WO2000071614A1 - Compositions de resine epoxy hautes performances au cyanate bismaleinimide pour circuits imprimes et agents d'encapsulation - Google Patents

Compositions de resine epoxy hautes performances au cyanate bismaleinimide pour circuits imprimes et agents d'encapsulation Download PDF

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Publication number
WO2000071614A1
WO2000071614A1 PCT/US2000/013943 US0013943W WO0071614A1 WO 2000071614 A1 WO2000071614 A1 WO 2000071614A1 US 0013943 W US0013943 W US 0013943W WO 0071614 A1 WO0071614 A1 WO 0071614A1
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composition
cyanate ester
resin
curing agent
resin composition
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PCT/US2000/013943
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English (en)
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Miguel Albert Capote
Edward Smiley Harrison
Yong-Joon Lee
Howard Arthur Lenos
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Miguel Albert Capote
Edward Smiley Harrison
Lee Yong Joon
Howard Arthur Lenos
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Application filed by Miguel Albert Capote, Edward Smiley Harrison, Lee Yong Joon, Howard Arthur Lenos filed Critical Miguel Albert Capote
Priority to JP2000620000A priority Critical patent/JP2003500509A/ja
Priority to EP00936140A priority patent/EP1196485A4/fr
Priority to AU51501/00A priority patent/AU5150100A/en
Publication of WO2000071614A1 publication Critical patent/WO2000071614A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
    • H01L23/49866—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials
    • H01L23/49894—Materials of the insulating layers or coatings
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/226—Mixtures of di-epoxy compounds
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/36—Epoxy compounds containing three or more epoxy groups together with mono-epoxy compounds
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4042—Imines; Imides
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/065—Preparatory processes
    • C08G73/0655—Preparatory processes from polycyanurates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • 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
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

Definitions

  • This invention relates generally to printed circuits or encapsulated electronics devices, such a silicon chips, coated with curable resin compositions comprising epoxy resins, cyanate esters, bismaleimides, and a co-curing agent.
  • Epoxy resins which represent some of the most widely used resins, are characterized by easy processability, good adhesion to various substrates, high chemical and corrosion resistance, and excellent mechanical properties.
  • epoxy resins have relatively poor performance at high temperatures, have high dielectric constants, and exhibit significant water absorption.
  • Epoxy resins are generally cured by amines and anhydrides. The cured materials typically contain relatively large proportions of hydrophilic groups such as hydroxyl groups which increase water absorption. Epoxy resins thus are sensitive to hydrolysis at high temperature and high humidity.
  • the chemical resistance of epoxy resin is not as good as that of cyanate esters and bismaleimides.
  • Cyanate ester resins have improved performance relative to conventionally cured epoxy resins.
  • Polyfunctional cyanate esters are normally needed to achieve high crosslinking densities and high glass transition temperatures (Tg).
  • Tg glass transition temperatures
  • polyfunctional cyanate esters are typically solid or semi-solid at ambient temperatures and thus the formulated resin systems have relatively high viscosities. These resin systems often require significant amounts of solvents.
  • thermosetting resin Another leading thermosetting resin is bismaleimide which is characterized by excellent physical property retention at high temperatures and high humidities and stable (non-fluctuating) electrical properties over a wide temperature range.
  • bismaleimide particularly suitable for advanced composites and electronics.
  • Bismaleimides are capable of good performance at temperatures of up to about 230 °C to 250 °C with good hot- wet performance.
  • bismaleimide homopolymers are brittle and as a result are susceptible to microcracking.
  • the chemical resistance of bismaleimides is poor in the presence of base compounds.
  • bismaleimide is combined with cyanate ester to create a resin class generally known as BT resins. These resins provide improved glass transition temperature performance and other improved properties as compared to epoxy resins. They are also less expensive than cyanate ester resins.
  • the mixture of cyanate esters and bismaleimides exhibits little co-polymerization, therefore, the combination has inferior properties compared to pure cyanate ester or bismaleimide resins.
  • thermosetting resins demonstrating both high temperature performance and improved physical toughness, especially for microvia and encapsulated electrical interconnect electronics applications, such as printed circuits, flip chips, BGAs and chip scale packages.
  • This invention relates to a resin system comprising a mixture of epoxy resins, bismaleimides, cyanate esters and low viscosity co-curing agents that can be applied to a printed circuit, a silicon chip or wafer, or other electronic component, encapsulating it with a dielectric. Openings can be created in the encapsulating resin by conventional methods such as laser drilling, photoimaging, plasma, or other techniques known in the art. These openings can be metallized to form highly reliable electrical interconnections.
  • the inventive resin system demonstrates the excellent processability, adhesion, chemical and corrosion resistances, and mechanical qualities normally associated with epoxy resins; the system also exhibits superior physical and chemical properties as well as the stable electrical properties associated with bismaleimides and cyanate esters. All of these are highly desirable characteristics for encapsulants, microvia and interconnection applications.
  • the invention is directed to a curable composition that includes: (a) a cyanate ester;
  • a co-curing agent having the structure R ⁇ Ar-R 2 wherein Ar is at least one unsaturated aromatic carbox lic moiety, R 1 is at least one unsaturated aliphatic moiety and R 2 is at least one epoxide moiety with the proviso that when two or more unsaturated aromatic carboxylic moieties are present, at least one of the unsaturated aromatic carboxylic moieties has an unsaturated aliphatic moiety and an epoxide moiety attached thereto;
  • Preferred curing agents are 2-allylphenyl glycidyl ether and 2,2'-bis (3- ally-4-glycidoxy phenyl) isopropylidene, hereinafter referred to as 2,2' - diallylbisphenol A diglycidyl ether.
  • the co-curing agent reacts with the cyanate ester, epoxy resin and bismaleimide.
  • the viscosity of the co-curing agent is low enough at room temperature so that no solvent is generally necessary.
  • the crosslinking density of the cured composition can be varied over a wide range by adjusting the relative proportions of each component in the resin mixture.
  • the invention is based in part on the integration of (i) a glycidyl group, which is reactive with cyanate ester, and (ii) an unsaturated aliphatic group such as an allyl group, which is reactive to bismaleimide, into a co-curing agent molecule.
  • this co-curing agent in the inventive resin system not only makes it possible to co-cure cyanate ester and bismaleimide, in addition, it reduces the viscosity of the resin system because of the low viscosity of the co- curing agent. Furthermore, the combination of epoxy resin with the cyanate ester by means of well-established curing reactions produces a cured composition with the before mentioned desirable properties. For example, the thermal stability, high temperature performance and hot-wet resistance of the cured inventive resin system are superior to those of conventional amine and anhydride cured epoxy resins. In addition, the uncured resin exhibits excellent processability while the cured resin system demonstrates toughness and chemical resistance that are superior to those from bismaleimide or cyanate ester homopolymers.
  • Figure 1 are tan delta dynamic mechanical analyzer (DMA) scans from two resin mixtures showing the glass transition temperatures of two test resin mixes, one with and one without the co-curing agent APGE;
  • Figure 2 is the thermogravimetric scans for a cyanate ester-bismaleimide- epoxy resin mixture with APGE;
  • Figure 3 are thermal decomposition weight loss scans for (i) resins having APGE (ii) resins having DADE, and (iii) FR-4 epoxy laminate;
  • Figure 4 is the DMA scan of an inventive resin composition
  • Figure 5 is the DMA scan of an inventive resin composition
  • Figure 6 is the thermal mechanical analyzer scan of same inventive resin composition of Figure 5;
  • Figure 7 are differential scanning calorimetry scans of bismaleimide-co- curing agent mixtures with and without a free-radical initiator;
  • Figures 8, 9, and 10 illustrate encapsulation of an electronic device with a resin composition;
  • Figures 11, 12, and 13 illustrate encapsulation of a printed circuit board with a resin composition.
  • the present invention is based in part on the development of a resin system comprising cyanate ester resins, bismaleimides, co-curing agents and epoxy resins.
  • the co-curing agent comprises two different reactive groups: (i) a moiety having an unsaturated aliphatic group capable of reacting with bismaleimides, e.g. , an allyl group, and (ii) a glycidyl ether, that is capable of reacting with cyanate esters.
  • the physical properties of the pre and post cured inventive resin system can be varied by employing different proportions of cyanate esters, epoxy resins, bismaleimides, and co-curing agents.
  • Advantageous characteristics of the inventive resin system include, for example:
  • the hot- wet performance of the cured composition is much better than that of conventionally cured epoxy resins.
  • the co-curing agent has the structure R 1 -Ar-R 2 where Ar comprises is at least one aryl moiety, R 1 is at least one unsaturated aliphatic moiety and R 2 is at least one glycidyl ether moiety.
  • Ar preferably has one aryl moiety but it is understood that it can comprise multiple aromatic moieties linked linearly (e.g. a novolac), or by branching (e.g. triphenyl, tetraphenyl).
  • each aryl moiety has at least one of (i) an unsaturated aliphatic moiety and (ii) a glycidyl moiety attached thereto, with the proviso that the co-curing has at least one of each moiety.
  • the number of aromatic moieties in Ar is typically less about than
  • aryl refers to an unsaturated aromatic carbocyclic group of 6 to 14 carbon atoms having a single ring (e.g., phenyl) or multiple condensed rings (e.g. , naphthyl or anthryl).
  • Preferred aryls include phenyl, naphthyl and the like.
  • Preferred co-curing agents have structure I or II:
  • each of R 1 and R 2 is preferably H, CH 3 or CF 3 .
  • Both structures can be further substituted with, for example, lower alkyls having preferably 1-6 carbons more, preferably 1-3 carbons and halides CI, Br or F.
  • Particularly preferred co- curing agents are 2-allylphenyl glycidyl ether (APGE), and 2,2' -diallylbisphenol A diglycidyl ether (DADE) which have the following structures III and IN, respectively:
  • APGE and DADE can be synthesized in accordance with the following well-established reaction mechanism:
  • Suitable cyanate esters are polyfunctional molecules or oligomers having at least two -OCN groups. Cyanate esters are self reactive and also cure in the presence of epoxy resin or bismaleimide. Suitable polyfunctional cyanate esters are described, for example, in U.S. Patents 4,831,086, 5,464,726, 4,195,132, 3,681,292, 4,740,584, 4,745,215, 4,776,629 and 4,546,131, which are incorporated herein. Preferred polyfunctional cyanate esters include the following:
  • x is any suitable divalent moiety, such as -O-, a lower alkylene -(CH ⁇ ) m - where m is 1-6, preferably 1-3, and most preferably 1, -CH 3 CH 2 -, -CH 3 CH 3 CH 2 - ,or other functional divalent group.
  • a preferred polyfunctional cyanate ester used for its superior dielectric properties is:
  • n is an integer from 0 to 200 and preferably from 0 to 1.
  • n has an average value of about 0.4.
  • the polyfunctional cyanate serves to increase the density of cured resin composition.
  • the polyfunctional cyanates react with the epoxy resin and the epoxide group in the co-curing agent thereby forming crosslinked polymeric networks.
  • Polyfunctional cyanate esters are typically solid at ambient temperatures ( 25 °C) but dissolve readily in the co-curing agent and the epoxy resin, although some warming may be needed to bring about solution.
  • Suitable epoxy resins include any of a variety of polyfunctional epoxy resins that are known or commercially available. Suitable epoxy resins are described, for example, in U.S. Patent 5,464,726, which is incorporated herein. Preferred commercially available epoxy resins include, for example, bisphenol A epoxy resins, e.g. Shell EPON 800 series, bisphenol F, epoxy novolac, epoxy cresol novolac, N,N-diglycydyl-4-glycidoxy aniline, and 4,4'-methylenebis(N,N- diglycidylaniline).
  • bisphenol A epoxy resins e.g. Shell EPON 800 series
  • bisphenol F epoxy novolac
  • epoxy cresol novolac epoxy cresol novolac
  • N,N-diglycydyl-4-glycidoxy aniline and 4,4'-methylenebis(N,N- diglycidylaniline).
  • exemplary commercially available epoxy resins are available as Dow Tactix 742, Shell RSL-1107, EPON 825, EPON 828, EPON 1031 , SU-3, SU-8, and Ciba-Geigy Araldite LT8011 , LT8052, LT8047,
  • R is any suitable divalent functional moiety such as, e.g., a lower alkylene -(CHi),..-, where m is 1-6, preferably 1-3, and most preferably 1.
  • a preferred divalent functional moiety is:
  • Suitable bismaleimides are further described, for example, in U.S. Patents 5,464,726 and 4,978,727, which are incorporated herein.
  • a preferred bismaleimide is MDA Bismaleimide Resin 5292A from Ciba Geigy.
  • heat triggered initiators There are two preferred types of free radical initiators: heat triggered initiators and energetically-triggered initiators. Examples of heat triggered initiators are lauryl peroxide and tert-butyl peroxide. Heat triggered initiators operate by decomposing at the trigger temperature, thereby creating free radicals as follows: heat R O O R »- 2 R O •
  • the newly formed free radical continues the chain reation.
  • energetically-triggered initiators also produce free radicals which initiate the chain growth polymerization of unsaturated bonds in the bismaleimide and the co-curing agent.
  • these are triggered by actions of energetic photons, as from an ultraviolet light source, or electrons, as from a plasma or electron beam, instead of by heat.
  • the free radical initiator agent when employed, comprises about 0.1 % to 3 % , preferably 0.1 % to 2% and more preferably 0.5% to 1.5% by weight of the curable composition.
  • Cyanate esters can homopolymerize to produce symmetrical aryl cyanurate rings:
  • Ar groups are aryl groups.
  • Cyanate esters and epoxides co-polymerize through a complex series of rearrangement and substitution reactions, forming heterocyclic 5- or 6-membered rings.
  • Specific examples include oxazoline rings and oxazolidinone rings:
  • Bismaleimides are known to free-radical polymerize with heat, with or without the presence of free radical initiators, as follows:
  • Incorporating epoxy resins into the polymer also provides for improved adhesion of the polymer to surfaces as compared to pure cyanate esters and/or bismaleimide resins. This combination of improved characteristics— lower dielectric constant, lower thermal expansion, higher glass transition temperature, better toughness, lower water absorption, better chemical resistance, better adhesion and higher decomposition temperature— is essential for producing printed circuitry and encapsulants for silicon and other electronic devices.
  • co-curing agents are generally very low viscosity liquids at or near room temperature so they function as excellent solvents for the cyanate esters and bismaleimides. Alone, or in combination with liquid epoxy resins, the co-curing agents dissolve the cyanate esters and bismaleimides to form room temperature or hot melt liquid resin mixtures that are completely free of volatile solvents. This is an important property in the fabrication of encapsulants and microvia dielectric layers as it permits creation of liquid pastes and resins that can be applied in relatively thick layers to electronic components in one step and cured without evolution of volatile solvents that create voids.
  • solvents include, for example methyl ethyl ketone, chloroform, methylene chloride, acetone, and 1-methyl 2-pyrrolidinone.
  • Another significant advantage of the inventive resin composition is that the addition of free-radical polymerization initiators creates resin systems that can be multistage-cured. This allows application of the resin composition in liquid form, which is subsequently hardened by heat or ultraviolet light.
  • a thermally-initiated, low-temperature triggered free radical initiator such as lauryl peroxide
  • lauryl peroxide allows polymerization to be initiated at a temperature between about 100°- 130°C.
  • a resin composition comprising such an initiator can be used to coat an electronic component or circuit board with a liquid encapsulant that is then partially cured by heating to the initiator trigger temperature. This creates a partially polymerized solid, which, though not completely polymerized, will no longer flow like a low-viscosity liquid.
  • Such a resin composition can be applied by screen printing, curtain coating or other method known to one skilled in the art. The coated component or circuit can then be heated rapidly to a temperature at which the free radical polymerization can occur to complete the polymerization.
  • a pre-cured or partially cured resin composition allows easy post processing by means of laser or plasma etching, two common methods used in the creation of microvias.
  • the low polymerization density of the polymer at this first stage of curing allows very rapid and low-energy laser drilling and plasma etching to occur, thereby greatly speeding up the laser drilling process. This provides substantial advantages in the manufacture of microvia components where speed translates into significant cost and manufacturing advantages.
  • Another approach to free radical polymerization is to use an ultraviolet sensitive photoinitiator. Instead of heat, radiation (e.g. , electrons or ultraviolet light) is used in the first stage of curing and solidifying the liquid resin composition. After this first light-initiated cure, the coated part can be laser or plasma drilled as previously indicated.
  • radiation e.g. , electrons or ultraviolet light
  • the photoinitiator induces a chain reaction or chain growth polymerization of unsaturated carbon-carbon bonds. This type of curing is effective for achieving a first stage crosslinking for photoimaging.
  • the mask can be made of any suitable UN blocking/absorbing material with openings through which UN radiation can be transmitted.
  • the non-exposed portions of the resin composition will form the microvias which typically have a diameter of about 20 ⁇ m to 200 ⁇ m. Any unexposed resin composition can then be dissolved away, leaving the image of the mask. Then the image can be completely hardened with heat.
  • the polymer can be applied in thin coats or layers that can be instantly UN-cured to a gel-set by the UN light initiated reaction.
  • the unexposed resin composition can then be washed away with a suitable solvent. Finally heat is applied to effect a deep and complete cure of the polymer resin.
  • the resin composition is prepared as a viscous liquid and is then applied to an electronic component or printed circuit board.
  • a very high viscosity composition is preferred since it will remain in place without polymerization while the ultraviolet light is used to image the microvias through a photomask. This selective exposure produces some regions in the resin which are cured partially and other regions which are completely uncured by being masked from the ultraviolet light by the photomask.
  • the coated component or printed circuit board is developed in an aqueous or organic solution of KOH.
  • the developer dissolves the unexposed resin regions away, leaving behind the ultraviolet polymerized portions of the resin on the component or printed circuit board.
  • microvias are present in the resin system. This allows a rapid and inexpensive way to fabricate many microvias at one time using simple photo exposure techniques.
  • Subsequent full hardening of the resin occurs by heating the coated component, with its microvias, to the final curing temperature of the resin to produce a fully polymerized polymer with its final ideal properties. For this reason, a combination of heat and UN is most effective for photoimaging.
  • cyanate ester and bismaleimide are each capable of self- polymerization.
  • concentrations of cyanate ester and bismaleimide can each vary from 1 to 99% of the molar concentration of the resin composition and still achieve complete polymerization.
  • the epoxy resin which does not self-polymerize needs the cyanate ester for the reaction to occur.
  • it is necessary to account for the epoxide in the co-curing agent as this reactive group also will consume cyanate esters during polymerization.
  • the epoxide molar equivalent concentration in the resin composition is preferably equal to or less than the cyanate ester molar equivalent concentration.
  • the co-curing agent concentration is preferably less than the lesser of the cyanate ester or the bismaleimide molar equivalent concentrations. Any resin composition prepared within these "proportional" limitations, will provide a fully polymerized polymer when cured.
  • the cyanate ester comprises about 3 to 5 molar equivalent parts of the composition
  • the epoxy resin comprises 1.5 to 5 molar equivalent parts of the composition
  • the bismaleimide comprises 0.5 to 1.5 molar equivalent parts of the composition
  • the co-curing agent 0.5 to 1.5 molar equivalent parts of the composition, subject to the above proportional limitations.
  • the above molar equivalent proportions are based on resin compositions containing no solvents, catalysts, fillers, e.g. , silica, or free-radical initiators, which are optional. More preferred are resin compositions comprising these proportions and also comprising 100 to 500 parts per million of cyanate ester weight of a cyanate catalysts such as copper (II) acetyl acetonate.
  • preferred resin compositions are those that are stoichiometrically balanced and which use minimal amounts of co-curing agent and bismaleimide.
  • preferred resin compositions include 5 to 6 molar equivalent parts cyanate ester, 1.5 to 5 molar equivalent parts epoxy resin, 200 to 400 parts per million of cyanate ester equivalent of a cyanate catalysts such as copper (II) acetyl acetonate catalyst, and 0.75 to 1.25 molar equivalent parts each of bismaleimide and co-curing agent, with the proportions of bismaleimide and co-curing agent being equal.
  • the components are mixed and heated in order to melt the bismaleimide and the polyfunctional cyanate ester which are solids.
  • the mixture is heated to a temperature range of about 70°C to 115°C until the mixture is a liquid.
  • a solvent such as methyl ethyl ketone or acetone can be added to the formulation to facilitate processability.
  • the co-curing agent and the bismaleimide monomers can be first pre-reacted. This can be done by stirring the two components under heat at about 115° C for four or five hours. This pre- reaction causes the allyl in the co-curing agent and the bismaleimide to co-react, forming a light slurry which readily dissolves with the cyanate ester and the epoxy during resin mixing.
  • the inventive resin composition can be cured by heat.
  • the curing temperature range is from about 100°C to 250°C, more preferably from 130°C to 225 °C and most preferably from 150°C to 220°C.
  • the system is initially cured at a lower temperature of about 120°C to 140°C for about 2 hours and is followed by post curing treatment (at 210° C to 230 °C) for another hour.
  • the cured resins have high glass transition temperatures ranging from 200°C to 250°C, depending on the component ratios; and the cured resins also exhibit thermal stability against decomposition to a temperature of at least between 350°C and 400°C.
  • the effectively tailored properties from epoxy and bismaleimide include the good adhesion properties, chemical resistance, low water absorption and high heat distortion temperature.
  • a catalyst for trimerization of the cyanate ester is required.
  • Acetylacetonates of various transition metals e.g., Cu, Co, Zn, can be employed at very low concentrations, e.g., a few hundred parts per million.
  • APGE was synthesized from 2-allyl phenol (AP) and epichlorohydrin (EPH) in the presence of aqueous sodium hydroxide at 115° C under nitrogen.
  • the reaction was optimized by using 10 times excess (molar ratio) of EPH and minimizing water in the reaction.
  • water was produced by the reaction between 2-AP and EPH. Since water and EPH form an azeotrope, water was removed from the reaction by azeotropic distillation, which also drives the reaction forward. Collected EPH was returned as needed to the mixture to prevent undesirable side reactions. After 4 hours, the resultant salts were separated from the product.
  • the product was then purified by extraction of the oil phase with toluene, followed by removal of excess EPH and aqueous phase with toluene, which was also used as an azeotropic agent.
  • the product obtained was a thin, yellowish, transparent liquid. Yield was about 90% .
  • Distillation at low pressure (0.3mm of Hg) yielded a water white mobile liquid with a boiling point of 72-72°C. Atmospheric distillation produced a boiling point of 272- 274 °C.
  • the non-optimized curing cycle for the two mixtures was: 2 hour at 125°C, 2 hours at 150°C, 1 hour at 175°C, 2 hours at 200°C.
  • DMA scans of tan delta for the APGE mixture are shown in Figure 2, indicating this mixture had a glass transition at 220 °C.
  • the DMA scans of the DADE mixture were very similar.
  • Figure 3 shows the thermogravimetric scans for the two resins, compared with epoxy FR-4 glass laminate. As is apparent, the glass transition of the FR-4 occurs at less than 150°C.
  • the resins clearly deliver superior thermal properties compared to conventional epoxy resin.
  • Example 5 (cured resin composition 3) To demonstrate thermal characteristics of high epoxy-content resin compositions, a resin mixture was made with the following components:
  • the curing cycle for the mixture was: 2 hours at 125°C, 2 hours at 150°C, 1 hour at 175°C and 2 hrs at 200°C.
  • dynamic mechanical analyzer scans of the cured composition indicate that the glass transition temperature is 242°C.
  • Example 6 (cured resin composition 4)
  • the bismaleimide and APGE were "pre-staged" to minimize loss of the APGE during curing.
  • Equimolar quantities of CIBA 5292A and APGE were pre-mixed. This mixture was co-reacted in a metal can for four hours in a forced-air oven, at about 113°C with continual stirring to produce the bismaleimide- APGE co-reactant. The 113°C temperature was selected to insure safety when staging large batches of this combination of reactants. During this period the initially heavy slurry was transformed to a still heterogeneous but much lower viscosity condition. After cooling to room temperature, the slurry readily dissolved in cyanate resin mixed with epoxy resin. No precipitation of the bismaleimide occurs upon mixing. The mixture showed no changes in visible characteristics at room temperature over long periods of time.
  • a resin composition was mixed with the following molar proportions:
  • a flow control agent CABOSIL PTG (a high-surface area silica ) was added.
  • a surface finish agent for the flow control agent, Z-6040 (Dow Corning) was also employed.
  • the finish agent is an epoxy-containing monomer which couples the silica through the epoxy by co-reacting with the cyanate groups in the resin.
  • To the above mixture was added 5 wt% CABOSIL PTG followed by an additional 0.5 wt% of Dow Z-6040 epoxy silane (trimethoxyglycidoxypropyl silane).
  • a high-shear blender was used to disperse the powder.
  • the final composition consisted of a thixotropic paste that could be readily screen printed through a 100 mesh screen.
  • the curing cycle for the mixture was: 2 hours at 125 °C, 2 hours at 175 °C, 2 hours at 200° C then 1 hour at 225 °C and finally 1 hour at 250° C.
  • dynamic mechanical analyzer scan of the composition indicates that the glass transition temperature is 213 °C.
  • the cured resin's thermal mechanical analyzer scan is shown to have a coefficient of expansion of about 42 ppm/°C below the glass transition temperature.
  • the paste produced in this example was screen printed onto a silicon wafer with a 100 mesh screen and cured per the above cure cycle.
  • the resultant encapsulant was observed to encapsulate the wafer uniformly and without voids or bubbles.
  • Example 7 (cured resin composition 5)
  • FIG. 6 illustrates the effect of the free radical.
  • the top DSC scan is for the mixture without the free radical initiator while the bottom scan is for the mixture with the initiator. Comparing the two scans, the second exotherm that peaks at about 370 °C in the top scan is observed to be unaffected by the free radical by appearing in both scans. However, the two exotherms that peak at about 250 °C in the upper scan have disappeared and have been replaced with a new exotherm at 102° C in the bottom scan.
  • Example 8 (cured resin composition 6)
  • the photoinitiator absorbs UN radiation followed by a subsequent reaction to give a free-radical initiator.
  • a thin layer of the photosensitive resin composition from a chloroform solution (i.e. , 2 ml/2 g concentration) was applied to an epoxy printed circuit boards. The thickness of the layer was not carefully controlled, but was about 0.001 in thick.
  • the "image” was developed by using either an acetone/water mixture (5 volume parts acetone to 1 volume part water) or a saturated aqueous solution of sodium carbonate. The edge of the exposed to unexposed region was readily discernable in the resin.
  • the developed resin was dried and post cured at 125 °C for 2 hours followed by 175 °C for 2 hours. The curing was monitored by Fourier Transform
  • FTIR Infrared
  • Figure 8 shows a flip chip or ball grid array device 1 which has electrical interconnection pads 2 on its surface.
  • the pads are encapsulated with a layer of the inventive resin 3.
  • Microvias 4 are created in the encapsulating resin layer 3 to expose the electrical interconnection pads 2 as shown in Figure 9 and Figure 10 shows that the microvias have been filled with electrically conductive interconnect material 5 e.g., solder.
  • Figure 11 shows a printed circuit board 6 having electrical interconnections pads 7 where the board 6 is encapsulated with a layer of the inventive resin composition 8.
  • Figure 12 the presence of microvia openings 9 in the encapsulating resin layer to expose the electrical interconnection pads 6.
  • Figure 13 shows the printed circuit board 6 wherein the microvias 9 and surface of the encapsulant 8 have been plated with electrically conductive interconnect material 10 e.g., copper.
  • electrically conductive interconnect material 10 e.g., copper.
  • the device has a patterned of the electrically conductive interconnect material that produces selected electrical interconnections between various microvias 11.

Abstract

Cette invention concerne une composition utile comme agent d'encapsulation pour composants électroniques et comme couches diélectriques avec voies d'interconnexion microscopiques pour circuits imprimés. Cette composition réunit les avantages de chaque composant et compense la faiblesse d'autres composants grâce au mélange d'un cyanate ester, d'un bismaléimide, d'un agent co-durcisseur avec des fractions aliphatiques et glycidyliques insaturées, une résine époxy et, en option, un initiateur de radicaux libres.
PCT/US2000/013943 1999-05-21 2000-05-22 Compositions de resine epoxy hautes performances au cyanate bismaleinimide pour circuits imprimes et agents d'encapsulation WO2000071614A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2000620000A JP2003500509A (ja) 1999-05-21 2000-05-22 プリント回路及び封止材用の高性能シアネート−ビスマレイミド−エポキシ樹脂組成物
EP00936140A EP1196485A4 (fr) 1999-05-21 2000-05-22 Compositions de resine epoxy hautes performances au cyanate bismaleinimide pour circuits imprimes et agents d'encapsulation
AU51501/00A AU5150100A (en) 1999-05-21 2000-05-22 High performance cyanate-bismaleimide-epoxy resin compositions for printed circuits and encapsulants

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US13535699P 1999-05-21 1999-05-21
US60/135,356 1999-05-21
US09/346,001 1999-06-30

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Cited By (7)

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Publication number Priority date Publication date Assignee Title
WO2010075006A1 (fr) * 2008-12-16 2010-07-01 Dow Global Technologies Inc. Compositions homogènes de bismaléimide/triazine/époxy utiles à la fabrication de stratifiés électriques
CN102250349A (zh) * 2011-04-10 2011-11-23 苏州大学 一种改性双马来酰亚胺/氰酸酯树脂及其制备方法
WO2012083727A1 (fr) * 2010-12-23 2012-06-28 广东生益科技股份有限公司 Composition de résine sans halogène et de tg élevée et préimprégné et stratifié fabriqués à l'aide de celle-ci
CN103173012A (zh) * 2013-03-01 2013-06-26 中国科学院深圳先进技术研究院 双马来酰亚胺-三嗪树脂复合材料、有机基板及其制备方法
EP2660269A1 (fr) * 2010-12-27 2013-11-06 Mitsubishi Gas Chemical Company, Inc. Composition de résine thermodurcissable
CN104479130A (zh) * 2014-12-02 2015-04-01 中国科学院化学研究所 一种含氟低介电损耗的双马来酰亚胺树脂及其制备方法和应用
CN104877134A (zh) * 2015-05-28 2015-09-02 苏州生益科技有限公司 无卤阻燃聚酰亚胺树脂组合物及使用其制作的半固化片及层压板

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010075006A1 (fr) * 2008-12-16 2010-07-01 Dow Global Technologies Inc. Compositions homogènes de bismaléimide/triazine/époxy utiles à la fabrication de stratifiés électriques
WO2012083727A1 (fr) * 2010-12-23 2012-06-28 广东生益科技股份有限公司 Composition de résine sans halogène et de tg élevée et préimprégné et stratifié fabriqués à l'aide de celle-ci
EP2660269A1 (fr) * 2010-12-27 2013-11-06 Mitsubishi Gas Chemical Company, Inc. Composition de résine thermodurcissable
EP2660269A4 (fr) * 2010-12-27 2014-09-03 Mitsubishi Gas Chemical Co Composition de résine thermodurcissable
CN102250349A (zh) * 2011-04-10 2011-11-23 苏州大学 一种改性双马来酰亚胺/氰酸酯树脂及其制备方法
CN102250349B (zh) * 2011-04-10 2012-11-21 苏州大学 一种改性双马来酰亚胺/氰酸酯树脂及其制备方法
CN103173012A (zh) * 2013-03-01 2013-06-26 中国科学院深圳先进技术研究院 双马来酰亚胺-三嗪树脂复合材料、有机基板及其制备方法
CN103173012B (zh) * 2013-03-01 2015-09-16 中国科学院深圳先进技术研究院 双马来酰亚胺-三嗪树脂复合材料、有机基板及其制备方法
CN104479130A (zh) * 2014-12-02 2015-04-01 中国科学院化学研究所 一种含氟低介电损耗的双马来酰亚胺树脂及其制备方法和应用
CN104479130B (zh) * 2014-12-02 2017-02-22 中国科学院化学研究所 一种含氟低介电损耗的双马来酰亚胺树脂及其制备方法和应用
CN104877134A (zh) * 2015-05-28 2015-09-02 苏州生益科技有限公司 无卤阻燃聚酰亚胺树脂组合物及使用其制作的半固化片及层压板

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