CA2373154A1 - Thermosetting polymer systems and electronic laminates - Google Patents
Thermosetting polymer systems and electronic laminates Download PDFInfo
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- CA2373154A1 CA2373154A1 CA002373154A CA2373154A CA2373154A1 CA 2373154 A1 CA2373154 A1 CA 2373154A1 CA 002373154 A CA002373154 A CA 002373154A CA 2373154 A CA2373154 A CA 2373154A CA 2373154 A1 CA2373154 A1 CA 2373154A1
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- resin
- hydrogen
- resin system
- maleic anhydride
- functional material
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Classifications
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- 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
- H05K1/0326—Organic insulating material consisting of one material containing O
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/12—Mountings, e.g. non-detachable insulating substrates
- H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
- H01L23/145—Organic substrates, e.g. plastic
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Abstract
A resin system including at least one epoxy resin that is essentially free of nitrogen and with essentially no chain extension, and at least hardener that is mixture of at least one phenolic resin and a copolymer of an allyl functional material and maleic anhydride.
Description
TITLE: Thermosetting Polymer Systems and Electronic Laminates BACKGROUND OF THE INVENTION
(1) Field of the Invention This invention concerns thermosetting polymers that, when cured, exhibit excellent to electrical and thermal performance while absorbing very little moisture.
This invention also concerns printed wiring board laminates made from thermosetting polymers. The laminates exhibit superior dielectric constants, dissipation factors, thermal performance, and reduced moisture absorption.
(2) Description of the Art Printed wiring boards are seeing increased use as substrates in high frequency microprocessor chip packages and as high-density substrates in high frequency telecommunications. Both end-uses require dielectric materials with: low dissipation factors to avoid signal loss and to maintain signal integrity; low moisture absorption to form stable substrates not requiring bake-out; and high thermal resistance to withstand higher wiring 2o temperatures. Board designers prefer the materials with low dissipation factors so that they can route lines at tighter spacing and to permit thinner laminates with closer inner layer distances. In addition, during the formation of higher density substrates, low moisture absorption is desirable to enhance the laminate stability and prevent mis-registration. Many printed wiring boards processing steps use aqueous baths, which can saturate a substrate causing resin swell. Drying substrates after aqueous exposure is a costly and lengthy process.
Finally, where substrates are used in packaging and in some chip on board applications, higher thermal resistance permits wire bonding temperatures increase wiring through put.
Circuit board laminate resin systems are well known in the prior art. U.5.
Patent No.
(1) Field of the Invention This invention concerns thermosetting polymers that, when cured, exhibit excellent to electrical and thermal performance while absorbing very little moisture.
This invention also concerns printed wiring board laminates made from thermosetting polymers. The laminates exhibit superior dielectric constants, dissipation factors, thermal performance, and reduced moisture absorption.
(2) Description of the Art Printed wiring boards are seeing increased use as substrates in high frequency microprocessor chip packages and as high-density substrates in high frequency telecommunications. Both end-uses require dielectric materials with: low dissipation factors to avoid signal loss and to maintain signal integrity; low moisture absorption to form stable substrates not requiring bake-out; and high thermal resistance to withstand higher wiring 2o temperatures. Board designers prefer the materials with low dissipation factors so that they can route lines at tighter spacing and to permit thinner laminates with closer inner layer distances. In addition, during the formation of higher density substrates, low moisture absorption is desirable to enhance the laminate stability and prevent mis-registration. Many printed wiring boards processing steps use aqueous baths, which can saturate a substrate causing resin swell. Drying substrates after aqueous exposure is a costly and lengthy process.
Finally, where substrates are used in packaging and in some chip on board applications, higher thermal resistance permits wire bonding temperatures increase wiring through put.
Circuit board laminate resin systems are well known in the prior art. U.5.
Patent No.
3,686,359 describes electronic circuit board laminates based on the curing of cycloaliphatic epoxies with anhydride curing agents. The reference discloses that laminates using the cycloaliphatic materials and anhydrides have attractive moisture absorption, low dielectric constants, and low dissipation factors. However, the formulations also have low Tg's.
U.5. Patent No. 4,623,578 discloses laminates based on epoxy crosslinked polyanhydrides. An anhydride based copolymer, such as styrene malefic anhydride is first 1o reacted with an amino aromatic compound forming a phenolic imide. The resulting polyimide is reacted with an epoxy to form a thermosetting network. Laminates made from this process have good thermal properties but suffer from high moisture absorption due to the imide moiety.
U.S. Patent No. 5,620,789 discloses a cure inhibited resin composition used in manufacturing electronic laminates. The thermosetting resin systems are cure inhibited using boric acid.
Most printed wiring boards laminates are manufactured as fiberglass polymeric substrates with fillers . being added to improve electrical properties or enhance board processing. Copper foils are typically clad on the laminate surfaces imparting a conductive 2o medium for circuit formation. In a general glass reinforced laminate, the system contains three phases and two interfaces: phases include the glass fiber, the resin matrix, and the copper foil; two interfaces are the region between the resin and glass and the region between the copper foil and the laminate surface.
The interface regions serve as adhesion layers binding the resin to the glass or bonding the copper foil to the laminate surface. Predominantly coupling agents coated on the glass fibers before impregnation and coated on the copper foil prior to lamination controls adhesion.
Coupling agents are silanes with a hydrolyzable silicon end group which reacts with the glass or copper surface and a reactive organic end group which bonds to the resin matrix. For controlling the laminate cohesive integrity and for maintaining circuit adhesion, the coupling agents are critical. Providing these interfaces are of high quality with proper adhesion, they effect little the laminate chemical, thermal, moisture or electrical properties.
Laminate electrical properties (specifically dielectric constant (Dk) and dissipation 1o factor (Df)) fundamentally depend on the resin matrix and the glass fabric.
Glass types such as D-glass or Q-glass can reduce the Dk and Df of a substrate. However, these glass types are more difficult to drill compared to the standard electrical grade, E-glass.
Hence, most interposer laminates are based on woven E-glass fabrics and the dielectric and dissipation properties must be controlled by the resin composition.
Thermal and moisture absorption characteristics are primarily controlled by the resin formulation. Moisture permeates into printed wiring board substrates by absorption into the resin phase and permeates negligibly into the glass fibers. The resin systems typically have lower thermal performance than glass, and are the weakest phase at elevated temperatures.
Using resin systems which resist moisture and have high thermal characteristics reflected in 2o high glass transition temperature will result in improved laminate substrates. Current FR4 based laminates that use dicyandiamide (DICY) as a curative with epoxy resins, show high dielectric constants, very high moisture absorption, and fail to give adequate thermal resistance. Using higher performing resins based on bismaleimide triazine, epoxy novolac, or polyimide, can improve the moisture absorption with an increase in thermal performance, but the level of moisture absorption still requires costly drying and handling steps, and the electrical properties do not meet the high frequency applications. Thus, there still remains a need for resin systems combining low dielectric constant and low dissipation factor, with high thermal resistance and low moisture absorption.
SiJMMARY OF THE INVENTION
This invention includes resin systems that, upon curing, have a low moisture affinity.
This invention also includes resin systems that, upon curing, pioduce cured materials with high performing electrical and thermal performance.
This invention further includes electronic materials and laminates produced using the resins systems of this invention which include good electric and thermal performance and low moisture absorption.
In one embodiment, this invention is a resin system comprising at least one epoxy resin with essentially no chain extension, and at least one hardener that is a mixture of at least one phenolic resin and a copolymer of an allyl functional material and malefic anhydride wherein the resin system is essentially nitrogen free.
In another embodiment, this invention is a laminate including a reinforcing material impregnated with one or more resin systems of this invention. In the laminate, the 2o reinforcing material may be unwoven or woven paper, cloth, glass, or any other material that are useful in manufacturing reinforced prepregs and cores used in the manufacture of circuit boards and circuitized substrates.
U.5. Patent No. 4,623,578 discloses laminates based on epoxy crosslinked polyanhydrides. An anhydride based copolymer, such as styrene malefic anhydride is first 1o reacted with an amino aromatic compound forming a phenolic imide. The resulting polyimide is reacted with an epoxy to form a thermosetting network. Laminates made from this process have good thermal properties but suffer from high moisture absorption due to the imide moiety.
U.S. Patent No. 5,620,789 discloses a cure inhibited resin composition used in manufacturing electronic laminates. The thermosetting resin systems are cure inhibited using boric acid.
Most printed wiring boards laminates are manufactured as fiberglass polymeric substrates with fillers . being added to improve electrical properties or enhance board processing. Copper foils are typically clad on the laminate surfaces imparting a conductive 2o medium for circuit formation. In a general glass reinforced laminate, the system contains three phases and two interfaces: phases include the glass fiber, the resin matrix, and the copper foil; two interfaces are the region between the resin and glass and the region between the copper foil and the laminate surface.
The interface regions serve as adhesion layers binding the resin to the glass or bonding the copper foil to the laminate surface. Predominantly coupling agents coated on the glass fibers before impregnation and coated on the copper foil prior to lamination controls adhesion.
Coupling agents are silanes with a hydrolyzable silicon end group which reacts with the glass or copper surface and a reactive organic end group which bonds to the resin matrix. For controlling the laminate cohesive integrity and for maintaining circuit adhesion, the coupling agents are critical. Providing these interfaces are of high quality with proper adhesion, they effect little the laminate chemical, thermal, moisture or electrical properties.
Laminate electrical properties (specifically dielectric constant (Dk) and dissipation 1o factor (Df)) fundamentally depend on the resin matrix and the glass fabric.
Glass types such as D-glass or Q-glass can reduce the Dk and Df of a substrate. However, these glass types are more difficult to drill compared to the standard electrical grade, E-glass.
Hence, most interposer laminates are based on woven E-glass fabrics and the dielectric and dissipation properties must be controlled by the resin composition.
Thermal and moisture absorption characteristics are primarily controlled by the resin formulation. Moisture permeates into printed wiring board substrates by absorption into the resin phase and permeates negligibly into the glass fibers. The resin systems typically have lower thermal performance than glass, and are the weakest phase at elevated temperatures.
Using resin systems which resist moisture and have high thermal characteristics reflected in 2o high glass transition temperature will result in improved laminate substrates. Current FR4 based laminates that use dicyandiamide (DICY) as a curative with epoxy resins, show high dielectric constants, very high moisture absorption, and fail to give adequate thermal resistance. Using higher performing resins based on bismaleimide triazine, epoxy novolac, or polyimide, can improve the moisture absorption with an increase in thermal performance, but the level of moisture absorption still requires costly drying and handling steps, and the electrical properties do not meet the high frequency applications. Thus, there still remains a need for resin systems combining low dielectric constant and low dissipation factor, with high thermal resistance and low moisture absorption.
SiJMMARY OF THE INVENTION
This invention includes resin systems that, upon curing, have a low moisture affinity.
This invention also includes resin systems that, upon curing, pioduce cured materials with high performing electrical and thermal performance.
This invention further includes electronic materials and laminates produced using the resins systems of this invention which include good electric and thermal performance and low moisture absorption.
In one embodiment, this invention is a resin system comprising at least one epoxy resin with essentially no chain extension, and at least one hardener that is a mixture of at least one phenolic resin and a copolymer of an allyl functional material and malefic anhydride wherein the resin system is essentially nitrogen free.
In another embodiment, this invention is a laminate including a reinforcing material impregnated with one or more resin systems of this invention. In the laminate, the 2o reinforcing material may be unwoven or woven paper, cloth, glass, or any other material that are useful in manufacturing reinforced prepregs and cores used in the manufacture of circuit boards and circuitized substrates.
DESCRIPTION OF THE CURRENT EMBODIMENT
The present invention relates to high Tg, low moisture absorbing resin systems and laminates, encapsulants, and underfills manufactured using the resin systems.
The resin systems of this invention use epoxy resins cured with phenolic and anhydride based resins and may include optional ingredients such as flexibilizing or toughening components or fillers.
An important aspect of this invention is the use of resin systems that do not include nitrogen-containing groups. Resins including nitrogen containing groups will usually produce products with undesirable electrical properties, low Tg, and high moisture absorption.
l0 Eliminating resin nitrogen and selectively using a defined class of epoxy resins with phenolic and anhydride hardeners will produce useful resin systems.
The epoxy resins used in this invention should not be formed by chain extension reactions or contain nitrogen. Chain extended epoxies suffer from low Tg do to high epoxy equivalent weights. When the epoxy contains nitrogen (for example aniline moieties) the Tg tends to be high, but moisture absorption also dramatically increases.
Furthermore, nitrogen containing epoxies are usually toxic and present processing difficulties.
Preferred resins are those that are essentially nitrogen free, those that have low hydrolizable chloride, low epoxy equivalent weights and combinations thereof.
The epoxy resins used in the resin systems of this invention should be essentially nitrogen free. It has 2o been determined that epoxy resins including nitrogen-containing groups produce undesirable electric properties, high moisture absorption properties in cured products. By eliminating nitrogen groups from the epoxy resin and from the other resin system ingredients, improved products can be achieved.
The present invention relates to high Tg, low moisture absorbing resin systems and laminates, encapsulants, and underfills manufactured using the resin systems.
The resin systems of this invention use epoxy resins cured with phenolic and anhydride based resins and may include optional ingredients such as flexibilizing or toughening components or fillers.
An important aspect of this invention is the use of resin systems that do not include nitrogen-containing groups. Resins including nitrogen containing groups will usually produce products with undesirable electrical properties, low Tg, and high moisture absorption.
l0 Eliminating resin nitrogen and selectively using a defined class of epoxy resins with phenolic and anhydride hardeners will produce useful resin systems.
The epoxy resins used in this invention should not be formed by chain extension reactions or contain nitrogen. Chain extended epoxies suffer from low Tg do to high epoxy equivalent weights. When the epoxy contains nitrogen (for example aniline moieties) the Tg tends to be high, but moisture absorption also dramatically increases.
Furthermore, nitrogen containing epoxies are usually toxic and present processing difficulties.
Preferred resins are those that are essentially nitrogen free, those that have low hydrolizable chloride, low epoxy equivalent weights and combinations thereof.
The epoxy resins used in the resin systems of this invention should be essentially nitrogen free. It has 2o been determined that epoxy resins including nitrogen-containing groups produce undesirable electric properties, high moisture absorption properties in cured products. By eliminating nitrogen groups from the epoxy resin and from the other resin system ingredients, improved products can be achieved.
The resin systems of this invention should be essentially nitrogen free and are preferably nitrogen free. The term "essentially nitrogen free" as used herein means that the resin system of this invention includes less than 1 wt% nitrogen. The term "nitrogen free" as used herein means that the resin system of this invention includes less than 0.1 wt% nitrogen.
Preferred epoxy resins useful in the resin systems of this invention are chosen from multifunctional types. These epoxy resins can be of the cresol novolac or phenol novolac variety. Preferably the epoxy resins are those derived from trisphenol resins prepared with low hydrolizable chloride content, low hydroxyl moieties, and with minimal chain extension reactions. These resins can be prepared in accordance with U.S. Patents 4,468,508 and 4,876, 1o 371 and 5,008.350, the specifications of each of which are incorporated herein by referenced.
Preferred epoxies useful in the resin systems of this invention have the formulas:
Xz R, ~ z Xz R~ ~ z Xz Ri C
C
X, OG ~ z X, oG ~ X
n and X; R, RS X, R, R3 X, R, ,_ C C
R~ X~ R. R X~ R~ R
OG = OG ~ OG
Rz OG Rz OG
n and X, R, p X, R, Rs Xi R, C C
Rz ~' ~ I RI OG ~ I Rz OG
R, C rR~ R,, _ C -~
X, R~
,x ~I I
Rz OG R; OG
n and mixtures thereof. In the resin formulations above, N is an integer. from 1 to 300; X, and Xz are each individually selected from hydrogen or from the halogens Cl, F and Br; R" Rz, R3, R4 and RS are each individually selected from hydrogen and alkyl groups wherein the term s "alkyl" refers to a straight or branched alkyl moiety having from 1 to 20 carbon atoms; and G refers to:
O
O = CH=C CH=
Non-exclusive examples of epoxy resins having the above-identified formulas are available as Quatrex 6410 (Ciba-Geigy), Bren 304 (Nippon Kayaku), ESCN-195X
l0 (Sumitomo), TNM574 (Sumitomo Chemical), EPPN 502H (Nippon Kayaku), and (Nippon Kayaku).
The resin system of this invention includes one or more hardeners. Those skilled in the art will know the hardener purpose is to react with the pendent oxirane rings in the epoxy resins creating a polymer network. The epoxy resins and hardeners are combined such that _7_ WO 00!69232 PCT/US00/08781 the epoxy equivalent to hardener equivalent ratio ranges from 0.7 to about 1.3. It is preferred that the epoxy to hardener equivalency ratios range from about 0.9 to 1.1.
Examples of hardeners include phenol novolacs, cresol novolacs, aromatic amines, cyanate esters such as polycresol cyanates, styrene malefic anhydride copolymers, aromatic anhydrides such as 4,4'-s (2-acetoxy-1,3-glycerol)-bisandhydrotrimellitate and vinyl alkyl malefic anhydride co-polymers such as poly(maleic anhyride-alt-1-octadecene) and mixtures thereof.
Preferred hardeners are phenolic resins in combination with a copolymer of an ally!
functional material and malefic anhydride. Phenolic resins that are especially useful in the preferred hardeners are compounds have the following formulas:
to Xs Rv I_ , i I I ..~. i 'X~ OH R~ I X' OH ~ X'~ OH
n or X, R, Ra X, R, Rs X, R, C C
R' OH X~ R~ R= ON X~ R~ R= OH
Rz OH R= OH
n or mixtures thereof wherein R" R2, and R3, are each individually selected from hydrogen and 15 alkyl groups wherein the term "alkyl" refers to a straight or branched alkyl moiety having from 1 to 20 carbon atoms and wherein n=1 to 300. Non-exclusive examples of useful _g_ phenolic resins having the above-identified structures include SDI711 (Borden Chemical), MU-12700 (Schenectady International), and MEH7500 (Meiwa Plastics).
The second component of the preferred hardner is a copolymer of an allyl functional material and malefic anhydride. A most preferred allyl functional material is styrene.
Generally the allyl functional material and the malefic anhydride will be combined in a weight ratio amount ranging from about 15:1 to about 1:1. Preferably, when the allylfunctional material is styrene, the styrene to malefic anhydride weight ratio is about S
to 1.
Preferred copolymers useful in the hardness of this invention have the following formula:
Re CHi -CH ~ C -C
R, o =~~ j = o y R, -__ i R.
wherein Ra is selected from X~ and branched and straight chain alkyl group having from 1 to 20 carbon atoms and combinations thereof, R, is as described above, and Rb and R~ are each individually selected from polymerization initiation or termination groups. Appropriate polymerization initiators are free radical type initiators. Such initiators are available from Du Pont and sold under the VAZO~ product line. The Du Pont initiators are substituted azonitrile compounds that thermally decompose and generate free radicals.
The most common azonitrile is 2,2-azobis(butyronitrile) (AIBN). AIBN produces two 2-cyanoisopropyl radicals which constitute the end groups Rb and Rc. Other useful initiators include VAZO 64 and VAZO 68 manufactured by Du Pont.
For the present invention, inappropriate epoxy hardeners are those based on dicyandiamide (DICY). The DICY based systems have significant nitrogen containing moieties. and produce a cured epoxy resin with much higher moisture contents, inadequate electrical properties, and lower Tg than produced by the hardeners of the present invention.
Besides the catalysts, all resin components should be essentially nitrogen free as defined above.
The resin compositions of the present invention may contain ingredients in addition to the epoxy resins and hardeners discussed above. Optional ingredients include inorganic fillers to such as a silica powder fine silicon oxide powders, talc and clay. Other optional ingredients may include flame retardants such as antimony trioxide phosphates and aluminum trihydrate;
flow control agents such as phenol terminated polyether sulfone, polyvinyl butyrate, magnesium hydroxide and polyether imide; and dyes or pigments to control color, and surfactants to control surface appearance.
The following examples illustrate preferred embodiments of this invention as well as preferred methods for using compositions of this invention. The Examples are not intended to limit the scope of the inventions which are set forth in the claims appended hereto.
This Example compares properties of laminates prepared using resin compositions of 2o this invention with a commercial FR-4 laminates prepared with a DICY
hardener system.
Each laminate was prepared by coating and drying the resins on 7628 woven glass and curing to an intermittent gel point (b-stage prepreg). The prepregs were layered to four layers between copper foil and fed under appropriate temperature and pressure into a press until cured. Press conditions followed loading at 180°F, bringing to pressure at 200 psi, ramping the temperature to 392°F at a rate of 10°F/min. under pressure.
The temperature is maintained at 392°F for 1 hour after which the laminate stack was cooled to room temperature before opening. The outer copper foil layers were etched in a conventional etchant to remove the s copper layers to form an unclad laminate. All laminates contained resin fractions on the order of about 40% by weight. The resin systems used to prepare the prepregs are set forth in Tables l and 2, below.
Table 1 Resin Formulations Formulation1 2 3 4 5 6 7 8 TMH 574 51.48 34.93 39.74 15.27 EPPN-502H 45.26 56.84 71.95 NC6000 50.86 Quatrex 56.40g 91.69g 54.13g 48.64g41.94g 56.17g BA59P 29.41 31.30 35.87 41.83 30.97 29.60 Bren 304 61.14 102.81 MEH7500 10.51 HRJ 12700 12.74 SMA EF30 102.71 102.87 109.31 108.16 109.18 103.37 SMA 2000P 98.65 SMA 1000P 84.73 PMA 84.80g 84.80g 84.80g 84.80g84.80g 84.80g 84.80g 84.80g Solvent MEK 75.20g 75.20g 75.20g 75.20g75.20g 75.20g 75.20g 75.20g Solvent 2 Methyl 0.11g 0.11g O.l 0.11g 0.11g 0.11g O.l 0.11g Imidazole 1g 1g Boric Acid0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.09 Total 400 ' 400 400 400 400 400 400 400 Table 2 Resin Formulations Formulation 9 10 11 TMH 574 51.48 51.48 51.48 uatrex 6410 56.40 56.40 56.40 BA59P 29.41 29.41 29.41 Bren 304 SMA EF30 102.71 102.71 102.71 PMA Solvent 84.80 84.80 84.80 MEK Solvent 75.20 75.20 75.20 2 Meth 1 Imidazole0.11 0.11 Boric Acid 0.09 Tetra butyl 0.48g Phos honium Acetate Total 400 400 400 Table 3, below sets forth the compositions and functions of the ingredients identified in Tables 1 and 2.
Table 3 Composition Descriptions In edient Formula Function TMH 574 Multifunctional a ox E ox resin EPPN 502H Multifunctional a ox E ox resin NC6000 Multifunctional a ox E ox resin uatrex 6410 Brominated a ox resin E ox BREN 304 Brominated a ox resin E ox BP 59P Brominated henolic Hardener resin MEH 7500 Phenolic resin Hardener HRJ 12700 Phenolic resin Hardener SMA EF30 S ene malefic anh drideHardener SMA 2000P S ene malefic anh drideHardener SMA 1000P S ene malefic anh drideHardener PMA Solvent 1-methox -2- ro anol Resin S stem Solvent acetate MEK Solvent Meth 1 eth 1 keone Resin S stem Solvent 2-Meth 1 imidazole 2-meth 1 imidazole Catal st Boric Acid Boric acid Catal st Terrabutyl PhosphoniumTetrabutyl phosphoniumCatalyst Acetate acetate Before determining laminate properties, all laminate samples were brought to equilibrium at 24°C and SO% relative humidity (RH). Moisture absorption at 85°C and 85%
RH was measured to the point, of saturation. Table 4 below, summarizes the results of the FR-4 DICY system compared against laminates of the current invention.
Table 4 FormulationPrior 1 2 3 4 5 6 7 8 Art Tg by DMA 160 221 221 228 231 234 212 212 225 C
Moisture 1.20 0.24 0.27 0.34 0.37 0.54 0.27 0.25 NA
Absorption (%) 85C, 85% RH
Barcol 96.5 97.0 93.9 102.3 92.3 98.5 91.6 NA NA
Hardness Z-axis 120.0 NA 100.0 92.9 84.1 103.0 92.5 NA NA
CTE
Dk 1.2GHz 4.55 4.01 4.02 4.09 4.15 4.31 3.92 NA NA
Dk 600MHz 4.55 4.01 4.01 4.08 4.17 4.31 3.93 NA NA
Dk 300MHz 4.58 4.04 4.04 4.04 4.19 4.34 3.94 NA NA
Dk 100MHz 4.62 4.07 4.07 4.12 4.23 4.39 3.97 NA NA
Df 1.2GHz 0.01120.0093 0.01020.0098 0.01150.0143 0.0090NA NA
Df 600 0.01180.0093 0.01000.0097 0.01170.0143 0.0090NA NA
MHz Df 300 0.01220.0089 0.0 0.0093 0.01130.0139 0.0087NA NA
MHz 096 Df 100MHz 0.0129_ _ 0.0093 0.01120.0136 0.0084NA NA
0.0086 0.0091 ~
The resin systems of this invention produce resins with significantly higher Tg values and with much lower moisture absorption in comparison to FR4 resin. Dielectric constants (Dk) are typically 0.3 to 0.6 lower than FR4 materials. Dissipation factors (Df) are low, with some formulations being under 0.0090.
This Example evaluates whether or not resin curing properties and the resulting laminate thermal characteristics can be improved by altering the resin catalyst package.
Laminates using resin systems of this invention were prepared according to Example 1. The resin systems used included various catalyst combinations. The laminate properties were evaluated according to the method described in Example 1 and the results are reported in Table 5, below.
Table 5 ('.atalvct Fffectc T b DMA C 160 221 220 220 Moisture 1.20 0.24 0.25 0.34 Absorption (%) 85C, 85% RH
Barcol Hardness96.5 97.0 93.5 95.2 Z-axis CTE 20- 120.0 NA 105.0 61.8 Dk 1.2 GHz 4.55 4.01 3.84 3.91 Dk 600 MHz 4.55 4.01 3.85 3.91 Dk 300 MHz 4.58 4.04 3.86 3.95 Dk 100 MHz 4.62 4.07 3.89 3.96 Df 1.2GHz 0.0112 0.0093 0.0088 0.0090 Df 600MHz 0.0118 0.0093 0.0087 0.0089 Df 300 MHz 0.0122 0.0089 0.0083 0.0086 Df 100 MHz 0.0129 0.0086 0.0081 0.0086 In the current invention a boric acid - imidazole catalyst package was used with good success. However, removing the boric acid to give a purely imidazole catalyzed system or using a phosphonium catalyst had no detrimental impact on the laminate properties.
Furthermore, removing the boric acid improved the laminate properties through the lowering is of the dielectric and dissipation factors.
Preferred epoxy resins useful in the resin systems of this invention are chosen from multifunctional types. These epoxy resins can be of the cresol novolac or phenol novolac variety. Preferably the epoxy resins are those derived from trisphenol resins prepared with low hydrolizable chloride content, low hydroxyl moieties, and with minimal chain extension reactions. These resins can be prepared in accordance with U.S. Patents 4,468,508 and 4,876, 1o 371 and 5,008.350, the specifications of each of which are incorporated herein by referenced.
Preferred epoxies useful in the resin systems of this invention have the formulas:
Xz R, ~ z Xz R~ ~ z Xz Ri C
C
X, OG ~ z X, oG ~ X
n and X; R, RS X, R, R3 X, R, ,_ C C
R~ X~ R. R X~ R~ R
OG = OG ~ OG
Rz OG Rz OG
n and X, R, p X, R, Rs Xi R, C C
Rz ~' ~ I RI OG ~ I Rz OG
R, C rR~ R,, _ C -~
X, R~
,x ~I I
Rz OG R; OG
n and mixtures thereof. In the resin formulations above, N is an integer. from 1 to 300; X, and Xz are each individually selected from hydrogen or from the halogens Cl, F and Br; R" Rz, R3, R4 and RS are each individually selected from hydrogen and alkyl groups wherein the term s "alkyl" refers to a straight or branched alkyl moiety having from 1 to 20 carbon atoms; and G refers to:
O
O = CH=C CH=
Non-exclusive examples of epoxy resins having the above-identified formulas are available as Quatrex 6410 (Ciba-Geigy), Bren 304 (Nippon Kayaku), ESCN-195X
l0 (Sumitomo), TNM574 (Sumitomo Chemical), EPPN 502H (Nippon Kayaku), and (Nippon Kayaku).
The resin system of this invention includes one or more hardeners. Those skilled in the art will know the hardener purpose is to react with the pendent oxirane rings in the epoxy resins creating a polymer network. The epoxy resins and hardeners are combined such that _7_ WO 00!69232 PCT/US00/08781 the epoxy equivalent to hardener equivalent ratio ranges from 0.7 to about 1.3. It is preferred that the epoxy to hardener equivalency ratios range from about 0.9 to 1.1.
Examples of hardeners include phenol novolacs, cresol novolacs, aromatic amines, cyanate esters such as polycresol cyanates, styrene malefic anhydride copolymers, aromatic anhydrides such as 4,4'-s (2-acetoxy-1,3-glycerol)-bisandhydrotrimellitate and vinyl alkyl malefic anhydride co-polymers such as poly(maleic anhyride-alt-1-octadecene) and mixtures thereof.
Preferred hardeners are phenolic resins in combination with a copolymer of an ally!
functional material and malefic anhydride. Phenolic resins that are especially useful in the preferred hardeners are compounds have the following formulas:
to Xs Rv I_ , i I I ..~. i 'X~ OH R~ I X' OH ~ X'~ OH
n or X, R, Ra X, R, Rs X, R, C C
R' OH X~ R~ R= ON X~ R~ R= OH
Rz OH R= OH
n or mixtures thereof wherein R" R2, and R3, are each individually selected from hydrogen and 15 alkyl groups wherein the term "alkyl" refers to a straight or branched alkyl moiety having from 1 to 20 carbon atoms and wherein n=1 to 300. Non-exclusive examples of useful _g_ phenolic resins having the above-identified structures include SDI711 (Borden Chemical), MU-12700 (Schenectady International), and MEH7500 (Meiwa Plastics).
The second component of the preferred hardner is a copolymer of an allyl functional material and malefic anhydride. A most preferred allyl functional material is styrene.
Generally the allyl functional material and the malefic anhydride will be combined in a weight ratio amount ranging from about 15:1 to about 1:1. Preferably, when the allylfunctional material is styrene, the styrene to malefic anhydride weight ratio is about S
to 1.
Preferred copolymers useful in the hardness of this invention have the following formula:
Re CHi -CH ~ C -C
R, o =~~ j = o y R, -__ i R.
wherein Ra is selected from X~ and branched and straight chain alkyl group having from 1 to 20 carbon atoms and combinations thereof, R, is as described above, and Rb and R~ are each individually selected from polymerization initiation or termination groups. Appropriate polymerization initiators are free radical type initiators. Such initiators are available from Du Pont and sold under the VAZO~ product line. The Du Pont initiators are substituted azonitrile compounds that thermally decompose and generate free radicals.
The most common azonitrile is 2,2-azobis(butyronitrile) (AIBN). AIBN produces two 2-cyanoisopropyl radicals which constitute the end groups Rb and Rc. Other useful initiators include VAZO 64 and VAZO 68 manufactured by Du Pont.
For the present invention, inappropriate epoxy hardeners are those based on dicyandiamide (DICY). The DICY based systems have significant nitrogen containing moieties. and produce a cured epoxy resin with much higher moisture contents, inadequate electrical properties, and lower Tg than produced by the hardeners of the present invention.
Besides the catalysts, all resin components should be essentially nitrogen free as defined above.
The resin compositions of the present invention may contain ingredients in addition to the epoxy resins and hardeners discussed above. Optional ingredients include inorganic fillers to such as a silica powder fine silicon oxide powders, talc and clay. Other optional ingredients may include flame retardants such as antimony trioxide phosphates and aluminum trihydrate;
flow control agents such as phenol terminated polyether sulfone, polyvinyl butyrate, magnesium hydroxide and polyether imide; and dyes or pigments to control color, and surfactants to control surface appearance.
The following examples illustrate preferred embodiments of this invention as well as preferred methods for using compositions of this invention. The Examples are not intended to limit the scope of the inventions which are set forth in the claims appended hereto.
This Example compares properties of laminates prepared using resin compositions of 2o this invention with a commercial FR-4 laminates prepared with a DICY
hardener system.
Each laminate was prepared by coating and drying the resins on 7628 woven glass and curing to an intermittent gel point (b-stage prepreg). The prepregs were layered to four layers between copper foil and fed under appropriate temperature and pressure into a press until cured. Press conditions followed loading at 180°F, bringing to pressure at 200 psi, ramping the temperature to 392°F at a rate of 10°F/min. under pressure.
The temperature is maintained at 392°F for 1 hour after which the laminate stack was cooled to room temperature before opening. The outer copper foil layers were etched in a conventional etchant to remove the s copper layers to form an unclad laminate. All laminates contained resin fractions on the order of about 40% by weight. The resin systems used to prepare the prepregs are set forth in Tables l and 2, below.
Table 1 Resin Formulations Formulation1 2 3 4 5 6 7 8 TMH 574 51.48 34.93 39.74 15.27 EPPN-502H 45.26 56.84 71.95 NC6000 50.86 Quatrex 56.40g 91.69g 54.13g 48.64g41.94g 56.17g BA59P 29.41 31.30 35.87 41.83 30.97 29.60 Bren 304 61.14 102.81 MEH7500 10.51 HRJ 12700 12.74 SMA EF30 102.71 102.87 109.31 108.16 109.18 103.37 SMA 2000P 98.65 SMA 1000P 84.73 PMA 84.80g 84.80g 84.80g 84.80g84.80g 84.80g 84.80g 84.80g Solvent MEK 75.20g 75.20g 75.20g 75.20g75.20g 75.20g 75.20g 75.20g Solvent 2 Methyl 0.11g 0.11g O.l 0.11g 0.11g 0.11g O.l 0.11g Imidazole 1g 1g Boric Acid0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.09 Total 400 ' 400 400 400 400 400 400 400 Table 2 Resin Formulations Formulation 9 10 11 TMH 574 51.48 51.48 51.48 uatrex 6410 56.40 56.40 56.40 BA59P 29.41 29.41 29.41 Bren 304 SMA EF30 102.71 102.71 102.71 PMA Solvent 84.80 84.80 84.80 MEK Solvent 75.20 75.20 75.20 2 Meth 1 Imidazole0.11 0.11 Boric Acid 0.09 Tetra butyl 0.48g Phos honium Acetate Total 400 400 400 Table 3, below sets forth the compositions and functions of the ingredients identified in Tables 1 and 2.
Table 3 Composition Descriptions In edient Formula Function TMH 574 Multifunctional a ox E ox resin EPPN 502H Multifunctional a ox E ox resin NC6000 Multifunctional a ox E ox resin uatrex 6410 Brominated a ox resin E ox BREN 304 Brominated a ox resin E ox BP 59P Brominated henolic Hardener resin MEH 7500 Phenolic resin Hardener HRJ 12700 Phenolic resin Hardener SMA EF30 S ene malefic anh drideHardener SMA 2000P S ene malefic anh drideHardener SMA 1000P S ene malefic anh drideHardener PMA Solvent 1-methox -2- ro anol Resin S stem Solvent acetate MEK Solvent Meth 1 eth 1 keone Resin S stem Solvent 2-Meth 1 imidazole 2-meth 1 imidazole Catal st Boric Acid Boric acid Catal st Terrabutyl PhosphoniumTetrabutyl phosphoniumCatalyst Acetate acetate Before determining laminate properties, all laminate samples were brought to equilibrium at 24°C and SO% relative humidity (RH). Moisture absorption at 85°C and 85%
RH was measured to the point, of saturation. Table 4 below, summarizes the results of the FR-4 DICY system compared against laminates of the current invention.
Table 4 FormulationPrior 1 2 3 4 5 6 7 8 Art Tg by DMA 160 221 221 228 231 234 212 212 225 C
Moisture 1.20 0.24 0.27 0.34 0.37 0.54 0.27 0.25 NA
Absorption (%) 85C, 85% RH
Barcol 96.5 97.0 93.9 102.3 92.3 98.5 91.6 NA NA
Hardness Z-axis 120.0 NA 100.0 92.9 84.1 103.0 92.5 NA NA
CTE
Dk 1.2GHz 4.55 4.01 4.02 4.09 4.15 4.31 3.92 NA NA
Dk 600MHz 4.55 4.01 4.01 4.08 4.17 4.31 3.93 NA NA
Dk 300MHz 4.58 4.04 4.04 4.04 4.19 4.34 3.94 NA NA
Dk 100MHz 4.62 4.07 4.07 4.12 4.23 4.39 3.97 NA NA
Df 1.2GHz 0.01120.0093 0.01020.0098 0.01150.0143 0.0090NA NA
Df 600 0.01180.0093 0.01000.0097 0.01170.0143 0.0090NA NA
MHz Df 300 0.01220.0089 0.0 0.0093 0.01130.0139 0.0087NA NA
MHz 096 Df 100MHz 0.0129_ _ 0.0093 0.01120.0136 0.0084NA NA
0.0086 0.0091 ~
The resin systems of this invention produce resins with significantly higher Tg values and with much lower moisture absorption in comparison to FR4 resin. Dielectric constants (Dk) are typically 0.3 to 0.6 lower than FR4 materials. Dissipation factors (Df) are low, with some formulations being under 0.0090.
This Example evaluates whether or not resin curing properties and the resulting laminate thermal characteristics can be improved by altering the resin catalyst package.
Laminates using resin systems of this invention were prepared according to Example 1. The resin systems used included various catalyst combinations. The laminate properties were evaluated according to the method described in Example 1 and the results are reported in Table 5, below.
Table 5 ('.atalvct Fffectc T b DMA C 160 221 220 220 Moisture 1.20 0.24 0.25 0.34 Absorption (%) 85C, 85% RH
Barcol Hardness96.5 97.0 93.5 95.2 Z-axis CTE 20- 120.0 NA 105.0 61.8 Dk 1.2 GHz 4.55 4.01 3.84 3.91 Dk 600 MHz 4.55 4.01 3.85 3.91 Dk 300 MHz 4.58 4.04 3.86 3.95 Dk 100 MHz 4.62 4.07 3.89 3.96 Df 1.2GHz 0.0112 0.0093 0.0088 0.0090 Df 600MHz 0.0118 0.0093 0.0087 0.0089 Df 300 MHz 0.0122 0.0089 0.0083 0.0086 Df 100 MHz 0.0129 0.0086 0.0081 0.0086 In the current invention a boric acid - imidazole catalyst package was used with good success. However, removing the boric acid to give a purely imidazole catalyzed system or using a phosphonium catalyst had no detrimental impact on the laminate properties.
Furthermore, removing the boric acid improved the laminate properties through the lowering is of the dielectric and dissipation factors.
Claims (13)
1. A resin system comprising at least one epoxy resin with essentially no chain extension, and at least one hardener that is a mixture of at least one phenolic resin and a copolymer of an allyl functional material and maleic anhydride wherein the resin system is essentially nitrogen free.
2. The resin system of claim 1 wherein the epoxy resin is selected from ~
and mixtures thereof wherein n=1 to 300; X, and X2 are each individually selected from hydrogen, Cl, F and Br; R1,R2,R3,R4 and R5 are each individually selected from hydrogen and straight and branched alkyl moieties having from 1 to 20 carbon atoms, and wherein G
is:
and mixtures thereof wherein n=1 to 300; X, and X2 are each individually selected from hydrogen, Cl, F and Br; R1,R2,R3,R4 and R5 are each individually selected from hydrogen and straight and branched alkyl moieties having from 1 to 20 carbon atoms, and wherein G
is:
3. The resin system of claim 2 wherein the epoxy resin is and wherein R1 is a tert-butyl group, and R2, R3 and X1 are each hydrogen and wherein n=1 to 300.
4. The resin system of claim 2 wherein the epoxy resin is wherein R1,R2,R3,R5 and X2 are each hydrogen and wherein X1 is bromine.
5. The resin system of claim 1 wherein the phenolic resin is selected from compounds having the following formulas:
and mixtures thereof wherein R1,R2, and R3, are each individually selected from hydrogen and straight or branched alkyl moieties having from 1 to 20 carbon atoms, wherein n=1 to 300, and wherein X1 and X2 are each individually selected from hydrogen, Cl, F and Br.
and mixtures thereof wherein R1,R2, and R3, are each individually selected from hydrogen and straight or branched alkyl moieties having from 1 to 20 carbon atoms, wherein n=1 to 300, and wherein X1 and X2 are each individually selected from hydrogen, Cl, F and Br.
6. The resin system of claim 1 wherein the phenolic resin is wherein R1,R2,R3 and X1 are each hydrogen and wherein n=1 to 300.
7. The resin system of claim 1 wherein the copolymer of an allyl functional material and maleic anhydride has the formula:
wherein R a is selected from and straight and branched alkyl moieties having from 1 to 20 carbon atoms and combinations thereof, R1 is selected from hydrogen and straight and branched alkyl moieties having from 1 to 20 carbon atoms, and R b and R c are each individually selected from polymerization initiation or termination groups.
wherein R a is selected from and straight and branched alkyl moieties having from 1 to 20 carbon atoms and combinations thereof, R1 is selected from hydrogen and straight and branched alkyl moieties having from 1 to 20 carbon atoms, and R b and R c are each individually selected from polymerization initiation or termination groups.
8. The resin system of claim 1 wherein the copolymer of an allyl functional material and maleic anhydride is styrene maleic anhydride.~
9. The resin system of claim 1 wherein the equivalence ratio of epoxy resins to hardeners ranges from about 0.9 to about 1.1.
10. The resin system of claim 1 wherein the allyl functional material and the maleic anhydride will be combined in a weight ratio amount ranging from about 15:1 to about 1:1.
11. A laminate including a woven material impregnated with the resin system of claim 1.
12. The laminate of claim 11 wherein the woven material is woven glass and the laminate is selected from a prepreg, a core, or a combination thereof.
13. An essentially nitrogen free resin system comprising an epoxy resin having the formula:
wherein G is R1,R2,R3,R5 and X2 are each hydrogen, X1 is bromine, and n= 1-300;
at least one hardener that is a mixture of at least one phenolic resin and a copolymer of an allyl functional material and maleic anhydride wherein the phenolic resin has the formula:
wherein R1,R2,R3 and X1 are each hydrogen and wherein n=1 to 300;
and wherein the copolymer of an allyl functional material and maleic anhydride is styrene maleic anhydride having the formula:
wherein R a is selected from R1 is selected from hydrogen and straight and branched alkyl moieties having from 1 to 20 carbon atoms, and R b and R c are each individually selected from polymerization initiation or termination groups.
wherein G is R1,R2,R3,R5 and X2 are each hydrogen, X1 is bromine, and n= 1-300;
at least one hardener that is a mixture of at least one phenolic resin and a copolymer of an allyl functional material and maleic anhydride wherein the phenolic resin has the formula:
wherein R1,R2,R3 and X1 are each hydrogen and wherein n=1 to 300;
and wherein the copolymer of an allyl functional material and maleic anhydride is styrene maleic anhydride having the formula:
wherein R a is selected from R1 is selected from hydrogen and straight and branched alkyl moieties having from 1 to 20 carbon atoms, and R b and R c are each individually selected from polymerization initiation or termination groups.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13315699P | 1999-05-07 | 1999-05-07 | |
| US60/133,156 | 1999-05-07 | ||
| US45158899A | 1999-11-30 | 1999-11-30 | |
| US09/451,588 | 1999-11-30 | ||
| PCT/US2000/008781 WO2000069232A1 (en) | 1999-05-07 | 2000-04-03 | Thermosetting polymer systems and electronic laminates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2373154A1 true CA2373154A1 (en) | 2000-11-16 |
Family
ID=26831102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002373154A Abandoned CA2373154A1 (en) | 1999-05-07 | 2000-04-03 | Thermosetting polymer systems and electronic laminates |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1203515A1 (en) |
| JP (1) | JP2002544332A (en) |
| KR (1) | KR20020003878A (en) |
| CA (1) | CA2373154A1 (en) |
| WO (1) | WO2000069232A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040101689A1 (en) | 2002-11-26 | 2004-05-27 | Ludovic Valette | Hardener composition for epoxy resins |
| KR100523621B1 (en) * | 2003-02-11 | 2005-10-24 | 주식회사 케이씨씨 | Epoxy resin composition for environmental frendly sealing semiconductor element |
| US20110224332A1 (en) * | 2009-06-05 | 2011-09-15 | He Yufang | Thermosetting resin composition and use thereof |
| KR20140066514A (en) * | 2012-11-23 | 2014-06-02 | 삼성전기주식회사 | Resin composition for printed circuit board, insulating film, prepreg and printed circuit board |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4042550A (en) * | 1975-11-28 | 1977-08-16 | Allied Chemical Corporation | Encapsulant compositions based on anhydride-hardened epoxy resins |
| US5008350A (en) * | 1987-12-16 | 1991-04-16 | Sumitomo Chemical Company, Limited | Glycidyl ethers of phenolic compounds and process for producing the same |
-
2000
- 2000-04-03 CA CA002373154A patent/CA2373154A1/en not_active Abandoned
- 2000-04-03 KR KR1020017014226A patent/KR20020003878A/en not_active Application Discontinuation
- 2000-04-03 JP JP2000617703A patent/JP2002544332A/en active Pending
- 2000-04-03 WO PCT/US2000/008781 patent/WO2000069232A1/en not_active Application Discontinuation
- 2000-04-03 EP EP00920046A patent/EP1203515A1/en not_active Withdrawn
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| Publication number | Publication date |
|---|---|
| KR20020003878A (en) | 2002-01-15 |
| JP2002544332A (en) | 2002-12-24 |
| WO2000069232A1 (en) | 2000-11-16 |
| EP1203515A1 (en) | 2002-05-08 |
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