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WO2000047655A1 - Compositions de resine thermodurcies pour hyperfrequences transparentes, feuilles electriques derivees de ces compositions et leur procede d'obtention - Google Patents

Compositions de resine thermodurcies pour hyperfrequences transparentes, feuilles electriques derivees de ces compositions et leur procede d'obtention Download PDF

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Publication number
WO2000047655A1
WO2000047655A1 PCT/US1999/002964 US9902964W WO0047655A1 WO 2000047655 A1 WO2000047655 A1 WO 2000047655A1 US 9902964 W US9902964 W US 9902964W WO 0047655 A1 WO0047655 A1 WO 0047655A1
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WIPO (PCT)
Prior art keywords
composition
laminate
group
styrene
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/US1999/002964
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English (en)
Inventor
Scott A. Lane
Donald C. Rollen
Timothy W. Austill
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Gil Technologies
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Gil Technologies
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Publication date
Application filed by Gil Technologies filed Critical Gil Technologies
Priority to JP2000598567A priority Critical patent/JP2002536518A/ja
Priority to EP99906926A priority patent/EP1173501A1/fr
Priority to AU26722/99A priority patent/AU2672299A/en
Priority to MXPA01008222A priority patent/MXPA01008222A/es
Priority to KR1020017010200A priority patent/KR20020013499A/ko
Priority to CA002362609A priority patent/CA2362609A1/fr
Priority to PCT/US1999/002964 priority patent/WO2000047655A1/fr
Publication of WO2000047655A1 publication Critical patent/WO2000047655A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/02—Noble metals
    • B32B2311/04—Gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/02—Noble metals
    • B32B2311/08—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/12—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/24—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2375/00—Polyureas; Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/24—Thermosetting resins

Definitions

  • the present invention relates to thermosetting resin compositions with excellent electrical properties; electrical laminates made therefrom; and methods of producing these.
  • Electrical laminates such as circuit boards are produced by laminating sheets of electrical conducting material onto a base substrate of insulation material. The performance of the finished circuit board is effected by the electrical characteristics of the base substrate material.
  • thermoset resin systems with acceptable electrical performance at high frequencies (> 350 MHZ) are restricted in their applications due to high cost.
  • the lower cost alternatives that are available do not perform satisfactorily at high frequencies due to unacceptable electrical properties, such as high dielectric constant (D k ), high dissipation factor (D f ), high variability of D k and D f with frequency, and consistency of D k and D t from lot to lot of production material.
  • Thermoplastic polymers such as polytetrafluoroethylene (PTFE) which have exceptional electrical performance at high frequencies are commercially available.
  • the primary drawbacks associated with these materials are very high raw material costs and special processing considerations that add substantial cost to the final product. Because of the physical properties, very high laminating temperatures and pressures are also required to fabricate an electrical laminate from PTFE. Furthermore, due to the inability to "wet" PTFE, costly and hazardous chemicals are required to modify its surface during fabrication of the circuit.
  • thermoset material would have much greater mechanical properties over a much broader temperature range. Additionally, since thermoset materials have better mechanical properties, this would allow the circuit board fabricator to use conventional cost effective processes.
  • thermosetting resin compositions and elect ⁇ cal laminates made therefrom, of low to moderate cost with acceptable electrical properties at frequencies up to at least 20 GHz.
  • Such compositions would have great utility as circuit board substrates and the laminates made from these thermosetting resins can be utilized in many applications such as in the rapidly growing wireless communication market, in high speed computers, in high definition televisions, and in various other electrical and related applications.
  • An object of the present invention is to provide a thermosetting resin composition which can be made flame retardant and which can be utilized in existing cost effective technologies to manufacture electrical laminates therefrom. Additionally, the present invention resin compositions can have utility as, for example, electrical insulators, encapsulants, insulating adhesives and in various other electrical and related applications generally know to those skilled in this art.
  • thermosetting resin composition comprising (a) a terminally unsaturated urethane resin selected from the group of 1):
  • R is H or CH 3
  • R 2 is an organic residue from a monohydric alcohol and R 3 is an organic residue from a diisocyanate; and 2):
  • R is H or CH 3
  • R 2 is an organic residue from a monohydric alcohol
  • R 3 is an organic residue from a diisocyanate
  • R 4 is an isocyanurate compound of the following structure
  • the ratio of (a) to the sum of (b)1) and (b)2) is less than 0.15, and the ratio of (b)1) to (b)2) is less than 1.2.
  • composition resins may also further contain monomers which would, for example, aid in the adhesion of a metal foil to the laminate; increase crosslink density and thermal performance; etc. Catalysts which, for example, induce free-radical cure may also be added.
  • Other components may include moisture scavengers, compounds which increase or reduce the dielectric constant, and/or reduce the dissipation factor, polyethylene fillers, other fillers, organic or inorganic, which modify rheology, surface agents, viscosity and performance modifiers, wetting agents, air release agents, defoaming agents, flame retardant synergists, adhesion promoters, and other additional monomers and conventional additives known in the art.
  • the present invention further provides electrical laminates from about 0.003 inches to about 0.120 inches thick which may or may not be clad with an electrical conducting material on one or both sides.
  • the electrical laminates of the present invention are produced by
  • compositions of the present invention are uniquely suitable to the continuous lamination methods of Barrel et al. (U.S. Patent No. 4,587,161 and No. 4,803,022).
  • the combination of materials in the outlined ratios provides lower viscosities then previous compositions, (U.S. Patent No. 4,420,509 and No. 4,446,173).
  • Lower viscosities provide more rapid impregnation of reinforcements to allow higher line-speeds and consequently higher machine output.
  • the desired composition is formulated with a free-radical source, (i.e., peroxide, azo-compound, etc.) to initiate cure.
  • the material is postcured in a batch convection oven to further lower the dissipation factor of the laminate. Therefore, we have found the combination of continuous lamination with additional batch cure provides unexpected improvements in electrical performance. While the continuous lamination temperatures and times are known in the art, we have found the optimum secondary batch oven cure profile to be 350°F for 1 hour dwell, (or range from 150°F for 3 hours to 450°F for 30 minutes), (b) The method to manufacture the laminate with a batch process involves 1) A layer of carrier film, such as polyethylene terephthalate of
  • Wire-wound rods are well known throughout the coatings industry.
  • the laminate was placed in a forced air convection oven at 150-250 for 15 minutes to 1 hour.
  • thermosetting resin composition may also further contain the thermosetting resin composition may also further contain the above mentioned added components and may be cured by electron beam processing, radiation, heat with or without pressure, ultra violet light processing, and other conventional curing methods in conjunction with the appropriate initiators.
  • the electrical laminates may further comprise an electrical conductive cladding on at least one side.
  • Fig. 1 is an enlarged cross-sectional view of a part of an electrical laminate which comprises an electrically conductive metal layer 1 and a cross linked thin-wall body of the invented composition 2.
  • Fig. 2 is an enlarged cross-sectional view of an electrical laminate which exemplifies a double-sided metal clad electrical laminate, further provided with two metal conductive layers 1 , and an electrically insulating thin-wall body of the invented composition 2.
  • Fig. 3 is an enlarged cross-sectional view of an electrical laminate which exemplifies a multilayered electrical laminate, of the structure of a combination of single-sided and double sided metal clad electrical laminates as illustrated in Fig. 1 and Fig. 2.
  • Fig. 4 is an enlarged cross-sectional view of an electrical laminate which comprises an electrically conductive layer 1 , a crosslinked thin-wall body of the invented composition 2, and an uniformly dispersed inorganic or organic filler 3.
  • Fig. 5 is an enlarged cross-sectional view of an electrical laminate which comprises an electrically conductive metal layer 1 , a crosslinked thin-wall body of invented composition 2, and nonwoven glass fibers 4.
  • Fig. 6 is an enlarged cross-sectional view of an electrical laminate which comprises an electrically conductive metal layer 1 , a crosslinked thin-wall body of invented composition 2, and woven glass cloth 5.
  • Fig. 7 is an enlarged cross-section view of part of an example of a double-sided metal clad electrical laminate of Fig. 6 further provided with an electrically conductive metal layer 1 on the other surface.
  • Fig. 8 is an enlarged cross-sectional view of an electrical laminate which comprises an electrically conductive metal layer 1 , a crosslinked thin-wall body of the invented composition 2, and an aramid non-woven sheet 6.
  • the present invention comprises resin compositions of moderate cost with excellent electrical properties up to at least 20 GHz which may be flame retardant and heat resistant.
  • the present compositions have utility as electrical insulators, electrical laminates, electrically insulating encapsulants, electrically insulating adhesives and other electrical and related applications.
  • compositions One component of these compositions is a terminally unsaturated urethane resin, known in the industry as a urethane vinyl ester:
  • R is H or CH 3
  • R 2 is an organic residue from a monohydric alcohol
  • R 3 is an organic residue from a diisocyanate.
  • This resin is manufactured by reacting a diisocyanate with two molar equivalents of monohydric alcohol containing a vinylidene group in the presence of a polar solvent (typically styrene) which also acts as a reactive monomer for crosslinking. Examples of this art are well known throughout the industry.
  • the diisocyanate utilized may be aromatic or aliphatic, monomeric or polymeric, etc. The only requirements are that the diisocyanate contain isocyanate groups capable of reacting with the monohydric alcohol and not interfere with the subsequent crosslinking reactions.
  • diisocyanate examples include 2,4 toluene diisocyanate, 2,6 toluene diisocyanate, 2,4'- diphenylmethane diisocyanate, and 2,6'-diphenyl methane diisocynate.
  • monohydric alcohol that contains a vinylidene group examples include hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, and hydroxypropyl acrylate.
  • compositions Another component of these compositions is a terminally unsaturated urethane resin, known in the industry as an isocyanurate vinyl ester:
  • R is H or CH 3
  • R 2 is an organic residue from a monohydric alcohol
  • R 3 is an organic residue from a diisocyanate
  • R 4 is an isocyanurate compound of the following structure
  • This resin is manufactured by the methods of Kuehn et al. (U.S. Patent No. 4,145,544 and No. 4,243,788). For examples of these resins refer to the aforementioned patents.
  • the main embodiment thereof is a printed circuit board laminate suitable for microwave antennas and the like.
  • the preferred ratio for terminally unsaturated urethane resin to ethylenically unsaturated monomer has been determined to be less than 0.15. Or in the case where 1 mole of 2,4'-toluene diisocyanate is reacted with 2 moles of hydroxylpropyl methacrylate, less than 27% by weight of this resin (without monomer) is desired in ethylenically unsaturated monomer. In the case where an isocyanurate vinyl ester is manufactured from the same materials in different ratios, less than about 35% by weight of resin (without monomer) is desired in ethylenically unsaturated monomer.
  • Examples 2 & 3 of TABLE 1 contain a urethane modified vinyl ester with a molecular weight of approximately 4200, styrene monomer of molecular weight 104.15, and dibromostryene of average molecular weight 263.95. Using this information, the ratios of urethane modified vinyl ester to total monomer would be 0.01 and 0.02 for Examples 2 & 3 respectively. Additionally, the ratio of styrene to dibromostyrene would be 0.50, and 1.16 for Examples 2 & 3 respectively.
  • the second main component of these compositions is an ethylenically unsaturated monomer from the group of 1) styrene and 2) bromostyrene.
  • bromostyrene include monobromostyrene, dibromostyrene, and tribromostyrene.
  • the ideal molar ratio of styrene to bromostyrene has been found to be less than 1.2. Maintaining the desired ratios provides a composition with excellent elect ⁇ cal properties at microwave frequencies along with desirable thermal and mechanical properties.
  • An optional component may be divinyl benzene (referred herein as DVB), or any other ethylenically multiunsaturated monomer.
  • DVB can be about 0.1% to about 10% by weight; preferably about 0.5% to about 5% by weight of the total composition; more preferably about 1% to about 4%
  • Divinyl benzene increases the crosslink density and therefore thermal performance of the composition.
  • Other polyfunctional crosslinking monomers may also be used such as divinyl toluene and the like.
  • the third and fourth components contribute to the mechanical and thermal properties of a composition but do not need to be present to obtain the excellent electrical properties.
  • Catalysts and polymerization and U.V. initiators may also be components of the compositions of the present invention. There are many choices available; particularly, catalyst which induce free-radical cure.
  • the preferred catalyst is t-butyl peroctoate at about 0.1 to about 2% by weight of the total composition (preferably about 0.2% by weight of the total composition); benzoate at about 0.1 to about 2% by weight of the total composition (preferably 0.25% by weight of the total composition).
  • Alternate catalysts include benzoyl peroxide, cumene hydrogen peroxide and others known to those skilled in this art. Combination of catalysts may also be used. Curing mechanisms may be utilized including electron beam processing and ultra-violet light processing in conjunction with UV initiators, radiation, heating with or without pressure, and other 5 conventional curing methods in conjunction with the appropriate initiators. Additional components, such as moisture scavengers may also be added. Free moisture in the composition will negatively affect the dissipation factor. Therefore a component, such as 3-ethyl-2-methyl-2-(3- methylbutyl)-1 ,3-oxazolidine (available from Angus Chemical Co.) can be
  • the oxazolidine compound will chemically react with the water to eliminate it.
  • a molecular sieve could be utilized. Molecular sieves are well known as moisture reducers throughout the coatings industry. Molecular sieves function by physically trapping the free water.
  • Another additional component may be titanium dioxide which increases the dielectric constant, but reduces the dissipation factor. This combination of electrical properties is desirable for some specific high frequency applications.
  • the titanium dioxide may be in a range of from about 1 to about 60% by weight of the total composition; preferably about
  • polyethylene filler such as expanded polyethylene compound, available from American Fillers and Abrasives.
  • the polyethylene will lower both the dielectric constant and
  • the polyethylene may be in a range of from about 1 to about 60% by weight of the total composition; preferably about 5 to about 40% by weight of the total composition; more preferably about 10% by weight of the total composition.
  • additives include organic and/or inorganic fillers, for example
  • calcined kaolin to modify rheology; surface active agents, to aid processing; other monomers, such as methyl methacrylate to modify viscosity and possibly performance; epoxies; colorants; fluorescent dyes; U.V. blocking agents; wetting agents; air release agents; defoaming agents; flame retardant synergists (for example, antimony compounds); adhesion promoters (for example, epoxy resin "EPON 828" Shell Chemical Co.); additional monomers including styrene, vinyl toluene, t- butyl styrene, para-methyl styrene, diallyl phthalate, 2,4-ethyi-methyl imidazole, and other conventional additives.
  • additional monomers including styrene, vinyl toluene, t- butyl styrene, para-methyl styrene, diallyl phthalate, 2,4-ethyi-methyl imidazole, and other conventional
  • the present invention further comprises electrical laminates utilizing the thermosetting resin compositions herein described which have excellent elect ⁇ cal properties and which may be flame retardant and heat resistant.
  • the present thermosetting resin compositions can also be utilized in existing cost effective technologies to manufacture various types of electrical laminates. Examples of these technologies include, but are not limited to, continuous lamination, such as that described in U.S. Patent No. 4,803,022 to Barell et al. which is incorporated herein by reference; production of printed circuit boards, such as described in U.S. Patents Nos. 4,671 ,984 and 4,751 ,146 to Masahiko Maeda et al. which are incorporated herein by reference; production of electrical laminates such as described in U.S. Patent No.
  • An electrical laminate of the present invention is produced by infiltrating or impregnating at least one substrate, or multiple substrates, with a resin composition of the present invention to prepare resin- infiltrated or resin-impregnated substrates which are laminated by passage between rolls while removing interiaminar gas bubbles. Subsequently, the resulting laminate is heated, with or without pressure, to cure the resin composition whereby the electrical laminate is obtained. Other cure mechanisms can also be utilized.
  • the electrical laminate of this invention can be continuously produced.
  • organic peroxides can be used as curing catalysts.
  • the organic peroxides include, for example, t-butyl perbenzoate, t-butyl peroxide, benzoyl peroxide, t-butyl peroctoate, t-butyl peroxy benzoate, dicumyl peroxide, etc.
  • the curing can be controlled by use of curing accelerators or polymerization inhibitors. Characteristics of the resin composition can be improved by incorporating therein to plasticizers, stabilizers, thickeners, fillers, coloring agents, lubricants, etc.
  • a copper-clad laminate can be obtained by subjecting substrates impregnated with an uncured resin composition and copper foil to laminated molding to unite them in a body, or by inserting an adhesive between substrates impregnated with an uncured resin and copper foil and then subjecting them to laminated molding to unite them in a body.
  • a copper-clad laminate can be obtained by also preparing a laminate by laminate molding and then unite this laminate and a copper foil laminate in a body through an adhesive. Adhesives such as epoxy resins, butyryl- modified epoxy resins, etc. can be used.
  • the present elect ⁇ cal laminates may be from about 0.001 to about
  • Suitable cladding metals include aluminum, silver, gold, brass and most preferably copper.
  • the metal cladding may be in various forms and weight. The weight may range from about 0.25 to about 5 oz/ft 2
  • the form can be any conventional type, such as, foil, an electrodeposited layer or rolled annealed metal, such as for example, rolled annealed copper.
  • a preferred embodiment comprises a copper clad electrical laminate suitable for subsequent processing as a circuit board, stripline, microstripline microwave components and other related applications. The preferred embodiment of this composition is an electrical laminate from 0.003 to 0.120 inches thick with metal foil clad on one or both sides.
  • Suitable reinforcement components include organic or inorganic fillers, woven fiberglass, glass paper, glass mat, glass cloth, polyimide paper (such as "THERMOUNT” from DuPont), woven polymeric fibers and non-woven polymer fiber reinforcements and the like.
  • the reinforcement components of the laminates of the present invention may be in the range of about 25% to 75% by weight of the total laminate, preferably about 30% t ⁇ about 40%, and more preferably about 35%.
  • the unsaturated urethane resins are manufactured according to U.S. 5 Patent Nos. 4,587,161 and 4,803,022 of Kuehn et al., manufactured according to methods known in the art, or commercially available as Palatal 48001 KR (BASF, Germany) or 580-05 (Reichold Chemicals Inc., USA) in the case of a urethane vinyl ester, and as ITP 1041 and ITP 1070 (Reichold Chemicals Inc., USA), in the case of a isocyanurate vinyl ester.
  • the ethylenically unsaturated monomers styrene and dibromonostyrene are commercially available.
  • the general method of preparing the resin compositions is as follows.
  • the mixture could be degassed in a vacuum (25 -29 o inches of Hg).
  • thermoset resin a. 20 minutes at 210 degrees F, optionally up to 225 degrees F. Temperatures greater than 250°F produce 5 undesirable reactions during cure and yield poor quality product. Lower temperatures than 210°F may be used with longer times. b. Depending upon the desired product, a post- cure is often necessary to optimize the electrical properties. 0 One to three hours at 350°F is preferred. Examples 1 to 9
  • the general method of preparing elect ⁇ cal laminates from the resin compositions is as follows.
  • Examples 1 to 9 were made as indicated below and as further indicated in TABLE 1 which follows below. All laminates are 30 mil dielectric thickness with 18-20% by weight E-glass reinforcement.
  • the mixture is heated to 85-100 degrees Fahrenheit, or any temperature below the point at which the catalyst undergoes considerable decomposition to form free radicals.
  • the resin mixture is heated to facilitate impregnating the reinforcement.
  • the composition is utilized with one of the following processes: a.
  • the resin mixture is used to impregnate the reinforcement(s) in the lab according to the method outlined in application No. 08/483,086, incorporated herein by reference.
  • the residence times and temperatures can be found in TABLE 1. It has been discovered, that when using this lamination process, temperatures above 250°F will produce poor quality laminates, and thus should be avoided, b.
  • the resin composition is used to impregnate the reinforcement(s) in the lab according to the same method as above (a), with the following exceptions. Rather than curing the laminate in an oven, the appropriate catalysts and promoters are chosen, and the laminate is left undisturbed and allowed to cure at room temperature for 1 to 24 hours.
  • the catalyst half-life, quantity of catalyst, and type and amount of promoters will dictate the amount of time needed to cure at room temperature. These examples can be found in TABLE 1 under "Room Temp.” Cure Method. c. Alternately, the composition can impregnate the reinforcement by our patented continuous lamination process, (Barrell et al. U.S. Patent No. 4,803,022). These examples can be found in TABLE 1 under "Continuous” Cure Method. 5) The laminate is post-cured for 1 hour at 350°F. Post-cure reduces the dissipation factor of the laminate. Therefore, a post-cure is desirable, but not required.
  • Db/inch is the insertion loss (S21 parameter) of a 50 ohm micr ost ⁇ p transmission This is an indication of the suitability of the material at microwave frequencies
  • Copper Adhesion Values are In pound per inch width as outlined in Test Method IPC-TM-6502 4 9 Glass Transition Values are in degree Celsius and are obtained by Test Method IPC-TM-65024 24B

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une composition de résine thermodurcie dotée d'excellentes propriétés électriques renfermant (a) une ou plusieurs résines d'uréthanne insaturées au niveau de sa ou leur terminaison, (b) un styrène et (c) un styrène bromé. La composition trouve une application comme feuille de carte à circuit imprimé utilisée au niveau des hyperfréquences.
PCT/US1999/002964 1999-02-12 1999-02-12 Compositions de resine thermodurcies pour hyperfrequences transparentes, feuilles electriques derivees de ces compositions et leur procede d'obtention Ceased WO2000047655A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
JP2000598567A JP2002536518A (ja) 1999-02-12 1999-02-12 マイクロ波透過性熱硬化性樹脂組成物、それより得られる電気的積層体及びそれらの製造方法
EP99906926A EP1173501A1 (fr) 1999-02-12 1999-02-12 Compositions de resine thermodurcies pour hyperfrequences transparentes, feuilles electriques derivees de ces compositions et leur procede d'obtention
AU26722/99A AU2672299A (en) 1999-02-12 1999-02-12 Microwave-transparent thermosetting resin compositions, electrical laminates obtained therefrom, and process of producing these
MXPA01008222A MXPA01008222A (es) 1999-02-12 1999-02-12 Composiciones de resinas termoestables transparentes a las microondas, laminados electricos obtenidos a partir de las mismas y proceso para su produccion.
KR1020017010200A KR20020013499A (ko) 1999-02-12 1999-02-12 마이크로파-투과 열경화성 수지 조성물, 그로부터 얻어진전기적 적층판 및 이들의 제조방법
CA002362609A CA2362609A1 (fr) 1999-02-12 1999-02-12 Compositions de resine thermodurcies pour hyperfrequences transparentes, feuilles electriques derivees de ces compositions et leur procede d'obtention
PCT/US1999/002964 WO2000047655A1 (fr) 1999-02-12 1999-02-12 Compositions de resine thermodurcies pour hyperfrequences transparentes, feuilles electriques derivees de ces compositions et leur procede d'obtention

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1999/002964 WO2000047655A1 (fr) 1999-02-12 1999-02-12 Compositions de resine thermodurcies pour hyperfrequences transparentes, feuilles electriques derivees de ces compositions et leur procede d'obtention

Publications (1)

Publication Number Publication Date
WO2000047655A1 true WO2000047655A1 (fr) 2000-08-17

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Country Status (7)

Country Link
EP (1) EP1173501A1 (fr)
JP (1) JP2002536518A (fr)
KR (1) KR20020013499A (fr)
AU (1) AU2672299A (fr)
CA (1) CA2362609A1 (fr)
MX (1) MXPA01008222A (fr)
WO (1) WO2000047655A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10662304B2 (en) 2013-12-31 2020-05-26 Saint-Gobain Performance Plastics Corporation Composites for protecting signal transmitters/receivers

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115368725B (zh) * 2021-05-18 2023-08-11 万华化学集团股份有限公司 一种高介电常数，低介电损耗热塑性聚氨酯弹性体复合材料及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0527410A2 (fr) * 1991-08-14 1993-02-17 BASF Aktiengesellschaft Résines d'uréthane de vinylester modifiés au choc
WO1998006783A1 (fr) * 1996-08-12 1998-02-19 Ucb, S.A. Compositions de resines durcissant sous l'effet de rayonnements
WO1998011142A1 (fr) * 1996-09-12 1998-03-19 Hehr International Inc. Compositions de resine en prepolymere d'acrylique-urethane susceptibles d'etre traitees par energie rayonnante et procede de traitement
WO1998021250A1 (fr) * 1996-11-12 1998-05-22 Hehr International Inc. Oligomere multifonctionnel de polyacrylate et de polyurethanne, procede de preparation et produits et polymeres traites correspondants

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0527410A2 (fr) * 1991-08-14 1993-02-17 BASF Aktiengesellschaft Résines d'uréthane de vinylester modifiés au choc
WO1998006783A1 (fr) * 1996-08-12 1998-02-19 Ucb, S.A. Compositions de resines durcissant sous l'effet de rayonnements
WO1998011142A1 (fr) * 1996-09-12 1998-03-19 Hehr International Inc. Compositions de resine en prepolymere d'acrylique-urethane susceptibles d'etre traitees par energie rayonnante et procede de traitement
WO1998021250A1 (fr) * 1996-11-12 1998-05-22 Hehr International Inc. Oligomere multifonctionnel de polyacrylate et de polyurethanne, procede de preparation et produits et polymeres traites correspondants

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10662304B2 (en) 2013-12-31 2020-05-26 Saint-Gobain Performance Plastics Corporation Composites for protecting signal transmitters/receivers

Also Published As

Publication number Publication date
CA2362609A1 (fr) 2000-08-17
EP1173501A1 (fr) 2002-01-23
JP2002536518A (ja) 2002-10-29
MXPA01008222A (es) 2002-10-23
AU2672299A (en) 2000-08-29
KR20020013499A (ko) 2002-02-20

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