and the increased number of layers makes the manufacturing process of printed circuit boards more complex and requires a lot of effort. In particular, the formation of a large number of small holes has been known to significantly increase the manufacturing cost of the printed circuit board. See Joan Tourne, “Using New Interconnection Technology to Reduce Board Costs,” in the Fourth European Solidarity Bulletin (1997), pp. 167-174. Cited. For example, mechanically drilling holes smaller than 13 mils in diameter has been known to be counterproductive in terms of yield, throughput, and typical mechanical drill processing costs. This is mainly due to the increased amount of drill tool wear associated with drilling small holes in printed circuit boards. Drill tools occur when the drill contacts the glass fiber layer of the printed circuit board during drilling. Fiberglass fabrics are commonly used to reinforce each layer of a printed circuit board, improving the rigidity and strength of the printed circuit board. However, the fiberglass has the effect of grinding the drill tool and dulls the drill tool. Dull and worn tools degrade the quality of drilled hole walls, reduce the positional accuracy of machined holes, increase fiber breakage, burrs, nail-heading, and wicking. It is known to increase the incidence of drill defects such as roughness and roughness of vias, thereby adversely affecting the drill process.

In addition, as the performance requirements of integrated circuit devices are intensified, the power consumption requirements of these devices also tend to be enhanced. This causes the heat flux to be controlled to increase in order to prevent the device from failing, at the surface of the device. For example, the failure rate was estimated to increase about twice with every 10 ° C. increase in operating temperature of the device. Al, cited herein by reference. Tumbler and Lee. See page 168 of the "Microelectronics Packing Handbook" (1989), co-authored by Limazevsky. Improving the thermal conductivity of printed circuit boards by arranging the devices (eg by directly mounting the devices on a printed circuit board or by attaching a second level package containing the devices to the printed circuit board), thereby improving the performance and reliability of the device. You can.

Electronic support in the form of laminated plastic and printed circuit board with good drill processing characteristics and improved functionality, which can increase the life of the drill, reduce the wear of the drill tool, improve the quality of the hole wall, and reduce the cost of drilling There is still a need for alternative apparatus and methods for drilling printed circuit boards that can reduce the cost and integrate with existing drill operations without the need for additional machining steps.

The present invention relates generally to an electronic support and a method for manufacturing the same, and more particularly, to a resin penetration processing material, a laminated plastic, a plated laminated plastic, and a printed circuit board and a method for manufacturing the same. The present invention also relates to a method and apparatus for forming a hole in an electronic support made in accordance with the present invention, and more particularly, to a method for mechanically drilling a hole in a printed circuit board.

The present invention provides an electrical support, the electrical support comprising: (A) a resin impregnating material layer and (B) at least one layer in contact with at least a portion of at least one side of the resin impregnating material layer, wherein the resin impregnating material The layer comprises (1) at least one reinforcement and (2) at least one matrix material in contact with at least a portion of the reinforcement, the layer based on the total weight of the layer relative to the at least one inorganic filler and the solid substrate Up to 25% by weight of an adhesive.

The present invention also provides a method of forming an electronic support, the method comprising the steps of: (A) forming a resin impregnating workpiece layer having at least one matrix material and at least one reinforcing material, (B) at least one matrix At least partially setting the ash, (C) partially solvating a portion of the 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 It includes.

The present invention provides another method of forming an electronic support, the method comprising the steps of: (A) forming a resin impregnated workpiece layer having at least one matrix material and at least one reinforcement material, (B) Adhering at least one inorganic filler to at least a portion, and (C) at least partially setting at least one matrix material.

The present invention also provides a laminated plastic, the laminated plastic comprising: (A) a layer of laminated resin impregnated workpiece layers, and (B) a portion of at least one pair of adjacent layers of resin impregnated workpieces among the resin impregnated workpiece layers. At least one layer with at least one lubricant located.

The present invention also provides a method for forming an electronic support having at least one internal lubrication layer, the method comprising: (A) applying at least one lubricant to at least a portion of at least one side of the first prepreg material layer; Forming at least one lubricating layer, (B) further laminating at least one resin impregnating material layer on the first resin impregnating material layer, and at least one added resin impregnation with the first resin impregnating material layer. Disposing an at least one lubricant layer between the workpiece layers to form an internal lubrication layer, and (C) laminating the first resin impregnating workpiece layer and at least one additional resin impregnation workpiece layer to form an electronic support. Include.

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

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

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

4 is a cross-sectional view of an electronic support incorporating features of the present invention and having a hole therein;

5 to 7 are cross-sectional views of an alternative embodiment of an electronic support having a feature therein that includes features of the present invention, similar to FIG. 4;

8 is a schematic diagram of an apparatus for forming a hole that incorporates features of the present invention; And

9 is a plan view illustrating a first cutting edge of a drill tip.

The electronic support and the method for forming the electronic support according to the present invention have good drill processing characteristics, low processing costs, improved processing yield, good thermal conductivity, and improved functionality in the form of laminated plastics and printed circuit boards. The advantage is providing support. In addition, the method and apparatus of the present invention are particularly useful for forming holes in electronic supports, more particularly printed circuit boards.

As used herein, the term “electronic support” is used to mechanically support and electrically connect elements including, but not limited to, active electronics, passive electronics, printed circuits, integrated circuits, semiconductor devices, and other hardware. Interconnect structure, wherein the hardware is coupled with elements including but not limited to connectors, sockets, retaining clips, and heat sinks. Although not limited by the present invention, the electronic support may include, for example, a resin penetration processing material layer, a laminated plastic, a plated laminated plastic, and a printed circuit board. As used herein, the term "laminated plastic" refers to an electronic support made of a polymeric matrix material reinforced with a reinforcement, wherein "plated laminated plastic" or "panel" is in contact with at least a portion of at least one side. It means the laminated plastic provided with a material. Typically, laminated plastic is formed from two or more layers of prepreg materials. As used herein, "resin impregnating material layer" or "resin impregnating material" means a layer of reinforcement, preferably infused, with at least a portion applied with a polymeric matrix material. As used herein, the terms "printed circuit board (PCB)", "electronic circuit board", and "printed wiring board (PWB)" refer to an electronic support made of a polymer matrix material, and the electronic support is a reinforcing material. And at least one printed circuit and / or hole.

A printed circuit board is generally manufactured by injecting a polymer matrix material into a reinforcement such as a glass fiber reinforcement. Glass fiber reinforcements commonly used to make printed circuit boards include wovens, nonwovens (including but not limited to short, biaxial, triaxial fabrics), knits, mats (single and twisted mats), and multilayer fabrics. Fabrics such as, but not limited to, layers of fabric or other materials connected by embroidery to form a three-way fabric structure. In addition, the coated fabric owls used for warp and weft of the fabric may be braided or braided before weaving, and the fabric includes various combinations of warp and weft warp and twist. However, although not limited to the present invention, the fiberglass reinforcement is usually a woven fabric.

Although the present disclosure is described in the context of electronic supports in the form of printed circuit boards made approximately of electronic supports, in particular layers of resin impregnated workpieces, laminated plastics, and glass fibers, those skilled in the art will appreciate It will be understood that it is not limited to electronic supports made using stiffeners and includes any stiffener, including the materials described above. Moreover, the present invention is not only limited to reinforced laminated plastics and printed circuit boards, but also includes electronic supports in the form of unreinforced printed circuit boards. As used herein, the term "unreinforced printed circuit board" means a printed circuit board that is not provided with a reinforcement material. In addition, one of ordinary skill in the art, the method for forming a hole of the present invention includes both an electronic support, in particular a printed circuit board formed using the aforementioned reinforcement and a non-reinforced printed circuit board. It will be appreciated that it is useful for forming holes in a printed circuit board.

For purposes of detail, it will be understood that all numbers used in this specification and claims and express content of components, reaction conditions and the like are limited to the term "about" in all cases. Thus, unless indicated to the contrary, the numerical variables set forth in the following description and claims are approximations that may be modified in accordance with certain features obtainable by the present invention. At the very least, each numerical variable should be interpreted as a digital number of a reported size using conventional peripheral techniques, unless an attempt is made to limit the application of the principles corresponding to the claims.

Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are recorded as precisely as possible. However, any numerical value essentially has some error, which is due to the standard deviation that is inevitable found in each experimental measurement.

Referring to FIG. 1, an electronic support 10 is shown in accordance with one non-limiting embodiment of the present invention. The electronic support 10 has a resin impregnated workpiece layer 14 comprising at least a fabric reinforcement, at least one of which is applied to at least one matrix material 16. The at least one matrix material 16 comprises at least one inorganic filler 18. In one non-limiting embodiment of the invention, although not required, the inorganic filler 18 is a particulate inorganic filler. As used herein, the term "particulates" means isolated non-fiber particles. The inorganic filler 18 may have a particle size and shape suitable for a given finished product. In one particular embodiment of the present invention, there is no limitation, but the average particle size of the inorganic filler is 0.01 to 1000 micrometers at the maximum. The average particle size of the particles according to the invention can be measured by known laser dissipation techniques. In one non-limiting embodiment of the present invention, particle size is measured using a Beckman Culter LS230 laser diffraction particle size meter, which uses a laser beam having a wavelength of 750 nm under the assumption that the particle is spherical. Measure the size of the particles. "Particle size" refers to the smallest sphere that can completely enclose the particles. Examples of suitable particle shapes include, but are not limited to, cubes, particles with one side cut off, spherical particles, plate-shaped particles, and acicular particles.

If desired, another resin impregnating material layer is further secured to the resin impregnating material layer 14 to form the laminated plastic shown in FIG. 3 in a lamination process described in more detail below.

Although not limited herein, at least one matrix material 16 of the present invention is described in the general context of a polymeric matrix material. As used herein, the term "polymer matrix material" means a matrix material formed of macromolecules composed of long atomic chains, which are connected to each other and entangled in solution or in the solid state (Prentice Hall Polymer Science and Please refer to the inorganic polymer contributed by James Mark et al. On page 1 of the Engineering Series (1992). However, one of ordinary skill in the art will understand that other matrix materials such as ceramics and glass ceramics may be used as one matrix material according to an embodiment of the present invention, and are not limited to the above materials. Polymer matrix materials useful in the present invention include thermosetting materials and thermoplastic materials. Non-limiting examples of useful thermosetting polymer materials include one epoxy or oxirane in molecular form, such as thermoset polyester, vinyl ester, epoxide (polyglycidyl ether of polyhydric alcohol or thiols). ), Phenolic, aminoplasts, thermoset polyurethanes, and mixtures thereof. In one non-limiting embodiment of the present invention, a polymer matrix material for forming a laminated plastic for a printed circuit board is FR-4 epoxy resin, the epoxy resin is a non-functional brominated epoxy resin, polyamide and liquid crystal polymer Polyfunctional epoxy resins, such as the composition of these resins are well known to those skilled in the art. For more information on the composition of these resins, see pages 534-537 of Electronic Materials Handbooks (1989), published by ASM International.

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

Non-limiting special examples of formulas for polymeric matrices materials useful in the present invention include EPON 1120-A80 epoxy resins (commercially available from Cell Chemicals, Houston, TX, USA), dicyandiamide, 2-methyl Imidazole, and DOWANOL PM glycol ether (commercially available from Dow Chemical Co., Midland, Mich.).

Other components included in the prepreg layer 14 include, but are not limited to, colorants or pigments, lubricants or process additives, ultraviolet stabilizers, antioxidants, fillers such as flame retardants, and extenders.

In one non-limiting embodiment of the invention, the matrix material 16 comprises at least one non-fluorinated polymer material. In another non-limiting embodiment, the matrix material 16 comprises up to 50% by weight of the fluorinated polymer material relative to the total solid substrate. In another non-limiting embodiment, the matrix material 16 comprises up to 30% by weight of the fluorinated polymer material relative to the total solid substrate. In another non-limiting embodiment, the matrix material 16 comprises up to 10 weight percent fluorinated polymer material relative to the entire solid substrate. In one non-limiting embodiment of the invention, the matrix material 16 Contains little fluorinated polymer material. As used herein, the term “almost free of fluorinated polymer material” means that the polymer matrix material comprises up to 5 wt.% Fluorinated polymer material, preferably no fluorinated polymer material, relative to the total solid substrate. do. Although not limited herein, the fluorinated polymer is not suitable for use in this embodiment, because the addition of the fluorinated polymer matrix material to the polymer matrix material increases the dielectric constant of the polymer matrix material and is produced from the polymer matrix material. This is because it is thought that it may harm the overall performance of the electronic support. In addition, fluorinated polymers are expensive and can increase the price of the electronic support.

Referring to FIG. 1, inorganic fillers 18 useful in the present invention are made of inorganic materials including oxides, nitrides, carbides, borides, ceramic materials such as glass, metals, and minerals such as clay minerals, but these materials It is not limited to. Although not limited herein, in one non-limiting embodiment of the present invention, in order to minimize wear of the reinforcing agent during the manufacture of the laminated plastic, the hardness of the inorganic filler 18 is greater than the hardness of the reinforcing material 20. Should be small. The hardness of the inorganic filler 18 and the reinforcing agent 20 is determined by a conventional hardness measurement method such as beaker or Brinell hardness measurement method, but preferably determined by Mohs hardness measurement method showing the relative scratch resistance of the material surface. . Therefore, in one non-limiting embodiment of the present invention, for example, if the reinforcing material is manufactured from glass fibers having a Mohs hardness value of 6, the Mohs hardness value of the inorganic filler is 6 or less, and in another embodiment, the Mohs hardness value is 0.5 to 6 do. Mohs' hardness values of some examples of inorganic fillers suitable for use in the present invention are shown in Table A below.

Table A

Mineral filler Mohs hardness (circle meter) Boron nitride 2 (2) Graphite 0.5-1 (3) Molybdenum disulfide 1 (4) talc 1-1.5 (5) mica 2.8-3.2 (6) Kaolinite 2.0-2.5 (7) gypsum 1.6-2 (8) calcite 3 (9) Calcium Fluoride 4 (10) zinc oxide 4.5 (11) Zinc sulfide 3.5-4 (12) aluminum 2.5 (13) Copper 2.5-3 (14) iron 4-5 (15) gold 2.5-3 (16) nickel 5 (17) Palladium 4.8 (18) platinum 4.3 (19) silver 2.5-4 (20)

(2) K. Ludmer's Book Friction, Wear and Lubrication (p. 27 of 1996),

(3) Egg, published by CRC Press. In F-22 of the Chemistry and Physics Handbook (West 1975),

(4) Al. Lewis, Senior's book Holly, p. 793 of the Chemistry Dictionary (1993, 12th edition),

(5) Al. Lewis, Senior Book of Holly, page 1113 of the Chemistry Dictionary (1993, 12th edition),

(6) Al. Lewis, Senior's book Holly, page 784 of the Chemistry Dictionary (1993, 12th edition),

(7) pages F-22 of the Chemistry and Physics Handbook,

(8) pages F-22 of the Chemistry and Physics Handbook,

(9) 27 sides of friction, abrasion, lubrication,

(10) 27 faces of friction, wear, lubrication,

(11) 27 sides of friction, wear, lubrication,

(12) pages 4-158 of the Chemistry and Physics Handbook (1990, 71) published by CRC Press,

(13) 27 sides of friction, wear, lubrication,

(14) pages F-22 of the Chemistry and Physics Handbook,

(15) pages F-22 of the Chemistry and Physics Handbook,

(16) pages F-22 of the Chemistry and Physics Handbook,

(17) pages F-22 of the Chemistry and Physics Handbook,

(18) pages F-22 of the Chemistry and Physics Handbook,

(19) pages F-22 of the Chemistry and Physics Handbook,

(20) pages F-22 of the Chemistry and Physics Handbook.

As mentioned above, Mohs hardness measurement is related to the resistance of the material to scratching. Therefore, the present invention seeks to deal with inorganic filler 18 in which the surface hardness differs from the hardness inside the filler below the surface. More specifically, by modifying the surface of the particles in a manner well known in the art, by chemically modifying the surface properties of the particles using techniques known in the art, the surface hardness of the particles is less than the hardness of the glass fiber The hardness of the particles below the surface is greater than that of the glass fibers. Alternatively, the particles may be formed from a first material that is coated, plated, or encapsulated with one or more second materials to form a smooth surface composite. Alternatively, particles can be formed from a first material that is coated, plated, or encapsulated with another type of first material to form a smooth surface composite.

For example, without limiting the present invention, useful synthetic particles may be formed by providing silicon dioxide, carbonate or nanoclay coatings to inorganic particles formed from inorganic materials such as silicon carbide or aluminum nitride. In another non-limiting example, the inorganic particles can react with a binder having a function of electron covalent bonding thereto and a function of crosslinking with a film molding material or a crosslinking resin. Such binders are described in US Pat. No. 5,853,809, column 7 line 20 and column 8 line 43, which are incorporated herein by reference. Silane binders include glycidyl, isocyanato, amino, or carbamyl functional silane binders. In another non-limiting example, the silane binder with alkyl side chain reacts with the surface of the inorganic particles made of inorganic road oxide to provide synthetic particles having a smooth surface. Other examples include particles made from non-polymeric or polymeric materials and plated, encapsulated, or coated with other non-polymeric or polymeric materials. A non-limiting special example of such a synthetic particle is DUALITE, which is a synthetic polymer particle coated with calcium carbonate commercially available from Pierce & Steven, Buffalo, New York.

In one non-limiting embodiment of the present invention, at least one inorganic filler 18 is a non-hydroxide, to minimize the absorption of water into the electronic support of the present invention. As used herein, the term "non-hydroxide" The term means that the inorganic filler does not react with water molecules to form hydroxides and also does not contain water of hydroxides or water of crystals. A "hydroxide" is produced when a water molecule reacts with a substance that does not separate H-OH bonds. See pages 609-610 of Hollis's Chemistry Dictionary (1993, 12th edition), written by Al Lewis and Senior, and pages 186-187 of Chemistry (1967), written by Tiperos, which are incorporated herein by reference. Quote. In relation to the chemical formula of the hydroxide, water molecules are typically added as indicated by the central point, ie 3MgO. 4SiO ₂ .H ₂ O (talc), Al ₂ O ₃ .2SiO ₂ .2H ₂ O (kaolinite). Structurally, the hydroxide inorganic material comprises at least one hydroxyl group in the crystal lattice layer (does not include hydroxyl groups on the surface of the unit structure or material and the material absorbs moisture on its surface or by capillary action); The hydroxyl group, for example, is represented by the structure of kaolinite, shown in FIG. 3.8 on page 34 of the Soil Action Foundation (1976), written by J. Mitchell and 62 of Clay Colloid Chemistry (1977, 2nd Edition) by H. Van Olpen. 18 and 19, respectively, as shown in the structure of the 1: 1 and 2: 1 mineral layer, which is hereby incorporated by reference. The "layer" of the crystal lattice is a sheet bond, which is a bond of the crystal plane of atoms. See pages 196-199 of the Soil Environment Minerals (1977), published by the Soil Science Society of the United States, which is incorporated herein by reference. The collection of layers and interlayer materials (such as cations) is called unit structure.

Hydroxide is added to electrostatic energy without (1) controlled moisture that incorporates cations in the hydroxide material but is not removed without destroying the structure and / or (2) occupies a gap in the structure and does not destroy the balance of charge. Contains structural moisture See page 276 of Al Evans' Introduction to Crystal Chemistry (1948), which is incorporated herein by reference.

In one non-limiting embodiment of the present invention, at least one inorganic filler 18 comprises up to 80% by weight of hydroxide filler relative to the total solid substrate. In another embodiment, the inorganic filler 18 comprises up to 30% by weight of hydroxide filler relative to the total solid substrate. In yet another embodiment of the present invention, the inorganic filler 18 comprises little hydroxide filler. As used herein, the term "contains almost no hydroxide filler" means that the inorganic filler 18 comprises less than 5 wt%, more preferably less than 1 wt% hydroxide filler relative to the total solid substrate. Means that.

In another embodiment of the present invention described in more detail below, the inorganic filler 18 may comprise at least one filler made of hydroxide or hydroxide inorganic materials to be substituted for or added to the non-hydroxyl inorganic materials described above. Include. Examples of such hydroxylated inorganic materials are clay mineral foliates, including mica (such as mica), talc, montmorilite, kaolinite and gypsum.

Although not limited to the present invention, in one embodiment, the inorganic filler 18 is at least one inorganic solid lubricant. As used herein, the term "inorganic solid lubricant" refers to a solid inorganic material that serves to reduce the coefficient of friction between two surfaces, and the term "solid" refers to a material that is not perceptible to flow under normal stress. The material has a limited ability to resist the force to deform it and maintains a defined size and shape under normal conditions. See, page 2169 of the 3rd edition of Webster International English Dictionary (1971), which is incorporated herein by reference. Solids include both crystalline and amorphous materials. Although not limited to the present invention, for example, the inorganic solid lubricant performs anti-friction lubrication between the drill tool used to form a hole in the electronic support comprising the filler 18 and an adjacent solid surface of the electronic support. . As used herein, the term "friction" means resistance to sliding of one solid onto another. Please refer to page 1 of the book, F. Clos, Solid Lubricants and Self-lubricating Solids (1972), which is incorporated herein by reference.

Although not meant to be bound by a particular theory, the printing made of the electronic support may be incorporated by incorporating the resin-penetrating material layer 14 having at least one inorganic solid lubricating filler 18 in the electronic support 10 of the present invention. It is considered that the drill processing characteristics of the circuit board can be improved. More specifically, it is believed that the solid lubricant acts as a drill additive (or drill lubricant) during the drilling process, reducing friction and wear of the tool. In addition, by incorporating the solid lubricant into the laminated plastic instead of externally applying the solid lubricant (as in the case of oil or other drilling lubricants), the intermediate interface between the drill tool and the electronic support, i.e. where the drill tool is worn out Lubrication is believed to occur.

Although not limited, the inorganic solid lubricant as disclosed herein has unique crystalline properties such that the solid lubricant can shear deformation into a thin, flat plate form, the plate easily slides onto another plate, Antifriction lubrication is carried out between the support, more specifically the fiberglass reinforcement and the adjacent solid face. One of the fiberglass reinforcement and the solid side is active. See page 712 of the book by E. Lewis, Senior, Holly's Definitive Chemistry Dictionary (1993, 2nd Edition), which is incorporated herein by reference. Although not required, in one non-limiting embodiment of the invention, the inorganic solid lubricant has a thin plate structure. The thin, solid inorganic lubricant consists of atomic sheets or atomic plates in the form of hexagonal arrays, the bonding strength in the sheet is strong, the van der Waals bonding strength between the sheets is weak, and the shear stress between the sheets is small. Page 125 of the book Friction, Wear and Lubrication, pages 19-22, 42-54, 75-77, 80-82, 90-102, 113-120 in the book Solid Lubricants and Self-lubricating Solids And, page 128, interface lubrication, published by ASME Research Committee on Lubrication (1969); See, page 202-203, Solid Lubricant, contributed by W. Campbell to the Journal of World Paper Evaluation, which is incorporated herein by reference.

Examples of suitable inorganic solid lubricants useful in the present invention having a thin plate structure include boron nitride, graphite, dichalcogenide metal, mica, talc, kaolinite, cadmium isoidide, boric acid, and mixtures thereof. In one embodiment of the invention, the inorganic solid lubricant is selected from boron nitride, graphite, dichalcogenide metal, and mixtures thereof. Examples of suitable dichalcogenide metals are molybdenum disulfide, molybdenum disulfide, tantalum disulfide, selenide tantalum, tungsten disulfide, iselenide tungsten, and mixtures thereof.

Other inorganic solid lubricants which are considered useful in the present invention and which have a thin plate structure include natural clays and synthetic clays, and organic cations are inserted between these clays. As used herein, the phrase "with an organic cation inserted" means that the organic cation is injected into the space between adjacent layers to at least partially separate the clay sheet (or layer). An example of clays deemed useful in the present invention and in which organic cations have been inserted is a nanoclay called NANOMER, which is commercially available from Nanoco Inc., Arlington Heights, Illinois, USA.

In one embodiment of the present invention, the boron nitride particles having a hexagonal crystal structure are solid lubricants in a thin plate form, and the lubricant is used as the inorganic filler 18 in the present invention. Hexahedron boron nitride particles suitable for use in the present invention include Polar Therm 100 Series (PT 120, PT 120, PT 140, PT 160, and PT 180), 300 Series (PT 350), and 600 Series ( Boron nitride powder particles (PT 620, PT 630, PT 640, and PT 670), which are available from Advanced Ceramics, Lakewood, Ohio, USA. Reference is made to Advanced Ceramic, Inc., Lakewood, Ohio, US technical report, "Thermal Fillers for Polaris, Polymeric Materials," which is incorporated herein by reference. The thermal conductivity of these particles is 250-300 W / nK at 25 ° C (298K), dielectric constant is 3.9 and volume resistivity is 10 ¹⁵ ohm-centimeters. The average particle size of the 100 series powder particles is 5 microns to 14 microns, the average particle size of the 300 series powder particles is 100 to 150 microns, and the average particle size of the 600 series powder particles is 16 to 200 microns. Without limiting the invention, the class of polar particles useful as fillers in the present invention is Polar Sum 160, which, as reported by the supplier, has a mean particle size of 6 to 12 μm, a particle size in the range of 70 μm below micron, And a particle size distribution as follows.

%> 10 50 90 Size (μm) 18.4 7.4 0.6

According to the distribution chart, 10% of the measured boron nitride particles of Polar Island 160 have an average particle size of 18.4 µm or more. As used herein, "average particle size" refers to the average particle size of a particle. The average particle size of the particles according to the invention can be measured according to known laser dissipation techniques. In one embodiment of the present invention, the particle size is measured using a Beckman Culter LS 230 laser diffraction particle size meter using a laser beam having a wavelength of 750 nm as described above under the assumption that the particle is spherical. By independently analyzing the particle size of the Polar Sum 160 boron nitride particle sample measured using the Beckman Culter LS 230 particle size analyzer, the boron nitride particles have an average particle size of 11.9 μm and from micrometers to 35 μm. It was found to have a size range and exhibit the following particle size distribution.

%> 10 50 90 Size (μm) 20.6 11.3 4.0

According to the above distribution, 10% of the Polar Sum 160 boron nitride particles have an average particle size of 20.6 µm or more.

Other examples of inorganic fillers that serve as inorganic solid lubricants and are considered suitable for use in the present invention include inorganic fillers having a fullerene structure (buckyball) and antimony oxide.

In one embodiment of the invention, the inorganic filler 18 is made of a non-hydroxylated thin inorganic solid lubricant.

Due to the presence of the layer of resin impregnating material 14 comprising the inorganic filler 18 in the form of the matrix material, which is an inorganic solid lubricant, the friction between the drill tool and the laminated plastic is slightly reduced, thereby preventing heat from being generated during the drilling process. It is possible to reduce the formation of resin stains in the drilled holes, and to further reduce the staining of the resins when the thermal conductivity of the solid lubricant is higher than that of the polymer matrix material 16 and the reinforcing material 20. I think it can be reduced. Without wishing to be bound by a specific theory, if a solid lubricant having high thermal conductivity is employed, the lubricant not only reduces the frictional heat generated during the drilling, but also dissipates the frictional heat generated quickly. In other words, heat is dissipated from the drilled interface, which lowers the temperature of the interface and prevents the resin from melting. In addition, the use of a high thermal conductivity filler can improve the heat dissipation characteristics of the finished printed circuit board made of the filler, thereby improving the performance and reliability of the integrated circuit elements attached to the printed circuit board. Can be improved. As used herein, the term " high thermal conductivity " means that the thermal conductivity of the material is at least 10 W / mK, preferably 20 W / mK, more preferably 30 W / mK at 300K.

One embodiment of the present invention uses a filler that is high in thermal conductivity and is a solid lubricant, but it is also conceivable to use a filler in the present invention that is high in thermal conductivity but does not have to be a solid lubricant.

Table B provides examples of materials having high thermal conductivity that are suitable for use as inorganic fillers in the present invention.

TABLE B

Mineral filler Thermal Conductivity (W / mK at 300K) Graphite Up to 2000 (21) molybdenum 138 (22) platinum 69 (23) Palladium 70 (24) aluminum 205 (25) nickel 92 (26) Copper 398 (27) gold 297 (28) iron 74.5 (29) silver 418 (30) Boron nitride 200 (31) Boron phosphide 350 (32) Aluminum phosphide 130 (33) Aluminum nitride 200 (34) Gallium nitride 170 (35) Gallium Phosphate 100 (36) Silicon carbide 270 (37) Silicon nitride 30 (38) Beryllium oxide 240 (39) Tantalum diboride 100 (40)

(21) J. Physics and Chemistry Solids (1973), Volume 34 Non-metallic Crystals with High Thermal Conductivity, published by Rat Slack on page 322,

(22) p. 174 of the Microelectronic Packing Handbook (1989), edited by Alteramarler,

(23) p. 174 of the Microelectronic Packing Handbook (1989),

(24) p. 37 of the Microelectronics Packing Handbook (1989),

(25) p. 174 of the Microelectronics Packing Handbook (1989),

(26) p. 174 of the Microelectronics Packing Handbook (1989),

(27) p. 174 of the Microelectronic Packing Handbook (1989),

(28) p. 174 of the Microelectronic Packing Handbook (1989),

(29) p. 174 of the Microelectronics Packing Handbook (1989),

(30) p. 174 of the Microelectronic Packing Handbook (1989),

(31) "High Thermal Conductivity Nonmetallic Crystals" by Rat Slack of J. Physics and Chemical Solids (1973), Book 34, page 322,

(32) "High thermal conductivity nonmetallic crystals" by rat slack on J. Physics and Chemical Solids (1973), Volume 34, page 325,

(33) "High thermal conductivity nonmetallic crystals" by rat slack in J. Physics and Chemical Solids (1973), Volume 34, page 333,

(21) J. Physics and Chemistry Solids (1973), Vol. 34, 329, by Slack of Rats, "The High-Conductivity Nonmetallic Crystals,"

(35) "High Thermal Conductivity Nonmetallic Crystals" by Rat Slack of J. Physics and Chemical Solids (1973), Book 34, page 333,

(36) "High thermal conductivity nonmetallic crystals" by rat slack on J. Physics and Chemical Solids (1973), Volume 34, page 321,

(37) p. 36 of the Microelectronics Packing Handbook (1989),

(38) p. 36 of the Microelectronics Packing Handbook (1989),

(39) p. 905 of the Microelectronics Packing Handbook (1989),

40 also ESK engineering ceramics, titanium diboride powders data sheet TiB _2/03/95, large-way Chemical Corp. commercially available.

In one embodiment of the present invention, the inorganic filler 18 has a high electrical resistivity. As used herein, the term "high electrical resistivity" means that the electrical resistivity of the material is at least 1000 μΩ-cm. For example, without limiting the present invention, a filler having a high electrical resistivity may be used in a conventional electronic circuit board in order to prevent the loss of an electrical signal caused by the conduction of electrons through the filler. For certain applications such as circuit boards for microwave, radio frequency interference and electromagnetic interference applications, high electrical resistivity fillers are not required. Although not limited by the present invention, the electrical resistivity of selected materials useful as the inorganic filler 18 in the present invention and having high electrical resistivity are shown in Table C below.

Table C

Mineral filler Electric resistivity (μΩ-cm) Boron nitride 1.7 × 10 ¹⁹ (41) Aluminum nitride Greater than 10 ¹⁹ (42) Silicon carbide 4 × 10 ⁵ to 1 × 10 ⁶ (43) Zinc sulfide 2.7 × 10 ⁵ to 1.2 × 10 ¹² (44) Diamond 2.7 × 10 ⁸ (45) Silicon nitride 10 ¹⁹ to 10 ²⁰ (46)

(41) p. 654 of Abimer's compilation, "Synthesis and processing of carbide, nitride and boride materials (1977)",

(42) p. 654 of Abimer's compilation, "Synthesis and processing of carbide, nitride and boride materials (1977)",

(43) p. 654 of Abimer's compilation "Synthesis and Processing of Carbide, Nitride and Boride Materials (1977)",

(44) pp. 12-63 of the Chemical and Physics Handbook (1990, 71), published by CRC Press,

(45) pages 12-63 of the Chemical and Physics Handbook (1990, 71), published by CRC Press,

46, A. Vimer's compilation, page 654 of "Synthesis and Processing of Carbide, Nitride and Boride Materials".

In one embodiment of the invention, the inorganic filler 18 is at least one solid lubricant having high thermal conductivity and high electrical resistivity.

Non-limiting examples of inorganic fillers with high thermal conductivity and high electrical insulation are inorganic boron nitrides.

In another non-limiting embodiment of the present invention, at least one inorganic filler 18 has low thermal expansion. As used herein, the term “low thermal expansion” means that it has a lower coefficient of thermal expansion (CTE) than the polymeric matrix material 16. Although not required, the material with a low coefficient of thermal expansion has a smaller CTE than the reinforcement. In one non-limiting example of the invention, the inorganic filler 18 has a negative CTE. That is, the inorganic filler 18 will shrink during heating. For example and although not limited thereto, in one embodiment the polymeric matrix material 16 is an epoxy material having a CTE in the range from 600-800 × 10 ⁻⁷ / ° C. in the range of 0 ° C. to 200 ° C. The solid filler 18 has a smaller CTE than the polymeric matrix material in the same temperature range and in particular has a CTE of less than 600-800 × 10 ⁻⁷ / ° C. in the same temperature range. In another non-limiting embodiment, the inorganic filler 18 has a CTE of less than 100 × 10 ⁻⁷ / ° C. in the range of 0 ° C. to 200 ° C. In another non-limiting embodiment, the inorganic filler 18 has a CTE of less than 50 × 10 ⁻⁷ / ° C. in the range of 0 ° C. to 200 ° C. Although not meant to be limited by any particular principle, the mixing of low thermal expansion fillers into the prepreg layer 14 results in the z-axis heat of the electronic supports 10 made therefrom. I believe it can reduce swelling. As used herein, the term “z-axis thermal expansion” generally refers to the thermal expansion of the electronic support in a direction parallel to the thickness of the electronic support and generally in a direction perpendicular to the major surfaces of the electronic support. it means. As used herein, the term “major surfaces” refers to the surfaces of the electronic support that are generally perpendicular to the thickness of the electronic support and generally parallel to the major dimension (ie, xy dimension) of the reinforcing material. The reduction in z-axis thermal expansion of the electronic supports can in particular reduce the mismatch between the coating on the walls of the polymeric matrix material and the holes formed therein, thereby improving the reliability of the printed circuit boards made therefrom. The reduction in thermal expansion mismatch between the polymeric matrix material and the coating can reduce the occurrence of cracking of the coating on the hole walls, sometimes referred to as barrel cracking, in printed circuit boards. Non-limiting examples of low thermal expansion materials believed to be useful in the present invention include those listed in Table D below.

Table D

Mineral filler Coefficient of Thermal Expansion (CTE) (× 10 ^-7 / ℃) Aluminum oxide 25 ℃ ⁴⁷ to 54 Magnesium oxide 25 ℃ ⁴⁸ to 104 Titanium dioxide 25 ℃ ⁴⁹ to 75 Silicon nitride 25 ℃ ⁵⁰ to 8 Invar ⁵¹ 2 at 25 ℃ ⁵² molybdenum 25 ℃ ⁵³ to 48 boron 25 ℃ ⁵⁴ to 48 Boron nitride 20K-1000K (-253 ℃ to 727 ℃) ⁵⁵ to 0.77-7.5 Silicon carbide 0 ℃ -200 ℃ ⁵⁶ to 26 Lithia Wite 20 ℃ -1000 ℃ ⁵⁷ to 9 Beta-quartz -3 to 25 ℃ ⁵⁸ Beta-eucryptite In 25 ℃ ⁵⁹ -60

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

⁴⁷ R. Tummala (Ed.), Microelectronics Packaging Handbook , (1989), page 637, by reference.

⁴⁸ Tummala Page 637

⁴⁹ ld.

⁵⁰ ld.

⁵¹ Invar Iron-Nickel Alloy

⁵² ld.

⁵³ ld.

⁵⁴ ld.

⁵⁵ Hlavac, J. The Technology of Glass & Ceramics: An Introduction , (1983), page 232, cooperated by reference.

⁴⁹ ld. Page 278, cooperate by reference.

⁵⁷ Hlavac, page 232.

⁵⁸ Tummala Page 637.

⁵⁹ Hlavac Page 232.

In another non-limiting embodiment of the invention, the at least one inorganic filler 18 is conductive anodic in the PCB which in turn reduces the electrical shorts in the PCB generated by the filaments. It is a material that suppresses the formation of filaments. Electrically conductive filaments are formed on a circuit board due to the electrochemical movement of metal ions, usually copper ions. Generally, these filaments are formed along the interface between the glass fiber reinforcement and the polymeric matrix material (usually epoxy) used to form the PCB. The interface between the glass fiber reinforcement and the epoxy is damaged in some ways, such as by filamentation or hydrolysis, and it is believed that CAF is formed when the PCB is exposed to high humidity and high bias conditions. If such conditions exist, an electrochemical corrosion cell can be established between the positively charged features. For example and without limitation, one can see that CAF occurs between reversely filled lines and holes and between lines and holes. In general, CAF occurs when water penetrates the interface between the glass reinforcement and the epoxy between the positive and negative charging characteristics (ie, the cathode). Ions, such as free chloride ions, which may be present in the epoxy itself or may be contaminants, form electrolytes and dissolve in water to create an electrochemical corrosion cell. Corrosion of the anode is caused by dissolution and transport of metal ions, in particular copper ions from the anode towards the cathode, through the electrolyte. Insulation resistance of the space between the anode and cathode tends to be reduced, such as the plate-out of a solution such as a precipitate of metal ions or a halide salt, and leakage of current can occur between these features. have. If an electrically conductive passageway or CAF is formed between the two features, an electrical short will occur. In other cases, some of the anode may be rapidly depleted in metal to cause electrical opening. Growth of such conductive filaments can be inhibited by trapping, binding, or reacting with metal ions in a manner that prevents 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 complex with metal ions, the absorption of metal ions on their surfaces and / or ends, traps or encapsulates metal ions within their lattice structure and / Or tends to suffer from ion exchange. Although not meant to be limited to this application, the use of inorganic fillers having a high affinity for metal ions, in particular copper ions, has been described above for slowing or preventing electrical short circuits caused by the formation of conductive anode filaments. It is believed to be beneficial. By placing the inorganic filler 18 having a high affinity for metal ions in the path of the mobile metal ions, for example, by diffusing the inorganic filler 18 in the polymeric matrix material 16, the polymeric matrix material ( Metal ions traveling through 16 may be sequestered or trapped by the inorganic filler 18, thereby inhibiting the growth of electrically conductive filaments and the resulting electrical shorts. Thus, in one non-limiting embodiment of the invention, the matrix material 16 may be formed of an inorganic filler 18 having a high affinity for metal ions that can prevent electrical shorts due to conductive anode filament formation. It contains a sufficient amount.

In one non-limiting embodiment of the invention, the inorganic fillers 18 having a high affinity for metal ions are clays having a cation exchange capacity of at least 20 milligram equivalents (meq / 100g) per 100 grams of dry filler. Minerals. As used herein, the term “cationic exchange capacity” or “CEC” refers to the amount of absorbable and internally layered exchangeable cations required for the balance of layer charge overlap in a material due to isotropic substitution of ions in the layer structure. it means. See D. Hillel, Fundamentals of Soil Physics , (1980), pages 71-74, and J. Mitchell, Fundamentals of Soil Behavior , (1976), page 32, which is particularly incorporated herein by reference. CEC, sometimes referred to as total exchange capacity, basic exchange capacity, or cation adsorption capacity, is usually measured by techniques well known to those skilled in the art, and it is not believed that the detailed description is needed in view of this disclosure. If more information is needed, see Rich, Removal of excess salt in CEC determination, Soil Science, vol. 93 (1962), pp. 87-94, Rich, Ca ⁺² determination for CEC determinations, Soil Science, vol. 92 (1961), pp. 226-231, and http://bluehen.ags.udel.edu/deces/prod-agric/chap9-95.htm (January 31, 2001).

Examples of clay minerals having a cation exchange capacity of at least 20 meq / 100 g include, but are not limited to, montmorillonite, nontronite, saponite, illite (hydrous micas), bare micalite, chlorite, sepiolite, Attapulgite, bentonite, hectorite, synthetic fluoromicas (as described below) and mixtures of those presented. See Hillel, page 44-45, which cooperates in particular here.

In another non-limiting embodiment of the invention, the filler 18, which has a high affinity for metal ions, has a cation exchange capacity of at least 80 meq / 100 g. Examples of clay minerals having a CEC of at least 80 meq / 100g cation exchange capacity include, but are not limited to, montmorillonite, nontronite, saponite, bare milite, bentonite, hectorite, illite, synthetic fluoromicas (As described below) and mixtures thereof. In another non-limiting embodiment of the invention, the inorganic fillers 18 having high affinity for metal ions are expandable clay minerals. As used herein, the term "elastic clay" means clay that can swell. In general, expandable clay minerals may be provided for cation exchange capacities of at least 80 meq / 100 g due to their high surface area and exchangeable inner layer cations. Non-limiting examples of expandable clay minerals useful in the present invention include montmorillonite, bare milite, saponite, illite, bentonite, hectorite, illite, expandable synthetic fluoromica, and mixtures of those presented. . Generally, although not required, expandable clay minerals have a negative layer charge (X) in the range from 0.1 to 0.9, balanced by the appearance of exchangeable inner layer cations. Minerals with less than 0.1 layer charge, such as kaolinite and talc, do not include internal layer charges; Thus minerals with a charge per formula unit of greater than 0.9, such as mica, comprise only non-exchangeable inner layer clays and are generally non-expandable in nonweather form. See JB Dixon et al. (Eds.), Minerals in the Soil Environment , (1977), pages 200, 221-232, and Mitchell, page 32, which are specifically incorporated herein by reference.

In another non-limiting embodiment of the present invention, a fluoroprophyte in which an expandable clay mineral having a high affinity for metal ions, particularly copper ions, is isoformally substituted (replaced) by lithium cations And fluorophlogopites with at least a portion of the potassium cation isoformally substituted by fluorophlogopites and sodium cations. Sodium fluoropropogite is a synthetic fluoromica, wherein at least some of the potassium on the inner layer is isotropically substituted with sodium cations. Sodium fluoropropogite is expandable, so non-climate mica is not expandable (as described above). Kirk-Othmer Encyclopedia of Chemical Technology , Vol. See 13 (2 ^th Ed., 1967), pages 412-413.

In another non-limiting embodiment of the invention, the inorganic filler 18 may be among the inorganic fillers described above that are surface treated or coated with a material having a high affinity for metal ions. For example, but not limited to, boron nitride particles may be treated with an organometallic ion synthetizer to form an inorganic filler having a surface having a high affinity for metal ions. Non-limiting examples of suitable organometallic ion syntheses include ethylenediamine, triethylenetetramine, ethylenediamine-tetraacetic acid (EDTA), polyvinylpyridine, and 2-aminopyrimidine Porphyrin species and amines. As used herein, the term "porphyrins" refers to a basic structure consisting of originating in livingmaterials and four internal connection rings, each of which consists of four carbon atoms and one nitrogen atom. It means complex components having a. Non-limiting examples of porphyrin species include red hemoglobin and green chlorophyll. See, in particular, J. Hunt, Petroleum Geochemistry and Geology , (1979), page 551, and G. Hawley, Hawley's Condensed Chemical Dictionary , (10 ^th Ed., 1981), page 843, which is particularly incorporated herein by reference. In another non-limiting example, inorganic filler particles, such as boron nitride and aluminum nitride, have nanocations having a cation exchange capacity of at least 20 meq / 100g to form filler particles having a surface having a high affinity for metal ions. (nanoclay) particles can be coated. In addition to the clay materials disclosed above, other silicate materials having a high affinity for metal ions, especially copper ions, may be used as the filler 18. For example and without limiting the invention, porous silicates, in particular organofunctional porous silicates, can be used as filler. In one non-limiting embodiment of the invention, the porous silicates with high affinity for metal ions have a CEC of at least 20 meq / 100g. In another non-limiting embodiment, the porous silicates having a high affinity for metal ions have a CEC of at least 80 meq / 100 g.

In another non-limiting embodiment of the invention, filler 18, which has a high affinity for metal ions, can be characterized by its capacity to remove, i.e., pump cations from, an aqueous solution. This dose is defined as the ratio of the amount of cation absorbed per gram of solution to the amount of cation remaining per millimeter of solution and is quantified by the distribution constant K _d expressed in ml / g. Materials that will remove selected metal ions from the aqueous solution, particularly those that will remove copper ions, are also expected to reduce CAF when incorporated into the matrix as described herein. The distribution constant K _d can be measured according to a method developed by Komarneni et al. In Material Research Laboratory, The Pennsylvania State University, University Park, PA. For more information about K _d , see Sridhar, Komarneni, Naofumi Kozai and Rustum Roy, "Novel function for anionic clays; selective transition metal cation uptake by diadochy", Journal of Material Chemistry, 8 (6) (1998), pp. 1329-1331; Sridhar Komarneni, William j. Paulus and Rustum Roy, " New Developments in Ion Exchange: Materials, Fundamentals and Applications, Proceedings of the International Conference on Ion Exchange , Tokyo (1991), pp. 51-56; Masamichi Tsuji and Sridhaar Kormarneni," An extended method for analytical evaluation of distribution coefficients on selective inorganic ion exchangers, " Separation Science and Technology, 27 (6) (1992), pp. 813-821; and Masamichi Tsuji and Sridhar Komarneni," elective exchange of divalent transition metal ions in crptomelance-type manganic acid with tunnel structure, " Jounal of Materials Research , 8 (3) (1993), pp. 611-616.

To determine K _d using the method developed by Komarneni, an aqueous 0.5N NaCl solution containing 0.0001NM ⁺ is prepared at room temperature, where M ⁺ is the cation to be studied. The sample of the solution is sealed in a vial for 24 hours and then analyzed using techniques well known to those skilled in the art, such as direct current plasma methods, to determine the exact amount of M ⁺ per million fraction (PPM) of the solution. This analysis provides a reference for determining how much M ⁺ is removed during the experiment. A 20 mg sample of the material is equilibrated for 24 hours in a sealed glass jar with a 25 ml solution. After the equilibrium, the solid and liquid phase are separated, the solution is analyzed to determine absorption of M ^+, are reported as K _d (M ^+).

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

Non-limiting examples of clay minerals and other silicates having acceptable K _d (Cu ²⁺ ) include bentonites, hectorites and porous silicates, and in particular porous organofunctional silicates. It includes.

In addition to the materials described above for reducing CAF, it is believed that other chelating agents and polymers can be used as filler materials having high affinity for metal ions to reduce CAF. Although not limited by the present invention, the chelate materials preferably include organic functional groups containing nitrogen atom (s), such as but not limited to amines and imines. Other non-limiting chelating agents and polymers that may support this purpose may have sulfur containing, oxygen containing, phosphorus containing organic functional groups or combinations of these chelating functional groups. Non-limiting examples of additional chelating agents that can be used for CAF reduction include "SILQUEST A1387", a silylated polyazamide commercially available from "Crompton Corporation of Greenwich, Connecticut; and Emery 6717". , Partially amidated polyethylene imine, and "Versamid 140", commercially available from "Cognis Corporation of Cincinnati, Ohio".

Referring to FIG. 1, the inorganic filler 18 mixed in the prepreg layer 14 will depend in part on the desired function of the inorganic filler. In one non-limiting embodiment of the invention, the inorganic filler 18 is provided in an amount sufficient to form a essentially continuous or interconnected phase 30 (see FIG. 1) through the PCB. . Without limiting the invention, the volume fraction of the inorganic filler 18 provided in the polymeric matrix material 16 may be at or above the percolation threshold (or limit) of the filler 18. As used herein, the term “percolation threshold” refers to the volume fraction of filler required to form a fundamentally interconnected path of filler through the matrix material. See Tummala (1989) pages 576-577, which is particularly coordinated by reference. In another non-limiting embodiment, the filler 18 is provided as a essentially continuous layer in the electronic support (as described in more detail below).

Nevertheless, polymeric matrix material 16 having a volume fraction of filler 18 below the percolation limit of the filler may be used therefrom, such as, but not limited to, thermal conductivity, electrical resistance, CAF resistance, gamma force, and CTE. It is natural for a person skilled in the art to be effective in providing desired characteristics to the electronic support to be made. In addition, it is difficult to add a large amount of inorganic filler to the polymeric matrix materials, so in one non-limiting embodiment of the invention, the polymeric matrix material comprises a smaller amount of inorganic filler than the percolation limit of the filler. It will be apparent to one skilled in the art that for a given volume fraction (or set) of spent inorganic filler, the actual weight fraction of the inorganic filler will depend on the densities of the particulate inorganic filler and the polymer matrix material.

In one embodiment of the invention, although not limited thereto, the at least one inorganic filler 18 is an inorganic solid lubricant, and the amount of the at least one inorganic filler 18 is equal to the at least one on a total solid basis. Ranging from 0.03 weight settling of the total combined weight of inorganic filler 18 and polymer matrix material 16 to 70 weight percent. In another non-limiting embodiment, the amount of the at least one inorganic filler 18 is from a 0.03 weight set of the total combined weight of the polymer matrix material 16 and the at least one inorganic filler 18 on a total solid basis. The range is up to 50 percent by weight. In another non-limiting embodiment, the amount of the at least one inorganic filler 18 is a 0.03 weight set of the total combined weight of the polymer matrix material 16 and the at least one inorganic filler 18 on a total solid basis. From 35 percent by weight.

In one non-limiting embodiment of the invention, wherein the at least one inorganic filler 18 has a thermal conductivity of at least 30 W / mK at 300 K, wherein the amount of the at least one inorganic filler 18 is on a total solid basis. Ranging from 0.3 weight set of the total combined weight of polymeric matrix material 16 and said at least one inorganic filler 18 to 70 weight percent. In another non-limiting embodiment, the amount of at least one inorganic filler 18 is 70 from a 10 weight set of the total combined weight of the polymer matrix material 16 and the at least one inorganic filler 18 on a total solid basis. The range is up to weight percent. In another non-limiting embodiment, the amount of the at least one inorganic filler 18 is a 35 weight set of the total combined weight of the polymer matrix material 16 and the at least one inorganic filler 18 on a total solid basis. To 70 percent by weight.

In one non-limiting embodiment of the invention, wherein the at least one inorganic filler 18 has a low coefficient of thermal expansion, and the amount of the at least one inorganic filler 18 is such that the polymer matrix material 16 on the total solid basis. And from a 5 weight set of the total combined weight of the at least one inorganic filler 18 to 80 weight percent. In another non-limiting embodiment, the amount of the at least one inorganic filler 18 is from a 20 weight set of the total combined weight of the polymer matrix material 16 and the at least one inorganic filler 18 on a total solid basis. The range is up to 75 weight percent. In another non-limiting embodiment, the amount of the at least one inorganic filler 18 is a 25 weight set of the total combined weight of the polymer matrix material 16 and the at least one inorganic filler 18 on a total solid basis. To 60 percent by weight.

In one non-limiting embodiment of the invention, wherein the at least one inorganic filler 18 has a high affinity for metal ions, wherein the amount of the at least one inorganic filler 18 is a polymer matrix material on a total solid basis. And from a 0.03 weight set of the total combined weight of the 16 and the at least one mineral filler 18 to 80 weight percent. In another non-limiting embodiment, the amount of at least one inorganic filler 18 is 80 from a 10 weight set of the total combined weight of the polymer matrix material 16 and the at least one inorganic filler 18 on a total solid basis. The range is up to weight percent. In another non-limiting embodiment, the amount of the at least one inorganic filler 18 is a 35 weight set of the total combined weight of the polymer matrix material 16 and the at least one inorganic filler 18 on a total solid basis. To 80 percent by weight.

Referring back to FIG. 1, as mentioned above, the reinforcing material 20 may be, for example, as described above, for example, woven and non-woven fabrics, mats, knits, and multilayer fabrics. Can be provided. Although not limited by the present invention, in one embodiment the reinforcing material 20 is a warven fabric. In another non-limiting embodiment, the reinforcing material 20 is a woven fabric comprising glass fibers, as shown in FIG. 1. Glass fibers useful in the present invention include "E-glass", "A-glass", "C-glass", "D-glass", "R-glass", "S-glass", and E-glass derivatives. And those prepared from the same fibrous glass components. As used herein, the term “fibrous” generally refers to a material that can be formed from continuous fibers, strands or yarns. As used herein, the term "twisted" means a plurality of individual fibers; The term “fiber” means individual filaments; And the term "thread" means twisted thread. As used herein, the term "E-glass derivatives" refers to glass components comprising small amounts of fluorine and / or boron, preferably fluorine-free and / or boron-free. Also, as used herein, “a small amount of fluorine” means a weight percent fluorine less than 0.5, preferably less than 0.1 weight percent fluorine, and “a small amount of boron” means a weight percent boron less than 5. , Preferably less than 2 weight percent boron. In one non-limiting embodiment of the invention, the glass fibers are formed from E-glass or E-glass derivatives. Such components and methods of making glass filaments therefrom are well known to those skilled in the art, and are not deemed necessary for the description thereof in view of the present disclosure. If additional information is needed, glass components and fiberization methods, in particular cooperated herein by reference, K. Loewenstein, The Manufacturing Technology Continuous of Glass Fibers, (3d Ed. 1993), pages 30-44, 47-60, 115-122 and 126-135; And US Patents 4,542,106 and 5,789,329.

Although not limited by the present invention, the reinforcing material 20 may comprise at least one glass and may be a glass fiber fabric in one non-limiting embodiment, although the reinforcing material 20 is not limited. , Fibrous non-glass inorganic materials, fibrous organic materials and mixtures and combinations thereof, may be formed from any form of fibrous material well known to those skilled in the art. The inorganic and organic materials may be materials made by humans or naturally occurring. It will be appreciated by those skilled in the art that the fiberizable inorganic and organic materials may also be polymeric materials. Examples of non-glass inorganic fibers suitable for use in the present invention include, but are not limited to, ceramic fibers formed from silicon carbide, carbon, graphite, mulite, aluminum oxide, and piezoelectric ceramic materials. Non-limiting examples of suitable animal and plant-derived natural fibers include cotton, cellulose, natural rubber, flax, cilithia, hemp, sisal, and wool. Suitable polymeric fibers are not limited, including polyamides (such as nylon and aramids), thermoplastic polyesters (such as polyethylene terephthalate and polybutylene terephthalate), acrylics (polyacrylonitriles) ), Polyolefins, polyurethanes, and vinyl polymers (such as polyvinyl alcohol). Non-glass fibers believed to be useful in the present invention are hereby incorporated by reference in Encyclopedia of Polymer Science and Technology , Vol. 6 (1967), pages 505-712, long. It is understood that mixtures and interpolymers of the above fiber materials and combinations formed from the above materials can be used in the present invention if desired.

As discussed above, various glass compositions may be used to form the reinforcement of the present invention, while in one embodiment of the present invention, the glass reinforcement is at least one having an iron component no greater than 11 weight percent of the total weight of the glass composition. It includes, but is not limited to, glass fibers. In another embodiment, the glass reinforcement comprises, but is not limited to, at least one glass fiber having an iron component no greater than 5 weight percent of the total weight of the glass composition. Glass fibers having an iron content of 11 percent or more are not used in applications because of their dark color. For example, basalt fibers generally having, but not limited to, 11 percent FeO component and 2 percent Fe 2 O 3 component, based on the total glass composition. As used herein, the expression "basalt fibers" refers to fibers formed from igneous rock that is low in quartz, dark in color, and relatively rich in iron and magnesium. See, in particular, page 335 of Advanced Inorganic Fibers, Processes-Structure-Properties-Applications, 2000 by F. Wallenberger et al. . Thus, in one embodiment of the present invention, the textile fiber reinforcement material is formed from at least one fiber without basalt fibers, but is not limited thereto. Regarding examples of basalt compositions specifically incorporated herein by reference, the Handbook of Reinforcements for Plastics, edited by J.Milewski and H. Katz, in particular by "Subbasal Fibers" by RVSubramanian (1987) 287-295). In one embodiment of the invention, the fabric fiber reinforcement is essentially free of basalt fibers. As used herein, the expression “essentially does not include basalt fibers” means that the textile fiber reinforcement comprises less than 1 weight percent of basalt fibers relative to the total weight of the textile fiber reinforcement, more preferably basalt fibers. It means not to.

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

The following reviews briefly describe methods for forming suitable glass fibers for use in the present invention, and do not limit the present invention and provide one possible method for forming glass fibers that can be used by the present invention. It means to explain. In conventional glass fiber forming operations, the taper is tapered through a plurality of openings in the bottom wall of the bushing and spinner to form a plurality of fibers. Almost immediately after formation, the fibers are coated with a sizing composition to protect their surface from abrasion and to provide the fibers with the necessary processing properties. The size or sizing used herein relates to the coating composition applied to the fibers after formation. The fibers are collected into strands for further processing into a package. Such methods of forming glass fibers are well known in the art, and additional disclosure of these methods is not considered necessary by the present invention. However, for more information on fiber forming methods, see pages 115-235 of Louiswenstein.

Conventional sizing compositions applied to glass fibers for use in the formation of textile fibers are disclosed on pages 238 to 244 of Louiswenstein, which is specifically incorporated herein by reference. In addition, the performance of threading is inserted between the warp yarns so that the slashing composition is generally applied during warping and beaming, in order to protect the warp yarns from weaving from wear. It is applied to pasted glass fibers. Such slashing compositions generally comprise compositions such as polyvinyl alcohol, which is well known in the art. While sizing and slashing compositions are generally effective in providing good weave of glass fiber strands and the yarns formed therefrom, they are generally incompatible with the polymeric matrix material forming the electronic supports. Thus, the fiber glass fabric formed therefrom is heated in the polymeric matrix material from the surface of the glass fibers prior to mixing, for example by heating the fabric at 380 degrees Celsius for 60 to 80 hours and / or by washing the fabric. It is usually used in industry to remove compatible compositions such as non-resins. Usually these kinds of operations include heat-laundry, oil separation, or degreasing, and optionally below are described for degreasing. The fibers are then recoated to finish sizing. Finish sizing, in general, consists of a silane bonding material and water, and is applied to fabrics to promote compatibility between the fibers and the polymeric matrix material to which the fibers are bonded. However, sizing removal treatments can be expensive and costly to the fabric. Therefore, in one embodiment of the present invention, the reinforcement material 20 comprises a woven glass fiber reinforcement material composed of glass fibers coated with a resin compatible with non-degreasing, sizing compositions. As used herein, “compatible resin” or “polymeric matrix material” is such that the coating composition applied to the glass fibers is compatible with the polymeric matrix material into which the glass fibers are mixed so that the coating composition (or selected coating elements) is characterized by the following characteristics: Name means at least one of the following: no separation prior to mixing with the matrix material (eg by degreasing or oil separation), and the high penetration of the matrix material throughout the mat or fabric in conventional processing and In mats or fabrics embodying the threading, it is possible to facilitate the high penetration of the matrix material throughout the individual bundle of fabrics and to obtain a final material with the desired physical properties and stability of hydrolysis. A resin compatible with the sizing composition may be applied to the glass fibers immediately after formation or after a predetermined time, for example after weaving. As used herein, a "non-degreasing" material or fabric is one that has not been subjected to conventional processing to remove the non-resin that is compatible with the sizing component from the material or fabric.

One embodiment of a resin compatible with a sizing composition not limited in the present invention includes one or more, preferably between one or more lattice between adjoining glass fibers and adhering to the fibers when applied to the fiber It contains a number of molecules that provide spaces. Examples of molecules include hexagonal boron nitride and hollow styrene acrylic polymer particles.

In addition to the particles, one embodiment of a resin compatible with the preferred sizing composition comprises one or more film-forming materials, such as glass, inorganic and polymeric materials. Examples of film-forming materials include, but are not limited to, vinyl polymers such as polyvinyl pyrrolidone, polyesters, polyamides, polyurethane-based and combinations thereof.

Instead of or in addition to the films forming the materials discussed above, one embodiment of a resin compatible with the sizing composition may include one or more glass fiber bonding materials such as organo-silane bonding materials, ionizing metal bonding materials, phosphorus Binding material, aluminum binding material, amino-comprising Warner binding material, and mixtures thereof.

One embodiment of compatible resins of sizing compositions further includes one or more softeners or surfactants. Non-limiting examples of such softeners include amine salts of fatty acids, alkyl imidazoline derivatives, acid solubilized fatty acid amides, fatty acids and condensates of amides in place of polyethylene imines and polyethylene imines.

Non-limiting examples of compatible resins of sizing compositions may further include one or more lubricating materials, which are chemically compatible with the polymeric materials and softeners discussed above for adding desired processing characteristics to the fabric strand during weaving. There is a difference. Examples such as ground acid esters useful herein include, but are not limited to, cetyl palmitate, cetyl myristate, cetyl laurate, octadecyl laurate, octadecyl myristate, octadecyl palmitate, and octadecyl sterate It doesn't work. Other useful fatty acid esters, lubricating agents include trimethylopropane tripelargonate, neutral spermatozoon and triglyceride oils, including but not limited to soybean oil, linseed oil, epoxidized soybean oil and epoxidized linseed oil. It is not limited. The lubricating materials also include nonpolar petroleum waxes and water soluble polymeric materials, including but not limited to polyalkylene polyols and polyoxyalkylene polyols.

Non-limiting examples of resins compatible with sizing compositions may further include a resin reactive diluent to further increase the lubricity of the coated fiber strands. As used herein, "resin reactive diluent" means that the diluent comprises functional groups capable of chemically reacting with the same resin that the coating composition is compatible with. The diluent can be any lubricant with one or more functional groups that react with the resin system. More preferably the functional group reacts with the epoxy resin system. Non-limiting examples of suitable lubricants include amine groups (eg modified polyethylene amines), alcohol groups (eg polyethylene glycols), anhydride groups, acid groups (eg fatty acids) or epoxy groups (eg epoxy Lubricated oil) and epoxidized linseed oil).

Non-limiting examples of resins that are compatible with the sizing composition further include one or more emulsifiers to emulsify or formulate components of the coating compositions, such as particles and / or lubricious materials. Suitable examples of emulsifiers or surfactants are polyoxyethylene block interpolymers, ethoxylated alkyl phenols, polyoxyethylene octylphenyl glycol ethers, obitol ester ethylene oxide derivatives, polyoxyethylated vegetables Oils, ethoxylated alkylphenols, and nonylphenol surfactants.

Other additives may include, but are not limited to, embodiments of the resin that are compatible with sizing compositions, such as crosslinking materials, plasticizers, silicones, fungicides, bactericides, and antifoams. In addition, a sufficient amount of organic and / or inorganic acid or base to provide a coating composition having a pH of 2 to 10 may be included in the resin compatible with the sizing composition.

Examples of resins compatible with sizing compositions are shown in Table E, where the values listed are the weight percentage of the total coated composition over the total solid base.

Table E

example ingredient A B C D E F G H PVP K-30 ⁶⁰ 13.7 13.4 13.5 13.4 15.3 14.2 STEPANTEX 653 ⁶¹ 27.9 27.3 13.6 12.6 A-187 ⁶² 1.7 1.6 1.9 1.9 2.8 2.3 1.9 1.7 A-174 ⁶³ 3.4 3.3 3.8 3.8 4.8 4.8 3.8 3.5 EMERY 6717 ⁶⁴ 2.3 2.2 1.9 1.9 2.5 2.4 MACOL OP-10 ⁶⁵ 1.5 1.5 1.7 1.6 TMAZ-81 ⁶⁶ 3.0 3.0 3.4 3.1 MAZU DF-136 ⁶⁷ 0.2 0.2 0.3 0.2 ROPAQUE OP-96 ⁶⁸ 39.3 38.6 43.9 40.7 RELEASECOAT-CONC 25 ⁶⁹ 4.2 6.3 6.4 3.8 4.5 POLARTHERMPT 160 ⁷⁰ 2.7 2.6 2.6 5.9 2.8 SAG 10 ⁷¹ 0.2 0.2 RD-847A ⁷² 23.2 23.0 DESMOPHEN 2000 ⁷³ 31.2 31.0 44.4 44.1 PLURONIC F-108 ⁷⁴ 8.5 8.4 10.9 ALKAMULS EL-719 ⁷⁵ 3.4 2.5 ICONOL NP-67 ⁷⁶ 3.4 4.2 3.6 POLYOX WSR 301 ⁷⁷ 0.6 0.6 DYNAKOLL Si 100 ⁷⁸ 29.1 28.9 SERMUL EN 668 ⁷⁹ 2.9 SYNPERONIC F-108 ⁸⁰ 10.9 EUREDUR 140 ⁸¹ 4.9 VERSAMID 140 ⁸² 4.8 FLEXOL EPO ⁸³ 13.6 12.6

⁶⁰ PVP K-30 polyvinyl pyrrolidone is commercially available from ISP Chemistry of Wayne, New Jersey.

⁶¹ STEANTEX 653 is available from Stephen's, Newwood, Jersey.

⁶² A-187 Gamma-glyoxideoxypropyltrimethoxysilane is commercially available from CT, Greenwich Chromton Corporation.

⁶³ A-174 gamma-methacryloxypropyltrimethoxysilane is commercially available from CT, Greenwich Chromton Corporation.

⁶⁴ EMERY 6717 Partially amidated polyethylene imine is commercially available at Cognis Corporation, Cincinnati, Ohio.

⁶⁵ MACOL OP-10 epoxidized alkylphenols; This material is similar to MACOL OP-10 SP except that OP-10 SP is post-treated to remove the catalyst; MACOL OP-10 SP is no longer available.

Ethylene oxide derivatives of ⁶⁶ TMAZ-81 sofital ester are commercially available from BASF Corporation of Parsippany, New Jersey.

⁶⁷ MAZU DF-136 Antifoam is available from BASF Corporation in Parsippany, New Jersey.

⁶⁸ ROPAQUE OP-96, 0.55 micron particle dispersion is commercially available from Rohm and Haas, Pennsylvania, Philadelphia.

⁶⁹ ORPAC BORON NITRIDE RELEASECOAT-CONC 25 Boron nitride dispersion is commercially available in ZYP coatings of Oak Ridge, Tennessee.

⁷⁰ POLARTHERM PT 160 Boron nitride powder is commercially available from Lakewood, Ohio's advanced ceramic corporation.

⁷¹ SAG 10 Antifoam is available from Connecticut, Chrometon Corporation, Greenwich.

⁷² RD-847A polyester resins are commercially available from Columbus, Ohio.

⁷³ DESMOPHEN 2000 polyethylene adipate diol is commercially available from Bayer Corporation, Pittsburgh, Pennsylvania.

⁷⁴ PLURONIC F-108 polyoxypropylene-polyoxyethylene interpolymers are commercially available from Bust Corp., New Jersey.

⁷⁵ ALKAMULS EL-719 Polyoxyethylated vegetable oils are commercially available from Ron-Poulene / Rhodia, Princeton.

⁷⁶ ICONOL NP-67 alkoxylated nonyl is commercially available from BASF Corporation of Parsippany, New Jersey.

⁷⁷ POLYOX WSR 301 poly (ethylene oxide) is commercially available from Union Carb Corporation of Danbury, Connecticut.

⁷⁸ DYNAKOLL Si 100 resin is commercially available from Eka Chemical AB, Sweden.

⁷⁹ SERMUL EN 668 Benelux, available from CON BEA.

⁸⁰ SYNPERONIC F-108 Polyoxypropylene-Polyoxyethylene Interpolymer; European counterpart to the PLURONIC F-108

⁸¹ EUREDUR 140 polyamide resin is commercially available from Belgium, Ciba Gaiji.

⁸² VERSAMID 140 polyamide resin is commercially available from Cognis Corporation, Cincinnati, Ohio.

⁸³ FLEXOL EPO Connecticut, available from Union Carbide in Danbury.

Additional examples of glass fiber yarns having a resin compatible with sizing compositions include US Pat. No. 09 / 620,526, "Compressed Glass Fiber Strands, filed November 3, 2000, which is specifically incorporated herein by reference. It is disclosed, but not limited thereto.

Referring again to FIG. 1, although not limited by the present invention, the stiffener material 20 comprises a weight percentage of 40 to 70 of the prepreg layer 14 (including the weight of the inorganic mixture 18). It includes. One embodiment of the stiffener material 20 includes, but is not limited to, a weight percentage of 48 to 66 of the prepreg layer 14 (including the weight of the inorganic mixture 18).

In one embodiment of the electronic support 10 according to the invention, the electronic support 10 comprises at least one prepreg layer 14, at least one matrix in contact with at least a portion of the at least one reinforcing material 20. Material 16 includes, but is not limited to, at least one inorganic mixture 18. The prepreg layer 14 comprises at least one woven fiber reinforcement material 20 formed from at least one fiber free of basalt glass. The matrix material 16 comprises at least one non-fluorinated polymer. The inorganic mixture 18 comprises at least one non-hydrolyzable layered inorganic solid lubricant having a high electrical resistance, the total of at least one inorganic mixture 18 over the matrix material 16 and the total solid base. At least 6 weight percent of the combined weight. Additionally, although not required, at least one inorganic mixture 18 has one or more of the following properties: Moh hardness of 6 or less, temperature resistance in excess of 30 W / mK, small coefficient of thermal expansion, and iron High similarity to metals. In one embodiment of the invention of the electronic support 10 discussed above, the at least one particulate inorganic mixture 18 is, but is not limited to, hexagonal boron nitride.

In another embodiment of the electronic support 10 according to the invention, the electronic support 10 is at least one in contact with at least one prepreg layer 14, at least a portion of at least one reinforcing material 20. The matrix material 16 includes, but is not limited to, at least one inorganic mixture 18. The prepreg layer 14 comprises at least one woven fiber reinforcement material 20. The matrix material 16 comprises at least one non-fluorinated polymer. The inorganic mixture 18 comprises at least one non-hydrolyzable layered inorganic solid lubricant having a high electrical resistance, the total of at least one inorganic mixture 18 over the matrix material 16 and the total solid base. At least 10 weight percent of the combined weight. Additionally, although not required, at least one inorganic mixture 18 has one or more of the following properties: Moh hardness of 6 or less, temperature resistance in excess of 30 W / mK, small coefficient of thermal expansion, and iron High similarity to metals.

In one non-limiting embodiment of the invention described above, the at least one particulate inorganic filler 18 in the electronic support 10 according to the invention is a hexahedral boron nitride.

In an electronic support 10 according to another non-limiting embodiment of the invention, the electronic support 10 includes at least one prepreg layer 14 and at least one matrix material 16. The at least one prepreg layer 14 comprises at least one textile fiber reinforcement 20 formed from at least one fiber free of basalt glass. The at least one matrix material 16 is in contact with at least a portion of the at least one textile fiber reinforcement 20. The at least one matrix material 16 comprises at least one non-fluorite polymer and the at least one particulate inorganic filler 18. The at least one particulate inorganic filler 18 comprises at least one inorganic filler having high thermal conductivity and high electrical resistance. The at least one particulate inorganic filler 18 has at least 6% by weight of the total combined weight of the matrix material 16 and the at least one particulate inorganic filler 18 based on total solids. Additionally, although not required, the at least one inorganic filler has the following characteristics: Mohs hardness of 6 or less, thermal conductivity greater than 30 W / mK, low coefficient of thermal expansion, good lubrication characteristics (e.g., Solid lubricant), and a thin film structure. In the electronic support 10 according to the non-limiting embodiment of the present invention described above, the at least one particulate inorganic filler is hexahedron boron nitride.

In an electronic support 10 according to another non-limiting embodiment of the invention, the electronic support 10 includes at least one prepreg layer 14 and at least one matrix material 16. The at least one prepreg layer 14 comprises at least one textile fiber reinforcement 20 formed from at least one fiber free of basalt glass. The at least one matrix material 16 is in contact with at least a portion of the at least one textile fiber reinforcement 20. The at least one matrix material 16 comprises at least one non-fluorite polymer and the at least one particulate inorganic filler 18. The at least one particulate inorganic filler 18 comprises at least one inorganic filler having high thermal conductivity and high electrical resistance. The at least one particulate inorganic filler 18 has at least 10% by weight of the total combined weight of the matrix material 16 and the at least one particulate inorganic filler 18 based on total solids. Additionally, although not required, the at least one inorganic filler has one or more of the following characteristics: Mohs hardness of 6 or less, thermal conductivity greater than 30 W / mK, low coefficient of thermal expansion, good lubrication characteristics (e.g. Solid lubricant), and a thin film structure. In the electronic support 10 according to one non-limiting embodiment of the present invention described above, the at least one particulate inorganic filler is hexahedral boron nitride.

In an electronic support 10 according to another non-limiting embodiment of the invention, the electronic support 10 includes at least one prepreg layer 14 and at least one matrix material 16. The at least one prepreg layer 14 comprises at least one textile fiber reinforcement 20. The at least one matrix material 16 is in contact with at least a portion of the at least one textile fiber reinforcement 20. The at least one matrix material 16 comprises the at least one particulate inorganic filler 18. The at least one particulate inorganic filler 18 has an amount sufficient to inhibit conductive anode filament formation and to reduce electrical shorts in the electronic support. According to a non-limiting particular embodiment of the present invention, the at least one fiber reinforcement is a woven glass reinforcement. According to a non-limiting embodiment of the present invention, the filler has a high affinity for metal iron. Although not required, the filler having a high affinity for metal iron has a CEC of at least 20 meq / 100g, in another embodiment at least 80 meq / 100g. According to another non-limiting embodiment of the present invention, the filler having a high affinity for metal iron has at least 600 ml / g K _d (Cu ²⁺ ), and in other non-limiting embodiments at least 1500 ml / g K _d (Cu ²⁺ ), in another embodiment at least 15,000 ml / g K _d (Cu ²⁺ ) or at least 40,000 ml / g K _d (Cu ²⁺ ). The at least one inorganic filler has one or more of the following features: Mohs hardness of 6 or less, low coefficient of thermal expansion, good lubrication characteristics, high thermal conductivity, and high electrical conductivity. Non-limiting examples of fillers with high affinity for metal iron include, but are not limited to, montmorillonite, vermiculite, saponite, bentonite, hectorite, illite, nontrolite, chloride, attapulgite, porous silicates, synthetic fluorine Romickers and mixtures thereof. One non-limiting example of an expandable synthetic fluoromicon is sodium fluoropropcoite. One non-limiting example of a porous silicate is a porous silicate having an organic function.

In an electronic support 10 according to another non-limiting embodiment of the invention, the electronic support 10 includes at least one prepreg layer 14 and at least one matrix material 16. The at least one prepreg layer 14 comprises at least one textile fiber reinforcement 20. The at least one matrix material 16 is in contact with at least a portion of the at least one textile fiber reinforcement 20. The at least one matrix material 16 comprises at least one non-fluorite polymer and the at least one particulate inorganic filler 18. The at least one filler 18 has a high affinity for metal iron. The at least one particulate inorganic filler 18 has at least 10% by weight of the total combined weight of the matrix material 16 and the at least one particulate inorganic filler 18 based on total solids. In an electronic support 10 according to another non-limiting embodiment of the invention, the at least one textile fiber reinforcement 20 is formed from at least one fiber free of basalt glass. The at least one filler 18 has a high affinity for metal iron. The at least one particulate inorganic filler 18 has at least 6% by weight of the total combined weight of the matrix material 16 and the at least one particulate inorganic filler 18 based on total solids.

In an electronic support 10 according to another non-limiting embodiment of the invention, the electronic support 10 includes at least one prepreg layer 14 and at least one matrix material 16. The at least one prepreg layer 14 comprises at least one textile fiber reinforcement 20. The at least one matrix material 16 is in contact with at least a portion of the at least one textile fiber reinforcement 20 and at least one inorganic filler 18. The at least one filler 18 has a high affinity for metal iron. The at least one particulate inorganic filler 18 has a weight percent of 5 or less of the total combined weight of the matrix material 16 and the at least one particulate inorganic filler 18 based on total solids. In an electronic support 10 according to another non-limiting embodiment of the invention, the at least one particulate inorganic filler 18 has a high affinity for metal iron. The at least one particulate inorganic filler 18 has a weight percent of 10 or less of the total combined weight of the matrix material 16 and the at least one particulate inorganic filler 18 based on total solids. In an electronic support 10 according to another non-limiting embodiment of the invention, the at least one particulate inorganic filler 18 has a high affinity for metal iron. The at least one particulate inorganic filler 18 has a weight percent of 15 or less of the total combined weight of the matrix material 16 and the at least one particulate inorganic filler 18 based on total solids.

In an electronic support 10 according to another non-limiting embodiment of the invention, the electronic support 10 includes at least one prepreg layer 14 and at least one matrix material 16. The at least one prepreg layer 14 comprises at least one textile fiber reinforcement 20. The at least one matrix material 16 is in contact with at least a portion of the at least one textile fiber reinforcement 20 and at least one inorganic filler 18. The matrix material 16 includes at least one inorganic filler 18. The at least one inorganic filler is a chelating reagent selected from materials having organic functional group containing nitrogen, inorganic functional group containing sulfur, organic functional group containing phosphorus, and mixtures thereof. In an electronic support 10 according to another embodiment of the invention, the chelating reagent is no greater than 15 of the total combined weight of the matrix material 16 and the at least one particulate inorganic filler 18 based on the total solids. Weight percent.

It should also be appreciated that the at least one particulate inorganic filler 18 includes a number of different materials such that the filler material provides a combination of properties.

Although not required, if desired, any of the above embodiments of the electronic support 10 according to the present invention are in electrical contact with at least a portion of at least one surface of at least one of the one or more prepreg layers 14. It may further comprise a conductive material (not shown). Although not limited, the at least one surface may be an outer major surface. The term "outer major surface" as used in the examples of the present invention means the exposed major surface. Moreover, the electrically conductive material may comprise at least one circuit. The term "circuit (s)" as used in embodiments of the present invention means a feature formed in or by an electrically conductive material, for example, but not limited to providing the necessary electrical and / or thermal interconnection. To lines, pads, lands, and other features formed vertically on the printed circuit board. The electronic support 10 also includes at least one opening that extends at least partially through the electronic support as described below. Referring to FIG. 1, a non-limiting method of forming the electronic support 10 according to an embodiment of the present invention will be generally considered. The non-limiting method includes combining at least one inorganic filler 18 with at least one matrix material 16. The bonding step can be carried out by any method of combining the fillers with polymeric materials known in the art. For example and without limitation to the present invention, when at least one matrix material 16 comprises a thermosetting polymer, a solvent solution of the thermosetting polymer is formed and the at least one inorganic filler 18 is Mixed in solution. However, if the at least one matrix material 16 comprises a thermoplastic polymer, the thermoplastic polymer may be dissolved for the first time and the at least one inorganic filler 18 may be mixed into the dissolved polymer. Alternatively, a powder mixture of the thermoplastic polymer and the at least one inorganic filler 18 is formed and heated to dissolve the thermoplastic polymer or the powder mixture is mixed and passed through an injection molding machine to form an adjacent mixture, and the result The resulting mixture is calendared into flat sheet steel.

It will be appreciated by those skilled in the art that the inorganic filler 18 is pretreated with a binder or other affinity to improve the wettability of the matrix material 16 on the inorganic filler 18. Will be recognized. Additionally, although not required in the present invention, a binder may be added to the matrix material prior to adding the inorganic filler material to improve wettability. Treatment of inorganic fillers used in polymeric materials is well known to those skilled in the art and additionally it is not considered necessary to disclose a method of treating particulates. However, to obtain more information, it is preferred to refer to pages 65-115 of the handbook of plastic fillers in 1987 by H. Katz and J. Milewski Eds.

According to a non-limiting embodiment of the invention, the at least one inorganic filler 18 is pretreated with at least one solvent having affinity with the polymer matrix material 16, formed into a paste and the polymer matrix Is dispersed into the material 16. The phrase “at least one solvent having affinity with the polymer matrix material 16” used in embodiments of the present invention indicates that the at least one solvent can at least partially solvate or swell the polymer matrix material. it means. Although not required in the present invention, according to one embodiment of the present invention, the polymer matrix material is an epoxy material and the inorganic filler 18 is acetone, dimethylformamide (DMF), methylene chloride, gilcol ether, methyl Pretreated with at least one solvent selected from ethyl ketone (MEK), and mixtures thereof.

After bonding or dispersing the at least one inorganic filler 18 to the polymer matrix material 16, the polymer matrix material 16 is applied to the reinforcement 20 by any method well known to form prepregs. Is applied. For example, and without being limited to the present invention, when the reinforcement 20 has the form of a woven glass fiber structure, the reinforcement 20 is formed of the polymer matrix material having the at least one inorganic filler 18 ( 16) and then squeezed between sets of metering rollers to leave the measured amount of matrix material 16. Alternatively, the polymer matrix material 16 comprises the at least one inorganic filler 18 and is sprayed into the reinforcement 20 by well known methods. Other methods of applying the polymer matrix material 16 with the inorganic filler 18 such as electrostatic coating and painting are also envisioned in the present invention.

After forming the prepreg 14, the polymer matrix material 16 is typically at least partially set, for example by passing the prepreg through a dryer. The phrase “at least partially solidified” as used in embodiments of the present invention means that the polymer matrix material is at least partially dried, cooled and / or cured. The prepreg material is then cut to the required dimensions and, if desired, bonded to one or more additional prepreg layers. In general and not limited to the present invention, in conventional lamination operations, the prepreg material is cut (or punched) to the required dimensions, and two or more cut prepreg layers are stacked together and laminated, eg For example, between the plated steel plates at increased temperature and pressure for a predetermined length of time to cure the polymer matrix and form an electronic support in the form of a stack 310 of a desired thickness (as shown in FIG. 3). It is hardened by squeezing the stack. The method of forming the laminate according to the invention is described in detail below.

According to one non-limiting example of the method according to the invention, filler 18 comprises particulate boron nitride which is pretreated with acetone to form a paste. The paste is then dispersed in an epoxy resin comprising 45 to 65 weight percent solids prior to adding the boron nitride to form 13 to 17 weight percent epoxy resin based on the total solids. The epoxy resin comprising the dispersed particulate boron nitride is applied to a woven glass fiber reinforcement to form a prepreg layer. Thereafter, the epoxy resin of the prepreg layer solidifies at least partially. The boron nitride is more easily dispersed in the epoxy resin by boron nitride pretreated using this method.

2, another non-limiting example of an electronic support 210 in accordance with the present invention is shown in FIG. The electronic support 210 includes at least one prepreg layer 214. The at least one prepreg layer 214 includes at least one stiffener 220 and at least one matrix material 216. The at least one matrix material 216 is in contact with at least a portion of the at least one stiffener 220. At least one layer 217 having at least one inorganic filler 218 is in contact with at least one surface of the prepreg layer 214, for example a major surface 226 of the prepreg layer 214. Doing. Although not required, in a preferred case, as described below, the at least one layer 217 is located at one or more selected portions of at least one surface 226 of the prepreg layer 214 Provide at least a partial layer, or the at least one layer 217 is substantially located on all of at least one surface 226 of the prepreg layer 214 to form an essentially continuous layer or plane of the filler material 218. Form.

The at least one stiffener 220 may include any of the stiffeners 20 used in the electronic support according to the present invention. According to one non-limiting embodiment of the present invention, the reinforcement 220 is a glass fiber reinforcement. According to another non-limiting embodiment of the present invention, the reinforcement 220 is a woven glass fiber reinforcement. According to another non-limiting embodiment of the present invention, the reinforcement 220 is an undegreased resin-compatible fabric glass fiber reinforcement.

Moreover, the matrix material 216 can be any of the matrix materials 16 described above. The matrix material 216 may comprise any of the inorganic filler materials 18 described above. For example, but not by way of limitation, the at least one reinforcement 220 is an undegreased resin-compatible fabric glass fiber and the matrix material 216 is a total of the epoxy material and the boron nitride in total solids. It may be an epoxy material having up to 40% by weight of hexahedral boron nitride based on the weight of the bond.

The layer 217 may include one or more inorganic fillers described above. According to one non-limiting embodiment of the present invention, the at least one inorganic filler 218 is an inorganic solid lubricant (described above), a high thermal conductive material, a low thermally expandable material, a material having a high affinity for metal iron, high Electrical resistive materials, and combinations and mixtures thereof.

According to one non-limiting embodiment of the present invention, the at least one inorganic filler 218 is at least one inorganic solid lubricant. The inorganic solid lubricant is selected from hexahedral boron nitride, metal dichalcogenide, boric acid, antimony oxide, talc, and mixtures thereof. According to another non-limiting embodiment of the present invention, the inorganic solid lubricant is a non-hydrated inorganic solid lubricant having a thin film structure (described above). According to another non-limiting embodiment of the present invention, the non-hydrating inorganic solid lubricant having a thin film structure is hexahedral boron nitride.

According to another non-limiting embodiment of the present invention, the at least one inorganic filler 218 is a high thermal conductivity material. The high thermal conductivity material is selected from hexahedral boron nitride, aluminum nitride, graphite, and mixtures thereof. According to another non-limiting embodiment of the invention, the high thermal conductivity material has a thermal conductivity of at least 30 W / mK. According to another non-limiting embodiment of the invention, the high thermal conductivity material having a thermal conductivity of at least 30 W / mK is hexahedral boron nitride.

According to one non-limiting embodiment of the present invention, the at least one inorganic filler 218 is a low thermally conductive material. The low thermally conductive material is selected from hexahedral boron nitride, lithiarite, aluminum titanate, and mixtures thereof. According to another non-limiting embodiment of the present invention, the low thermal conductivity material has a coefficient of thermal expansion of 100 x 10 ^-7 / ° C. or less in the temperature range of 0 ° C. to 200 ° C. According to another non-limiting embodiment of the present invention, the low thermal conductivity material has a coefficient of thermal expansion of 50 × 10 ⁻⁷ / ° C. or less in the temperature range of 0 ° C. to 200 ° C. According to another non-limiting embodiment of the present invention, the low thermal conductivity material is hexahedral boron nitride.

According to one non-limiting embodiment of the present invention, the at least one inorganic filler 218 is a material having a high affinity for metal iron. The material has a CEC of at least 20 meq / 100g, and in another embodiment at least 80 meq / 100g. According to another non-limiting embodiment of the present invention, the filler having a high affinity for metal iron has at least 600 ml / g K _d (Cu ²⁺ ), and in other non-limiting embodiments at least 1500 ml / g K _d (Cu ²⁺ ), in another embodiment at least 15,000 ml / g K _d (Cu ²⁺ ) or at least 40,000 ml / g K _d (Cu ²⁺ ). Non-limiting examples of fillers with high affinity for metal iron include, but are not limited to, montmorillonite, vermiculite, saponite, bentonite, hectorite, illite, nontrolite, chlorite, attapulgite, porous silica, Synthetic fluoromicas, and mixtures thereof. According to one non-limiting embodiment of the present invention, the expandable synthetic fluoromica is sodium fluorophlogopite. According to one non-limiting embodiment of the present invention, the porous silica is an organic functionalized porous silica.

According to another non-limiting embodiment of the present invention, the at least one inorganic filler 218 is nitrogen having an organic functional group, sulfur having an organic functional group, oxygen having an organic functional group, phosphorus having an organic functional group or a combination thereof. Selected chelating reagent from.

According to one non-limiting embodiment of the present invention, the at least one inorganic filler 218 is a high electrical resistive material. The high electrical resistance material is selected from boron nitride, talc, mica, and mixtures thereof. According to one non-limiting embodiment of the present invention, the high electrical resistance material has an electrical resistance of at least 1000 μ-cm. Although not limited to the present invention, in an embodiment of the present invention, the high electrical resistance material having an electrical resistance of at least 1000 μ-cm is hexahedral boron nitride.

According to another non-limiting embodiment of the present invention, the at least one inorganic filler 218 has a Mohs hardness below the Mohs hardness of the at least one reinforcing material 220. According to another non-limiting embodiment of the present invention, the at least one inorganic filler 218 has a Mohs hardness of 6 or less. Although not limited to the present invention, in the embodiment of the present invention, the inorganic filler 218 having a Mohs hardness of 6 or less is hexahedral boron nitride.

Although not limited to the present invention, at least one inorganic filler 218 of the at least one layer 217 is in the total combined weight of the matrix material 216 and the at least one layer 217 in total solids. It may have 5 to 35% by weight. According to one embodiment of the invention, the at least one inorganic filler 218 may have from 10 to 30% by weight of the total combined weight of the matrix material 216 and the at least one layer 217 in total solids. have. According to another embodiment of the present invention, the at least one inorganic filler 218 may have 12 to 28% by weight of the total combined weight of the matrix material 216 and the at least one layer 217 in total solids. have.

The layer 217 may further include materials other than the inorganic filler material. For example, although not limited to the present invention, the layer 217 may include an organic lubricant such as polytetrafluoroethylene and sterite (such as sterite zinc); Particulate organic fillers such as rubber particles; And adhesives (to be described below). Although not limited to the present invention, according to one embodiment of the present invention, the at least one layer 217 is 10% by weight of the adhesive based on the total weight of the one layer 217 on a total solid basis It may have the weight below. According to another non-limiting embodiment of the present invention, the at least one layer 217 may have a weight of less than or equal to 5% by weight of the adhesive based on the total weight of the one layer 217 on a total solid basis. have. As used herein, the term “adhesive” means a polymeric material added to layer 217 to support adhesion between layer 217 and other materials such as other prepreg layers or electrically conductive layers. do. The adhesive may have the same or different chemical composition as the matrix material 216.

Mixing of adhesive material into layer 217 results in an increase in the overall resin (polymer) water of prepreg layer (214), which is inherently free of such adhesive material as compared to the preg layer comprising layer (217). What you can do will be known to those skilled in the art. Such an increase in overall resin may interfere with the properties of the electronic support mixed in the prepreg layer. As a result, although not limited internally, if the adhesive material is mixed into the layer 217, the amount of adhesive material and polymeric matrix material may range from 25 to 45 weight percent of the prepreg layer 214 (reinforcement based on the total bond weight). An overall resin of material 220, layer 217 based on the total bond weight of polymer matrix material 216 and based on the solid base may be tailored. In one non-limiting embodiment of the invention, the amount of adhesive material and polymeric matrix material may be tailored to the overall resin of the prepreg layer 214 in the range of 28 to 42 weight percent.

In another non-limiting embodiment of the invention, layer 217 is inherently free of adhesive material. As used herein, the phrase “inherently free of adhesive” includes that layer 217 does not exceed 0.1 weight percent of the adhesive based on the total solid base. Preferably, it includes no adhesive material.

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

Although not required, an electrical conductor (not shown in FIG. 2) may be located on at least one outer surface of the electronic support 210. As described in more detail below, at least one circuit may be formed in an electrical conductor.

In one embodiment, but not limited to, at least one layer 217 is located on at least a portion of the first surface 226 of the prepreg layer 214 and the electrical conductor is opposite the prepreg layer 214. At least a portion of the second surface to be formed.

Although not required, the electronic support 210 can further include at least one hole extending at least partially through the electronic support 210, as described below.

The non-limiting method of forming the electronic supports 210 will now be widely discussed. Referring again to FIG. 2, the prepreg layer 214 comprising at least one matrix material 216 and at least one reinforcing material 220 is formed in a conventional manner, and the at least one matrix material 216 is At least partially set. At least a portion of the at least partially set matrix material 216 is then at least partially solvated, and the at least one inorganic filler 218 is at least partially solvated to form at least one layer 217. Attached to at least a portion of 226.

Although not required, additional layers of matrix material and / or inorganic fillers 218 (not shown) may be applied over, added to layer 217, and at least partially set, as described above. have. The prepreg layer can be treated into a laminate as follows.

In one non-limiting embodiment of the invention, the prepreg layer is at least partially set, at least one layer 217 comprising at least one inorganic filler 218 is at least one inorganic filler 218. And by spraying an aerosol comprising a propellant, it is attached to at least a portion of at least one surface of the prepreg layer 214. Although not essential, at least one matrix material is suitable for the solvent. A non-limiting example of an aerosol foam of inorganic filler suitable for use in the present invention is a boron nitrate aerosol lubricant comprising boron nitric acid, acetone and propellant, the products of ZIP Co., Ltd., located in Tennessee, Oklahoma.

Alternatively, although not limited by the present invention, at least one layer 217 comprising at least one inorganic filler 218 is contained in a solvent bath containing at least one solvent and at least one inorganic filler 218. By briefly coating the prepreg layer 214, it may be applied to at least a portion of at least one surface of the prepreg layer 214. For example, but not limited to, the prepreg layer 214 is at least partially immersed in a solvent bath where at least one polymeric matrix material 216 and at least one inorganic filler 218 comprise at least one suitable solvent. Dry to form a prepreg layer 214 that is removed from the solvent furnace and includes at least one partial layer 217. Sublayer 217 is located on at least a portion of at least one surface 226 of prepreg layer 214.

Although not limited thereto, preferred solvents used in the above methods for forming the layer include the following. The solvent is suitably at least one polymeric matrix material 216 used to form the prepreg layer 214. While not meant to be based on a particular theory, one would like to use such solvents. When the prepreg is in contact with the solvent, the surface of the prepreg will become tacky due to the partial solvation of the at least one matrix material. As a result, the adhesion of the at least one inorganic filler to the surface of the prepreg will be improved. In addition, it is expected that the surface of the prepreg layer will be sticky. For that reason, in the course of progress, by reducing the deviation between the prepreg layers, lamination of the prepreg layer will be promoted. It will be appreciated by those skilled in the art that the choice of solvent depends on several factors, such as the amount of solvent required and the polymeric matrix material 216 to form the preg. Non-limiting examples of solvents used with pregs comprising polymeric matrix materials comprising epoxy include glycol ethers such as acetone, dimethylformamide (DMF), methyl chloride, methoxy isopropanol and other mixtures thereof, Glycol ethers such as methyl ethyl ketone (M) and mixtures thereof. Although not required, the solvent bath further includes other programming acids, such as, for example, polymeric matrix materials (such as epoxy), adhesives, particulate inorganic fillers, and dispersion media 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 adjusted to tailor to produce the required level of solvation for a given polymeric matrix material 216.

Although not required, the surface portion of prepreg layer 214 may be masked by conventionally known methods of coating to protect the adhesion of at least one inorganic filler 218 within the masking area. For example, the present invention is not so limited, but the masting tape is pre-formed prior to application of the inorganic filler 218 to protect the adhesive layer of the inorganic filler 218 of layer 217 on a selected portion of the preflag surface. It may be attached to selected portions of the surface of the flag layer 214. In addition, some or all of the surface of prepreg layer 214 may be applied at least partially or entirely to at least one inorganic filler 218 to form a continuous plane or layer 217.

In another non-limiting method of forming the electronic support 210 according to the present invention, at least one polymeric matrix material 216 can be used for at least one reinforcing material 220. Subsequently, when the polymer is still tacky, layer 217 comprising at least one inorganic filler 218 may at least partially contain at least one polymeric matrix material 216, for example, as described above. Prior to setting, it may be used in at least one portion 224 of prepreg layer 214. Inorganic filler 218 may be sprayed or blown on, for example, filler 218 over portion 224 of surface 226, or a portion of surface 226 when polymeric matrix material 216 is at least partially tacky. It can be used by depositing into the filler 218 on the field 224. If desired, additional layers of polymeric matrix material and / or inorganic filler 218 (not shown) may be superimposed on layer 217 and at least partially set. As described below, the preflag can be further mixed into the laminate.

Referring to FIG. 3, an electronic support 310 is shown that includes a laminate 312 and at least one layer 317. Laminate 312 includes a first preflag layer 314 and a second preflag layer 315 adjacent the surface 326 of the first preflag layer 314. At least one layer 317 includes at least one inorganic filler 318 between the first preflag layer 314 and the second preflag layer 315. As described above, even in one non-limiting embodiment of the present invention, the at least one layer 317, based on the total weight of the at least one partial layer on the entire solid base, comprises an adhesive material in the range of 25 weight percent. . In one non-limiting embodiment, at least one layer 317 is essentially free of adhesive material.

Although not limited by the present invention, as shown in FIG. 3, the first preflag layer 314 of the laminate comprises at least one reinforcing material 320, at least one polymeric matrix in contact with the at least one reinforcing material 320. Material 316 and at least one layer 317 comprising at least one inorganic filler 318 positioned at at least one portion 324 of surface 326 of prepreg layer 314. The second preflag layer 315 includes at least one reinforcing material 321 and at least one polymeric matrix material 336 in contact with 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, 321 are the same, and the polymeric matrix materials 316, 336 are the same.

Although not required, the preflag layer 316 also includes a layer similar to the layer 317 of the preflag layer 314 (not shown in FIG. 3) applied to at least a portion of the at least one preflag layer 315. . Laminate 312 further includes one or more additional preflag layers (not shown). If necessary further includes one or more layers similar to layer 317.

In one non-limiting embodiment of an electronic support in forming a laminate according to the invention, the laminate is with at least one layer comprising at least one inorganic filler located between at least a portion of at least one pair adjacent to the preflag layer. It includes a plurality of stacked preflag layers. In another non-limiting embodiment, the laminate includes a plurality of preflag layers stacked together with at least one layer comprising at least one inorganic filler located between at least a portion of each pair of adjacent preflag layers.

Referring to FIG. 3, in one non-limiting embodiment of the invention, the laminate includes a number of preflags. As described above, at least one prepreg layer 314 includes at least one layer 317, at least one prepreg layer 316, and at least one polymeric matrix material 336. Layer 317 includes at least one inorganic filler 318 in contact with at least a portion 324 of at least one surface 326 of the preflag. Prepreg layer 315 includes at least one reinforcing material 321. 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 of the invention, the laminate comprises at least one preflag layer. The preflag layer comprises at least one layer and at least one polymeric matrix material. At least one layer comprises at least one inorganic material in contact with at least a portion of the surface of the preflag and at least one of the at least one reinforcement material. At least one polymeric matrix material comprises at least one inorganic filler in contact with at least a portion of the reinforcing material.

Referring again to FIGS. 2 and 3, the aforementioned methods of forming the electronic supports 210, 310 in forming the preflag 214 and the laminate 312 are directed to the deposition of the reinforcing materials 220, 320. At least one including at least one inorganic filler 218, 318 to be previously incorporated into the electronic support 210, 310 without the high volume ratio of the inorganic filler directly into the polymeric matrix materials 216, 316. It is believed that there is an advantage in the way considering layers 217 and 317. In addition, due to the specified distribution of inorganic fillers 218, 318 in the electronic supports 210, 310, the layers 217 on the surfaces 226, 326 of the preflag layers 214, 314. The position and distribution of 317 can be adjusted more carefully by these methods.

In addition, as shown in FIG. 3, if necessary, at least one layer 317, including laminate 312, may essentially form a continuous inner layer or plane within laminate 312. Thus, by selecting inorganic filler materials to have specificity, for example, but not limited to, high thermal conductivity, good lubricity, low thermal expansion, low electrical conductivity, and / or high affinity, functionality and electronic supports for metal irons. The performance of 310 may be improved. This is advantageous when the electronic support 310 is used to form a PCB. Although not limited to this, if at least one inorganic filler is selected to have high thermal conductivity, the continuous inner layer is made by a layer 317 comprising an inorganic filler 318 that can operate as a heat spreader in the PCB. Is formed. Accordingly, it is possible to improve the performance of the active device mounted on the PCB. In addition, such inner layers can improve productivity during assembly by reducing or releasing warpage and other thermal expansion of the PCB during assembly by dissipating or enlarging heat from soldering.

In another non-limiting embodiment, the continuous layer 317 of the electronic support 310 can include at least one inorganic filler 318. At least one inorganic filler 318 has low thermal expansion. This can reduce the occurrence of cracking of the coating on the hole walls, called barrel cracking, in the PCB, as described above.

In another non-limiting embodiment, the continuous layer 317 can include at least one inorganic filler 318. The inorganic filler 318 has a high affinity for metal iron. As previously described, it is possible to prevent electrical shorts due to the conductive anode filament shape in the PCB.

In another non-limiting embodiment of an electronic support particularly preferred for use in drilling machine operation, layer 317 may comprise a lubricant. More specifically, the electronic support 310 can include a laminate of prelaminated layers 314 and 315 laminated together, and a laminate 312 provided with a layer 317 with lubricant. As initially described, layer 317 may be located between at least one pair of adjacent preflag layers of the stack of preflag layers, or between one of the outer major surfaces of the support. As used herein, the term "stack" means at least two items. For example, preflag layers, laminates, electronic supports and the like. They are arranged superimposed on one another to form a pile of these items. In one embodiment, but not limited to, layer 317 further includes a lubricant and no more than 25% by weight of the adhesive material based on the total weight of the layer on the entire solid base. 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.

It will now be described generally in another non-limiting embodiment of an electronic support which is particularly preferred for use in drilling machine operations. The method includes applying a lubrication material to at least a portion of at least one major surface of the first preflag layer to form a lubrication layer, and the first preflag layer and one or more additional preflag layers to form an internal lubrication layer. A lubrication layer positioned between the layers including laminating the first preflag layer with one or more additional preflag layers, and laminating the first preflag layer and one or more preflag layers together with forming an electronic support. do. Although not required, the at least one additional preflag layers can include a lubricant layer located over at least a portion of at least one surface thereof.

In another non-limiting embodiment of a method of forming an electronic support in forming a laminate according to the present invention, first, the inorganic filler can be attached to the corresponding site of the reinforcing material, and then the polymeric matrix material can be attached thereon. For example, but not limited to, the inorganic filler may be electrically disposed on the reinforcing material or the reinforcement may be briefly immersed in a slurry of inorganic filler, solvent, preferably water. After coating the reinforcing material, the polymeric matrix material can be coated by spraying or soaking the inorganic filler to attach the reinforcing material. The polymeric matrix material can then be partially set. Although not required, as described in detail above, additional layers of inorganic filler may be attached to the polymeric material after drying. As a result, the polymeric material can be at least partially set, or additional layers and / or inorganic fillers of the polymeric matrix material can be reinforced and erected as necessary. As described above, the preflag material can be cut and laminated to form an electronic support in the form of a laminate.

Next, in a non-limiting embodiment of the invention, the reinforcement is formed using a wet paper manufacturing process. At least one inorganic filler is used in the paper reinforcement during its formation. For example, but not limited to, the glass fiber paper reinforcement can be formed by dispersing chopped glass fibers into a white water solution with an inorganic fiber material. As used herein, the term "white water solution" means a solution such as, for example, an aqueous solution. It may include dispersants, thickners, softing and hardening chemicals, and dispersed and emulsified polymers. Such white water solutions are well known to those skilled in the art. If further information is required, see US Pat. No. 5,3898,379, which specifically includes the above.

Next, the dispersion or slurry can be deposited into the head box, which in turn can be cast (eg, deposited) by moving over the wire screen to form a glass fiber sheet. The sheet may then be at least partially dried by a suction and vacuum device to form a glass fiber paper reinforcement comprising the filler. Thus, the polymeric matrix material can be used with a paper reinforcement as described in detail above to form a preflag layer in accordance with the present invention. If desired, inorganic fillers may be used in the polymeric matrix to which paper reinforcement has been applied, as described above. And / or, a layer comprising one or more inorganic filler materials may be applied to the preflag layer. As described above, two or more preflag layers may be deposited and stacked. According to another non-limiting embodiment of the wet paper process used to form the filled, according to the glass fiber paper reinforcement according to the present invention, only the glass fiber and the one or more inorganic fillers can be used as one or more forming agents. ) Is dipped in water. A non-limiting example of a foaming material suitably used in the present invention is TRITON X100. This is ethoxylated octylphenol manufactured by Union Carbide of Denver, Connecticut. The dispersion is stirred to form a foam slurry. It is cast over a web and the foam is removed by vacuum and at least partially dried to form a field which is a glass fiber paper reinforcement. The polymeric matrix material can then be applied to the paper reinforcement, as described in detail above to form the preflag layer according to the present invention. If desired, the inorganic filler applied to the paper reinforcement as described above can be included in the polymeric matrix material. And / or one or more inorganic filler materials may be applied to the preflag layer. As described above, two or more preflag layers may be laminated and laminated.

The present invention can further plan electronic supports in forming printed circuit boards and clad laminates made from prepreg layers and laminates as detailed above. Referring back to FIG. 3, the electronic supports according to the present invention may include an electrically conductive layer 322. Electrically conductive layer 322 includes an electrically conductive material in contact with at least a portion 325 of at least one surface 327 of laminate 312 to form a clad laminate 313.

The conductive material layer 322 may be formed by a method well known to those skilled in the art. For example, but not limited to the present invention, a thin sheet or flake of conductive material that is not limited to a metal material on at least a portion 325 of the semi-cured or cured prepreg material 315 or one side 327 of the laminated plastic 312. May be stacked to form a conductive layer 322. As an alternative, a layer of conductive material on at least a portion 325 of one surface 327 of semi-cured or cured resin-permeable workpiece 315 or laminated plastic 312 using well known techniques including electroplating, walkie-talk plating or sputtering. May be deposited to form a conductive layer 322.

Suitable conductive materials for use as the conductive layer 322 include, but are not limited to, copper, silver, aluminum, gold, tin, alloys of tin and lead, platinum, and combinations and alloys thereof.

With continued reference to FIG. 3, a method for forming a plated laminated plastic 313 according to the present invention is schematically described. The method comprises the steps of laminating two or more layers of prepreg materials 314 and 315 and one or more layers of conductive material 323 and forming the plated laminated plastic 313 to form a layer of prepreg materials 314, 315) and stacking conductive layer 322. At least one of the resin penetration processing material layers 314 and 315 is manufactured by one of the resin penetration plastic manufacturing methods according to the present invention. In one embodiment, but not limited herein, at least one of the two or more layers of conductive material 323 is disposed to reside on at least one outer side surface 327 of the plated laminated plastic 313.

Those skilled in the art will appreciate that the resin penetration processing materials, laminated plastics and plated laminated plastics of the present invention are useful in making multilayer printed circuit boards well known in the art. As used herein, the term "multilayer printed circuit board" means a printed circuit board with at least one conductive material.

The inner layer may be in the necessary continuous plane or patterned to have one or more circuits as described below.

In the following, a non-limiting method of forming a printed circuit board according to the present invention will be described. The method of forming a printed circuit board according to the present invention comprises the steps of forming a clad laminate according to the present invention as mentioned above, and at least one conductive layer of the clad laminate by methods known in the art. Patterning one or more circuits on at least a portion. For example, but not by way of limitation, the photoresist may be developed after being applied to the conductive layer and photographed by methods known in the art. The exposed conductive layer can then be etched to form circuits on the surface of the electronic support. Such methods are well known in the art, and the above examples illustrate one suitable method of patterning a circuit and are not meant to be limited in this manner in the present invention. In addition to or in place of forming one or more circuits on at least one side of the laminate, one or more gaps or vias extending at least partially through the electronic support may be in accordance with the present invention. It may be perforated into the electronic support by methods known in the art to form a. At this time, the drilling of the gap or bias is not limited to the mechanical drilling or laser drilling.

In the following, a non-limiting method of forming a gap in an electronic support in a printed circuit board will be described according to the present invention.

Typically, the gaps are formed by drilling holes in the support as is well known in mechanical drilling to provide electrical interconnection between printed circuits on opposing surfaces of the electronic support. After forming the gap, a layer of conductive material is deposited on the walls of the gap. The gap is then filled with a conductive material to facilitate the required electrical interconnects and / or heat dissipation. As mentioned above, the drilling step is a critical step to determine not only the quality of the assembled printed circuit board but also the overall production and price. If the perforated holes are not located correctly or the walls of the holes are rough, the resin applied or defective panels are broken. In addition, if a puncture defect occurs after the patterning of the circuit, the scraping cost of the panel will increase considerably. If the gap forming device used to form gaps in a printed circuit board or electronic support wears out during the drilling process, the quality and location accuracy of the perforated holes and the overall quality of the printed circuit board are degraded. As a result, productivity is lowered, thereby increasing production costs.

The gap formation method according to the present invention has particular advantages in forming a gap in the electronic support during the production of a printed circuit board. That is, it can potentially contribute to extending the life of the drill, can reduce the wear of the drill tool, improve the quality of the hole inner wall, improve the accuracy of the hole drilling position, and reduce the drilling cost. Furthermore, the method and apparatus according to the invention can be integrated into existing drilling schemes without the need for significant equipment changes or the introduction of additional processing steps. In addition, other printed circuit board processes such as routing, edging, dicing and finishing can benefit from the methods described herein.

Hereinafter, a non-limiting method of forming a gap in the electronic support in accordance with the present invention is described.

Referring to FIG. 4, the method according to the present invention includes positioning the electronic support 410 in a registry using the gap forming device 412. Although not limiting, electronic support 410 is an electronic support formed in the manner described in detail above, and may include layers incorporating a matrix member and / or fillers as described herein. Nevertheless, the method according to the invention is suitable for use in conventional electronic supports which are readily commercialized by various manufacturers. As used herein, "aperture forming device" means any device capable of mechanically forming a gap in an electronic support. Although not limiting in the present invention, in the embodiment shown in FIG. 4, the crevice 412 uses a drill bit 413 to form a crevice 414. Examples of commercially available crevice forming devices 412 suitable for use in the present invention include, but are not limited to, Hitachi-H Mark 10D5 head (spindle) machines, Uniline 2000 single head machines, and Pluritec single spindle multistation drilling machines. Do not.

After positioning the electronic support 410 in the registry using the crevice 412, the crevice 412 contacts the at least a portion 417 of the electronic support 410 to penetrate the electronic support 410. A gap 414 is formed that extends at least partially the thickness 416 of the. In one non-limiting embodiment of the invention, between the drill bit 413 and the electronic support 410 of the gap forming device 412 as the drill bit proceeds into the electronic support 410 during at least a portion of the gap forming process. Fluid stream 420 including solid lubricant 422 and carrier 423 is distributed adjacent to crevice 412 such that solid lubricant 422 contacts at least a portion 424 of interface 426. . The method as mentioned above can be used to create gaps in conventional laminates as well as laminates incorporating a filler material as described herein.

In one non-limiting embodiment of the invention, preferably the solid lubricant 422 is an inorganic solid lubricant. Any of the above-mentioned inorganic solid lubricants and the like for use as the inorganic filling material 18 (see FIG. 1) may be used as the inorganic solid lubricant 422 according to the gap forming method according to the present invention. For example, although not limiting, suitable inorganic solid lubricant particles having a lamellar structure include boron nitride, boric acid, graphite, metal dichalcogenides, mica, talc, kaolinite kaolinite, cadmium iodide and mixtures thereof. Suitable metal dikelcogenides 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 invention, an inorganic solid lubricant is used for the fluid flow 420.

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

Carrier 423 of fluid flow 420 may be liquid or gas. If the carrier 423 is a liquid, the solid lubricant 422 can be present in a dispersed, suspended or emulsion state in the liquid. Non-limiting examples of liquid carriers suitable for use in the present invention include oils such as water, mineral oil or petroleum-based oils, alcohols, other organic solvents, and mixtures thereof. In this case, the organic solvent may be acenon, methyl ethyl ketone (MEK), methylene chloride, toluene. A non-limiting example of a dispersion suitable for use in the present invention is ORPAC BORON NITRIDE RELEASECOAT-CONC 25. It is a dispersion of 25% by weight of hexagonal boron nitride particles in water and is commercially available from ZYP Coatings, Inc., Oak Ridge, Tenn. (Technical Newsletter "ORPAC, published by ZYP Coatings, Inc.). BORON NITRIDE RELEASECOAT-CONC ". According to the suppliers, the hexagonal boron nitride particles in this product have an average particle size of 3 μm or less. This dispersion contains 1% magnesium-aluminum silicate. This serves as a dispersant to maintain the setting of boron nitride and helps to bind the hexagonal boron nitride particles to the substrate to which the dispersion is applied. Independent testing of ORPAC BORON NITRIDE RELEASECOAT-CONC 25 boron nitride using a Beckman Coulter LS 230 particle size analyzer showed that the average particle size of the dispersion was 6.2 μm and the particles range from submicrometer to 35 μm. It has been found that it has a particle distribution as follows.

%> 10 50 90 Size (μm) 10.2 5.5 2.4

According to this distribution, 10% of the ORPAC BORON NITRIDE RELEASECOAT-CONC 25 boron nitride particles were determined to have an average particle size of greater than 10.2 μm.

Other products sold by ZYP Coatings, Inc. of Oak Ridge, Tennessee, include BORON NITRIDE LUBRICOAT paint, BRAZE STOP and WELD RELEASE products. Non-limiting examples of gaseous carriers suitable for use in the present invention include compressed air, nitrogen, argon, and include propellants such as butane or propane (but not necessarily due to flammability).

Although not based on any particular theory, the fluid stream 420 containing the solid lubricant 422 is placed near the crevice 412 such that the solid lubricant 422 contacts a portion 424 of the interface 426. By dispersing, the wear of the drill bit 413 during drilling can be prevented to some extent, thereby extending the life of the drill. In addition, the heat generated during the drilling process will be reduced by reducing friction between the crevice 412 and the electronic support 410. Thereby, the resin smear in the perforated clearance 414 can be reduced. The reduction in heat generated can be improved by using a solid lubricant with high thermal conductivity, such as but not limited to hexagonal boron nitride, to induce heat away from interface 426. Thereby, resin smear can be reduced. Solid lubricants with high thermal conductivity suitable for use in fluid flow 420 are used as inorganic fillers 18, 218 (see FIGS. 1 and 2) as mentioned above. Fluid flow 420 is distributed by methods known in the art. For example, fluid flow 420 may be sprayed through a nozzle or atomizer (not shown). In a non-limiting embodiment of the invention, a fluid flow comprising a solid lubricant and a liquid carrier extends at least partially through the interior of the drill bit 413 of the crevice 412 (not shown). It is provided through. Fluid flow 420 is distributed at the interface between the drill bit and the electronic support by discharging the fluid flow through the hollow channel and out of at least one hole extending from the outer surface of the drill bit into the hollow lining. Another method of dispensing a fluid stream 420 comprising a solid lubricant 422 and a liquid carrier 423 involves painting and dipping the electronic support 410 to be applied with the solid lubricant 422 immediately before drilling. will be. The size and number of gaps 414 formed in the electronic support 410 may be changed as necessary. For example, a gap 414 having a diameter of 0.025 mm (0.001 inch) to 12.7 mm (0.50 inch) can be formed in the electronic support 410 in accordance with the method of the present invention.

The gap 414 formed in the electronic support 410 may extend partially through the thickness 416 of the electronic support (ie, blind vias or buried vias), or in FIG. 4. As shown, it may extend completely through the thickness 416 of the electronic support 410 (ie, through hole). Also, if desired, the electronic support 410 may include one or more discrete types of gaps 414 as mentioned above, as well as may include gaps of different diameters. In addition, the gaps 414 may be filled with a conductive material such as solder.

In a non-limiting embodiment of the gap forming method of the electronic support according to the present invention, the electronic support is located in the registry of the gap forming device, and the fluid flow containing the solid lubricant impinges on the gap forming device. The gap forming device then comes into contact with at least a portion of the electronic support, and a gap is formed that extends through at least a portion of the thickness of the electronic support. Fluid flow may be supplied to an intermittent basis during at least a portion of the gap forming process, or may continuously invade the gap forming device during the gap forming step.

5 to 7, in a non-limiting embodiment of the gap forming method of the electronic support according to the present invention, the electronic support 510 is a surface 518 of the electronic support 510 to the gap forming device 512 It is located in the registry of the gap forming device 512 to be close. The layer 520 containing the inorganic solid lubricant 522 is positioned along at least a portion of the top surface 518 of the electronic support 510 between the surface 518 of the electronic support 510 and the gap forming device 512. do. A gap 514 extending through at least a portion of the thickness 516 of the electronic support 510 is formed by the drill bit 513 of the gap forming device 512. In so doing, the drill bit 513 forms a gap 524 that extends completely through the thickness 526 of the layer 520. A second layer 530 containing an inorganic solid lubricant 532 can be positioned along the opposite side 528 of the electronic support 510 as shown in FIG. 5.

In one non-limiting embodiment of the invention, layer 520 is a single layer. As used herein, the term "single layer" described with reference to layer 520 means that layer 520 is not supported on the secondary support substrate. The layer 520 may be a single layer applied directly to the surface 518 of the electronic support 510 or may be a self supporting layer inserted between the surface 518 and the crevice 512 prior to drilling.

In another non-limiting embodiment of the invention, layer 520 is positioned 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, or may consist of multiple layers, as described above. For example, although not limited by the present invention, the layer 520 supports the layer 520 before the layer 520 is placed between the surface 518 of the electronic support 510 and the gap forming device 512. It may be adhered or laminated to a secondary support substrate (not shown) in order to allow it to do so.

In another non-limiting embodiment of the present invention, the inorganic solid lubricant is hexagonal boron nitride, and hexagonal nitriding by spraying or painting a dispersion of boron nitride onto the outer surface of a phenol-paper entry board. A layer of boron may be applied directly onto the outer surface of the phenol-paper entry board. Such entry board materials are well known in the art and are commercially available under the trade name "thick paper core phenolic back up EB-95" by Centerlin of Baltimore, Maryland. By spraying or painting the surface 518, e.g., top, of the surface of the electronic support 510 in an amount sufficient to penetrate boron nitride first to achieve the desired drilling properties prior to forming the gap 514. A layer of hexagonal boron nitride may be applied directly onto the electronic support 510.

Although not based on any particular theory, when the drill bit 513 of the gap forming device 512 cuts the lubrication layer 52, a portion of the inorganic solid lubricant 522 clings to the drill bit 513. Or lubricate into the gap during drilling or lubrication. Additionally, if the inorganic solid lubricant 522 has high thermal conductivity as mentioned above, the temperature of the drill 513 is lowered by the thermal conduction that occurs when the drill penetrates through the layer 520.

Layer 520 may contain one or more solid lubricants as mentioned above. In a 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, as desired. In another non-limiting embodiment of the invention, layer 520 contains at least one binder to bond the individual particles of solid lubricant 522 together. However, solid lubricant 522 bonded together without using a binder to form layer 520 can be used in accordance with the present invention. Non-limiting examples of binders useful in the present invention include polyvinyl alcohol, polyvinylpyrrolidone, polyurethane, polyvinylacetate, polyacrylate, polyester, fatty acid ester, polyester, polyglycidyl methacryl Polymers such as polyglycidal methacrylate; And waxes such as paraffin. In addition to binders and inorganic solid lubricants, layer 520 may contain organic lubricants such as, for example, zinc stearate, polytetrafluoroethylene, paraffin wax, fatty acids, fatty acid esters, and polyethylene glycols.

Layer 520 may have a thickness 526 necessary to provide the desired drilling characteristics. In a non-limiting embodiment of the present invention, layer 520 is made as thin as possible while providing the necessary drilling and handling properties.

Multiple electronic supports can be stacked and drilled in a single gap formation process using the method according to the invention. As best seen in FIG. 6, in one non-limiting embodiment of the invention, one first electronic support 610 and second electronic support 611 may be stacked one on top of the other. In this case, the lower surface 628 of the first electronic support 610 is adjacent to the upper surface 618 of the second electronic support 611. Before forming the gap 614 in the electronic support 610, 611 using the gap forming device 612, the layer 620 containing the inorganic solid lubricant 622 may have a top surface 619 of the first electronic support 610. Is located adjacent to the Those skilled in the art will appreciate that electronic supports 610 and 611 are shown in a single layer in FIG. 6, although not limited thereto, as are well known in the art and in various forms, such as multiple laminates and printed circuit boards. It can be understood that this can be.

The lubricant layer may be located between selected adjacent electronic supports during the gap formation process. As best seen in FIG. 7, the layer 740 containing the inorganic solid lubricant 742 may have a lower surface 728 of the first electronic support 710 and an upper surface of the second electronic support 711 prior to gap formation. And may be located between 718. Multiple lubricant layers may be used in the gap formation process. As noted above, FIG. 5 shows the electronic support 510 with two lubricant layers 520, 530 located along the opposing major surfaces 518, 528 of the electronic support 510. In another non-limiting embodiment of the present invention as well illustrated in FIG. 7, there are multiple electronic supports 710, 711 and the layer 740 containing the organic lubricant 742 is the first electronic support 710. ) And the second electronic support 711. And, any other layer 720 containing the inorganic solid lubricant 722 may be formed of the first electronic support 710 before the gap 714 is formed in the electronic supports 710 and 711 using the gap forming apparatus 712. It may be positioned adjacent to the top surface 719.

In one non-limiting embodiment according to the present invention, multiple electronic supports can be stacked together and a layer containing an inorganic solid lubricant can be positioned between adjacent electronic supports of the multiple electronic supports. In addition, a lubricant layer may be positioned adjacent to either or all of the exposed opposing major surfaces of the electronic supports stacked together.

In another non-limiting embodiment of the gap forming method of the electronic support according to the present invention, the at least one electronic support is located in the registry of the gap forming device such that an upper surface of the at least one electronic support is adjacent to the gap forming device. A layer containing hexagonal boron nitride is positioned between the top surface of the at least one electronic support and the gap forming device, and the gap is formed such that the gap at least partially penetrates the thickness of the at least one electronic support using the gap forming device.

One of ordinary skill in the art would, in the method of forming a crevice as mentioned above, that a layer containing an inorganic solid lubricant may be located along at least a portion of the perforated electronic support prior to placing the electronic support in the registry of the crevice. have.

In another non-limiting embodiment of the invention, a solid lubricant can be incorporated into the crevice forming device. As best seen in FIG. 8, the crevice forming device 812 includes a drill bit 813 having an outer surface 848 and a coating material 850 having a lamellar solid lubricant 852. At this time, the lamellar solid lubricant 852 is located on at least a portion 854 of the outer surface 848. In a non-limiting embodiment of the invention, the lubricant 853 is hexagonal boron nitride. Although not limited by the present invention, the coating material 850 is located on at least some of the outer cut faces of the drill bit 813.

Coating material 850 located on at least some 854 of outer faces 848 of drill bit 813 is applied using methods well known in the art. For example, the coating material 850, particularly the coating material containing hexagonal boron nitride, may be applied by spraying, painting, sputtering, chemical vapor deposition (CVD), plasma deposition or pulsed laser deposition. Alternatively, a coating containing solid lubricant 852 may be formed by chemical methods. For example, in applying a coating material containing hexagonal boron nitride, a reactant formed by reacting boric acid with melanin is exposed to a drill bit for 60 minutes at a temperature of 800 ° C. or higher to form a hexagonal boron nitride layer, and It can be applied to the exposed surface of the drill bit.

In another non-limiting embodiment of another method of forming the gap forming apparatus 812 according to the present invention, an inorganic solid lubricant 852, such as powdered hexagonal boron nitride, includes one or more powder metals. And / or drill bits 813 formed through carbides, sintering aids and known powder metallurgy methods. For further information, see September 2, 1991, Newmedia International Japan, Japanese New Materials High-Performance Ceramic, "Cemented Carbide with Self-Lubricant Boron Nitride."

Those skilled in the art will appreciate that the gap forming device 812 as mentioned above can be used in any method of forming gaps in the electronic support, or alternatively can also be used in conventional gap formation processes. In particular, when the gap forming device 812 is used to form a gap in the electronic support, the electronic support is a gap having a drill bit having an outer surface at least partially coated with a coating material containing hexagonal boron nitride. It is located in the registry of the forming apparatus (1). The gap forming device contacts (2) at least a portion of the first side of the electronic support. A gap extending at least partially through the electronic support is formed through the at least first side of the electronic support (3).

The present invention further pays attention to the fabrication of electronic supports and printed circuit boards using the gap forming method mentioned above in detail.

The following examples illustrate non-limiting embodiments of the invention.

Yes

A series of electrical grade prepregs and laminates embodying the features of the present invention were prepared through the following procedure.

Laminate A: An electric grade 7628-style E-glass fabric, heat-washed and silane-finished, was injected and manufactured by Nelco International Corporation using commercial prepregging equipment and techniques to form prepregs. B-step curing (ie, partially curing). The injection resin was a FR-4 epoxy resin with a Tg of 140 ° C. and designated 4000-2 epoxy resin by Nelco. Eight prepregs were laminated between the press plates of the laminating press. At this time, 1oz of copper thin film was placed on the top and bottom of the stack. The press plates of the laminating press were preheated to a temperature of 93 ° C. (200 degrees Fahrenheit) and the stack was pressurized for 4 minutes at a pressure of 0.1 MPa (16 psi). The temperature was increased at a rate of 4.4 ° C. (8 ° F.) to 6.6 ° C. (12 ° F.) until the press plates reached 177 ° C. (350 ° F.).

The laminating pressure is increased to 2.3 MPa (350 psi) and maintained for 60 minutes. The temperature of the laminate is lowered by circulating water around the press plates for 25 minutes. At this time, the laminating pressure is maintained as it is. Then, the pressure is released and the laminate is removed from the laminating press. Next, the laminate is cut out to form laminate A. The glass component contained in each laminate accounts for 60 to 65% by weight. Laminate A is 45.7 cm wide by 61.0 cm long (ie, 18 inches wide by 24 inches long).

Laminate B: A layer of boron nitride was prepared in the same manner using the same material as laminate A, except that each prepreg set was applied between each of the prepreg layers, i.e., the eight pregreg layers and the seven boron nitride layers. In particular, each boron nitride layer is applied manually by spraying the main surfaces of the seven prepregs with a boron nitride aerosol lubricant until a visible inspection is seen in a range. Boron nitride aerosol lubricants are commercially available from ZYP Coatings, Inc., Oak Ridge, Tennessee and include boron nitride, acetone and propellants. The total amount of boron nitride included in the seven layers is 50 to 70 g. Boron nitride does not apply to any side of the prepreg that terminates as the outer major side of the laminate. Because spray coating is applied manually, the amount of boron nitride varies from layer to layer, from laminate to laminate. However, it is believed that boron nitride in the range of 2.56 to 3.58 mg per square cm of prepreg will be included in each layer. The glass component contained in each laminate accounts for 70 to 75% by weight.

Laminate C: Brushes are applied to uniformly apply and disperse 120 g of Nelco 4000-2 FR-4 epoxy resin to the fabric in a 7628 style E-glass fabric 50.8 cm wide by 68.6 cm wide (ie, 20 inches wide by 27 inches wide). Coating manually. The coated fabric was B-staged in an air circulation oven for 3 to 5 minutes at a temperature of 154 ° C. (310 degrees Fahrenheit) to form prepreg. The fabric was heat-washed and silane-finished to make an electric grade 7628-style fabric, commercially available from Bedford Weaving, Lynchburg, VA. Laminates were then formed by stacking and pressing eight prepregs and two copper thin films together in the same manner as laminate A. The glass component contained in each laminate accounts for 70 to 75% by weight.

Laminate D: The FR-4 epoxy resin was prepared in the same manner using the same material as Laminate C, except that it contained boron nitride particles. In particular, 9 g of POLARTHERM 160 hexagonal boron nitride powder was mixed with 25 g of acetone (PA, commercially available from Fischer Scientific of Pittsburgh) to moisten the boron nitride and form a paste having 26% by weight of boron nitride. It became. The paste is dispersed in 120 g of Nelco 4000-02 epoxy resin to form an epoxy resin containing 11% by weight of boron nitride on the entire solid basis. The glass component contained in each laminate accounts for 70 to 75% by weight.

Test 1

Laminates A, B and D were measured for thermal conductivity and thermal resistance in air at a temperature of 300 K (70 degrees Fahrenheit) according to ASTM method C-177 (described herein by reference). For Laminate B, the laminate contains a total of 55 g of boron nitride. The thermal conductivity measured for each laminate is shown in Table 1 below.

Table 1

Laminate A B C Thickness (measured during the test) Inches 0.057 0.057 0.044 Cm 0.145 0.145 0.112 Temperature Fahrenheit 75.5 74.6 74.7 Celsius 24.2 23.7 23.7 Thermal conductivity Btu inches per square foot fahrenheit 1.50 2.24 2.18 Watts per meter K 0.216 0.323 0.314

Referring to Table 1 above, the thermal conductivity of laminates B and D (both containing boron nitride) is higher than that of laminate A. In particular, the thermal conductivity of laminate B (which characterizes the present invention) is 50% higher than that of laminate A. In addition, the thermal conductivity of laminate D (which characterizes the present invention) is 45% higher than that of laminate A.

Based on the data, in one non-limiting embodiment of the invention, a laminate-shaped electronic support (first prepreg layer; second prepreg layer positioned adjacent to a major surface of the first prepreg layer) At least one layer containing a hexagonal boron nitride powder positioned between the first prepreg layer and the second prepreg layer, wherein at least one layer is at least one portion located on the entire solid base; The thermal conductivity of the adhesive based on the total weight of the layer not exceeding 25% by weight) is at least 0.27 W / mK. In one non-limiting embodiment of the invention, the thermal conductivity of the electronic support is at least 0.29 W / mK. In another non-limiting embodiment of the invention, the thermal conductivity of the electronic support is at least 0.31 W / mK.

In another non-limiting embodiment of the present invention, there is provided an electronic support (laminate comprising two or more prepreg layers, wherein at least one of the two or more prepreg layers contains basalt glass). At least one woven glass fiber reinforcement formed from at least one fiber that does not have and at least one matrix material in contact with at least a portion of the at least one reinforcement material, wherein the at least one matrix material is at least one fluorinated At least one inorganic filler containing a non-polymeric polymer, an epoxy resin, and a hexagonal boron nitride powder, wherein the at least one inorganic filler is formed of at least one inorganic filler and at least one matrix material on the total solid support. Account for at least 6% by weight of the total weight) The conductivity is at least 0.27 W / mK. In another non-limiting embodiment of the invention, the thermal conductivity of the electronic support is at least 0.29 W / mK. In another non-limiting embodiment of the invention, the thermal conductivity of the electronic support is at least 0.31 W / mK.

Test 2

Laminates A, B, C and D were evaluated for wear of the drill tip. With reference to FIG. 9, the term "drill tip wear" as used herein means a reduction in the width 970 of the initial cutting edge 972 of the drill 974 as measured at the peripheral edge of the drill tip.

Drilling was performed on three high laminate piles with 0.0105 inch (0.2667 mm) thick aluminum entry and 0.082 inch (2.083 mm) thick paper core phenolic coated back-up. Drilling on three laminates at one time is a standardized process in the art. The drills are solid carbide micro drills sold by HAM of Schwendi-Horenhausen, Germany. The chip load applied during the drilling process is fixed at 0.00125. As used herein, "chip load" refers to the relative ratio of drill insertion rate expressed in inches to the measured spindle speed (rpm). The spindle speed is 1000,000 rpm and the insertion rate is 125 inches (317.5 cm) per minute. Shrinkage is 1000 inches (25.4 m) per minute. Drilling is carried out using a Pluritec single spindle, multi-workbench drilling machine available from Pluritec spa of Burolo, Italy.

Four piles of three laminates were drilled for each laminate type. 1000 holes were drilled in the first pile of each laminate type using a single drill, 2000 holes were drilled in the second pile of each laminate type using a single drill, 3000 holes using a single drill Were drilled into the third pile of each laminate type, and 4000 holes were drilled into the fourth pile of each laminate type using a single drill. The drill tip wear was measured after perforating each dummy.

In order to consider the change in laminate thickness and the total thickness drilled with each drill and to compare drill tip wear based on the total number of drilled holes, the drill wear factor for each drill was determined. As used herein, "drill wear factor" refers to the amount of drill tip wear per drilled distance, which is calculated by the following equation.

Drill tip wear

-------------------------------------------------- -------

3 × (Laminate Thickness) × (Number of Holes Perforated)

For example, if the drill tip wear is 6 m after drilling 3000 holes to penetrate a pile of 3 laminates each having a thickness of 1524 m (0.06 inch), the drill wear factor is 0.437 m / m, i. Drill tip wear of 0.437 meters per meter of board thickness. In addition, the drill wear factor of the perforated laminates is averaged to provide an average drill wear factor, _ave , based on 10,000 holes as mentioned above.

Table 2 below shows the average drill wear coefficients, _ave , for four sets of laminates.

TABLE 2

Drill Wear Factor (μm / m)

Laminate Thickness (mm) Number of perforated holes _ave 1000 2000 3000 4000 A 1.4224-1.4986 0.6534 1.0785 0.5392 0.5786 0.7124 B 1.6256-1.6764 0.5628 0.5668 0.5314 0.5038 0.5412 C 1.1684-1.1938 0.6376 0.6770 0.5786 0.4920 0.5963 D 1.1938-1.2954 0.5943 0.5274 0.5038 0.4605 0.5215

When comparing laminates A and B containing treated prepregs, the drill wear factor for boron nitride containing laminate B is less than boron nitride containing laminate A. Likewise, when comparing laminates C and D containing treated prepregs, the drill wear coefficient for boron nitride containing laminate D is less than that of boron nitride containing laminate C. These test results indicate that the addition of boron nitride to the laminate tends to reduce drill tip wear, whether boron nitride is included in the epoxy resin or added as a layer between the prepregs.

Although the above has been described with reference to a preferred embodiment of the present invention, those skilled in the art will be able to variously modify and change the present invention without departing from the spirit and scope of the invention as set forth in the claims below. It will be appreciated.

Claims (50)

A prepreg layer layer having at least one reinforcing member and at least one matrix member in contact with at least a portion of the at least one reinforcing member; And At least one layer in contact with at least a portion of at least one surface of the prepreg layer, the at least one layer having at least one inorganic filler and an adhesive member, the adhesive member being located on an entire solid basis And at least one layer of no more than 25% by weight, based on the total load of the electronic support. The electronic support of claim 1, wherein the at least one reinforcing member is a glass fiber reinforcing material. The electronic support of claim 2 wherein the glass fiber reinforcement is a woven glass fiber reinforcement. 4. The electronic support of claim 3 wherein the glass fiber reinforcement is a non-degreased woven glass fiber reinforcement. The electronic support of claim 1 wherein the at least one sublayer forms an essential continuous plane on the at least one side of the prepreg layer. The electronic support of claim 1, wherein the at least one inorganic filler is selected from an inorganic solid lubricant, a high thermal conductor, a high electrical resistor, a low thermal expansion material, and a material having a high affinity for metal ions. . 7. The electronic support of claim 6, wherein the at least one inorganic filler is at least one inorganic solid lubricant selected from boron nitride, molybdenum disulfide, boric acid, antimony oxide and mixtures of any of these. 8. The electronic support of claim 7, wherein the at least one inorganic filler is at least one inorganic solid lubricant having a lamellar structure. 9. The electronic support of claim 8, wherein the inorganic solid lubricant having a lamellar structure is hexagonal boron nitride. The electronic support according to claim 6, wherein the at least one inorganic filler is selected from boron nitride, graphite, lithiapyrite, aluminum nitride, aluminum titanate and mixtures of any of these. 7. The electronic support of claim 6, wherein the at least one inorganic filler is at least one high thermal conductor having a thermal conductivity of at least 30 W / mK. The electronic support according to claim 6, wherein the at least one inorganic filler is at least one low thermal expansion material having a coefficient of thermal expansion not exceeding 100x10 ^-7 / ° C in a temperature range of 0 ° C to 200 ° C. 7. The electronic support of claim 6, wherein the at least one inorganic filler is at least one material having a high affinity for metal ions and a cationic substitution capacity of at least 20 meq / 100 g. 7. The former of claim 6, wherein the at least one inorganic filler is at least one material having a high affinity for metal ions and having a distribution coefficient K _d (Cu ²⁺ ) of at least 600 mg / l. support. 7. The method of claim 6, wherein the at least one inorganic filler is montmorillonites, nontronites, saponites, illite (hydrated mica), vermiculite, chlorites, sepiolites. ), Attapulgite, bentonite, hectorite, synthetic fluoromicas and mixtures thereof. 7. The method of claim 6 wherein the at least one inorganic filler 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. agent). The electronic support of claim 1, wherein the at least one inorganic filler has a Mohs hardness of less than six. The method of claim 1, wherein the at least one inorganic filler is characterized in that from 5 to 35% by weight, based on the total load of the at least one layer and the at least one matrix member located on a total solid base. Electronic support. 19. The method of claim 18, wherein the at least one inorganic filler corresponds to 10 to 30 weight percent based on the total load of the at least one layer and the at least one matrix member located on a total solid base. Electronic support. The method of claim 1, wherein the at least one inorganic filler contains an adhesive member in an amount of no greater than 10% by weight based on the total load of the at least one partial layer located on the entire solid base. Electronic support. 21. The method of claim 20, wherein the at least one inorganic filler contains an adhesive member in an amount of no greater than 5 weight percent based on the total load of the at least one partial layer located on the total solid base. Electronic support. 22. The electronic support of claim 21 wherein said at least one inorganic filler does not contain an adhesive member. The method of claim 1, wherein the prepreg layer is a first prepreg layer, the electronic support comprises at least one additional prepreg layer, and the at least one additional prepreg layer is the at least one partial layer. And at least a portion of the first prepreg layer cut into thin pieces to be positioned between the first prepreg layer and the at least one additional prepreg layer. 24. The electronic support of claim 23, further comprising at least one conductive material located along at least a portion of at least one side of the electronic support. The electronic support of claim 24 wherein the at least one conductive material comprises at least one circuit. 2. The method of claim 1, wherein the at least one layer is located along at least a portion of the first side of the prepreg layer, and the at least one conductive material is located along at least a portion of the opposing second side of the prepreg layer. And electronic support. 27. The electronic support of claim 26, wherein the at least one conductive material comprises at least one circuit. The electronic support of claim 1, further comprising at least one gap extending through at least a portion of the electronic support. As a method of forming an electronic support, Forming a prepreg layer comprising at least one matrix member and at least one reinforcement member; At least partially setting the at least one matrix member; At least partially solvating a portion of the at least one matrix member at least partially set with at least one solvent; And Securing the at least one inorganic filler to at least a portion of the at least partially solvated matrix member. 30. The method of claim 29, wherein said at least one matrix member is an epoxy member. 30. The method of claim 29, wherein the at least one solvent is selected from acetone, dimethylformamide, methylene chloride, glycol ether, methyl ethyl ketone and mixtures of any of these. 32. The method of claim 31 wherein the step of securing comprises spraying the at least one inorganic filler over at least a portion of the at least partially solvated matrix member. 30. The method of claim 29, wherein the prepreg layer is laminated with the at least one additional prepreg layer such that the at least one inorganic filler is positioned between the prepreg layer and the at least one additional prepreg layer to form a laminate. laminating). 34. The method of claim 33, comprising placing at least one conductive material on at least a portion of at least one side of the laminate. 30. The method of claim 29 comprising positioning a conductive material on at least a portion of at least one side of the electronic support. As a method of forming an electronic support, Forming a prepreg layer comprising at least one matrix member and at least one reinforcement member; Securing at least one inorganic filler to at least a portion of the at least one matrix member while the at least one matrix member maintains tackiness; And And at least partially setting said at least one matrix member. 37. The method of claim 36, wherein the prepreg layer is laminated with the at least one additional prepreg layer such that the at least one inorganic filler is positioned between the prepreg layer and the at least one additional prepreg layer to form a laminate. laminating) the process of forming an electronic support. 38. The method of claim 37, comprising placing at least one conductive material on at least a portion of at least one side of the laminate. 37. The method of claim 36, further comprising placing a conductive material on at least a portion of at least one side of the electronic support. A stack of prepreg layers laminated together; And And at least one layer with at least one lubricant located between at least a portion of at least a pair of adjacent prepreg layers of the stack of prepreg layers. 41. The laminate of claim 40, wherein the at least one layer contains no more than 25 weight percent of an adhesive member based on the total load of the at least one layer located on a total solid basis. . 41. The laminate of claim 40, wherein said at least one adhesive member is selected from inorganic solid lubricants, organic lubricants, and mixtures thereof. 43. The laminate of claim 42, wherein said at least one lubricant is at least one inorganic solid lubricant selected from hexagonal boron nitride, boric acid, molybdenum disulfide, graphite, and mixtures thereof. 44. The laminate of claim 43, wherein said at least one inorganic solid lubricant is hexagonal boron nitride. 43. The laminate of claim 42, wherein said at least one lubricant is at least one organic lubricant selected from polytetrafluoroethylene, zinc stearate, and mixtures thereof. 41. The laminate of claim 40, further comprising a conductive material in contact with at least a portion of at least one side of the laminate. 41. The method of claim 40, wherein the at least one lubricant has at least one additional property selected from high thermal conductivity, high electrical resistivity, low thermal expansion, high affinity for metal ions, and Mohs hardness of less than 6. Laminate characterized by having. A method of forming an electronic support having at least one internal lubricant layer, Applying at least one lubricant to at least a portion of at least one side of the first prepreg layer to form at least one lubricant layer; Stacking the first prepreg layer together with the at least one additional prepreg layer such that the at least one lubricant layer is positioned between the first prepreg layer and the at least one additional prepreg layer to form an internal lubricant layer. stacking step; And Laminating the first prepreg layer and the at least one additional prepreg layer together to form an electronic support. 49. The method of claim 48, wherein the at least one additional prepreg layer comprises at least one lubricant layer containing at least one lubricant in contact with the surface thereof. 49. The method of claim 48, further comprising placing at least one conductive material on at least one surface of at least one of the prepreg layers prior to the laminating process.