CA1200640A - Bismaleimide triazine polymer compositions for making circuit boards - Google Patents
Bismaleimide triazine polymer compositions for making circuit boardsInfo
- Publication number
- CA1200640A CA1200640A CA000425433A CA425433A CA1200640A CA 1200640 A CA1200640 A CA 1200640A CA 000425433 A CA000425433 A CA 000425433A CA 425433 A CA425433 A CA 425433A CA 1200640 A CA1200640 A CA 1200640A
- Authority
- CA
- Canada
- Prior art keywords
- composition
- weight
- polymeric component
- bismaleimide
- bismaleimide triazine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
Abstract
BISMALEIMIDE TRIAZINE POLYMER COMPOSITIONS
FOR MAKING CIRCUIT BOARDS
Abstract of the Disclosure A composition suitable for making circuit boards containing a bismaleimide triazine polymer, a brominated epoxy polymer, and a solvent is provided.
FOR MAKING CIRCUIT BOARDS
Abstract of the Disclosure A composition suitable for making circuit boards containing a bismaleimide triazine polymer, a brominated epoxy polymer, and a solvent is provided.
Description
64~
BISMALEIMIDE TRIAZINE POLYMER COMPOSITIONS
FOR MAKING CIRCUIT BOARDS
Description of Invention Technical Field The present invention is concerned with a composition containing a bismaleimide triazine polymer. The com-positions of the present invention are especially ` suitable as the matrix material for printed circuit boards. In particular, the present invention is con-cerned with a solution containing a bismaleimide tri-azine polymer and solvent which exhibits extraordi-nary stability characteristics.
Background Art Cir,cuit boards find a wide variety of uses in the electxical industry such as for radios, televisions, appliances, and various electrical apparatus. A
widely employed technique or preparins circuit boards is to impregnate a ~oven fiberglass sheet with a resin composition and then laminate a copper sheet to one or both sides of the resin impregnated fiber-glass sheet. Next, an electrical circuit is etchedinto the copper to form the circuit board and then electrical connections can be soldered to the board when it is used.
~Z~.3()~
. dlO23 - 2 -Various resins have been suggested for the purpose ofimpregnating the fiberglass to prepare the circuit boards. For instance, polyimide resins have been used for such purpose. The use of the polyimide res-ins provides good quality circuit boards which pos-sess high resis~ance to elevated temperatures, low thermal expansion, and good electrical prsperties in-cluding high electrical resistivity. However, cir-cuit boards prepared from polyimide resins are rela-tively expensive when compared to circuit boards pre-pared from epoxy resin impregnated fiberslass sheets.
Circuit boards of epoxy resin impregnated fiberglass sheets, although much less e~pensive than those preC
pared using polyimide resins, are not especially re-sistant to high temperatures, have reduced electricalproperties and higher thermal expansion when compared to circuit boards of polyimide resin impregnated fi-berglass sheets. In addition, other types of resin systems have been suggested for this purpose. For instance, a combination of certain epoxy resins and certain specific bismaleimide materials are suggested in U.S. Patent Nos. 4,294,877 and 4,294,743.
Moreover, bismaleimide triazine resins have bee~ sug-gested as a possible binder or matrix material for printed circuit boards. However, such materials do not form a stable solution in various low boiling point solvents. It is desirable to use low boiling solvents to assist in the rapid application of the resin when attempting to employ such for the purposes of preparing printed circuit boards. One suggestion to prevent such resins from coming out of the solu-tion is to include a solvent such as dimethyl forma-mide or N-methyl pyrrolidone. Along these lines see page 11 of High Heat Resistant Polyimide Resin BT
Resin Bismaleimide Triazine (the third edition), Mitsubishi Gas Chemical Company, Inc.
r ~810~3 Resin composi~ion when cured should desirably e~hibit a relatlvely high gLass transition temperature and possess high resistance ~o elevated temperatures. Ac cordlngly, compositions to be suitable as the matri:~
material for integrated circuit boards must possess a - number of diverse characteristics including relative-ly high glass transition temperature when cured, solu-bility and s~ability in low boiling point solvents, adhesion to the fiberglass sheets, low thermal expan--10 sion and high electrical resistivity.
Summary of Invention The present invention provides a composition which ex-hibits extraordinary stability characteristics in low boiling point solvents. In addition, the composi-tions of the present invention have very high resis-tance to elevated temperatures and have very low thermal expansion characteristics when cured.
The composition of the present invention comprises about 70 to about 80% by weight of a bismaleimide tria-zine polymer, and about 20 to about 30~ by weight ofa brominated epoxy polymer. The above amounts are based upon the total amount of bismaleimide triazine an~ brominated epoxy pol~mer present in the composi-tion. The composition also includes a solvent in an amount of about 10 to about 70~ by weight based upon - the total weight of the bismaleimide triazine and epoxy polymer and solvent present in the composition.
The brominated epoxy polymer contains at least about 45~ by weight of bromine and is a tetrabrominated di-glycidyl ether of a phenol. The present invention is also concerned with a product comprising a fibrous substrate impregnated with the composition discussed above and a curing agent.
12~(~6~L~
~' Best and Various Modes for Carrying out the Invention The compositions of the present invention contain a bismaleimide triazine polymer as tile major solid com-ponent of the composition. Blsmaleimide triazine polymers are commercially available such as under the trade deslgnation BT resin*from Mitsubishi Gas Chemi~
cal Company, Inc., Tokyo, Japan. Discussions of bis-maleimide tria~ine resins can be found in the follow-10 ing:
High Heat Resistant Resin BT Resin (Bismaleimide Triazine), Mitsubishi Gas Chemical Company, Inc.
High Heat Resistant Resin BT Resin (Bismaleimide Triazine)(the second edition), Mitsubishi Gas Chemical Company, Inc.
High Heat Resistant Polyimide Resin BT Resin (Bismaleimide Triazine) (the third edition), Mitsubishi Gas Chemi-cal Company, Inc.
Chemical Economy and Engineering Re-view, March 1978, volume 10, number 3 (no. 115), Triazine Chemistry and Its Application Development-Triazine and BT
Resins as High Performance Materials~
Ayano.
Technical Bulletin BT Resin *(Bismaleimide Triazine Resin) BT 2420, Mitsubishi Gas Chemical Company, Inc.
Technical Bulletin BT Resin (Bismaleimide Triazine Resin) BT 212OA, Mitsubishi Gas Chemical Company, Inc.
The disclosures in the above-iden-ti~ied materials The bismaleimide triazine polymers employed according to the present invention are thermosetting polyimide resins of additional polymerization type containing * Trade mark r~
EN981023 _ 5 ~ 064~
triazine and bismaleimide moieties. Bismaleimide-tri zine is a polymer of bisphenol A-dicyanate and the bis-imide of 4, 4' diaminodiphenyl methane and maleic anhy-dride. The following is a representative model of bis-maleimide-triazine polymer.
C - C ~ ~ C ~_ ~ n + N C - O ~ C ~
A r ~ r Ar.
O ~.
- A r. - O - C C - O - Ar, - O - C C - C ~ , C ` C' C ~ N
`N'~ I I N-Ar,-~N
C', ' C~ "C ~ ` N ~
Ar. Ar, O\~ H . , ~ ,,0 0 1~ 0 -Ar--Ni C-N N C'' ~ ,`c~c-c~
~C,C~C~0-Ar--O-~ C~c' ~ C . C~ ,C~ ~
H H O O H
Il C--N
(1111 0 ~r.
11-'1 ~
The preferred resins employed according to the pres-ent invention are solid and are available under the trade designation BT 2000*Series and most preferably BT 2170*and BT 2120*A from Mitsubishi Gas Chemical Company, Inc. The preferred resins are obtained from mixturescontaininq at least about 50% by weight of the bisphenol-A-dicyanate.
The other essential polymeric material present in the compositions of the present invention is a brominated epoxy polymer. The brominated epoxy polymer must have at least 45% by weight and preferably at least about 50% by weight of bromine and must be a tetra-* Trade mark ~Z~6~D
r ~81023 - 6 -brominated diglycidyl 0ther of a phenol. The phenols are polynuclear dihydric phenols and are xepresented by the formula:
- (A)x (Al)y ~
HO Ar - Rl lr OH
wherein Ar ls an aromatic divalent hydrocarbon such as naphthylene and, preferably, phenylene, A and ~1 which can be the sa~e or different are alkyl radicals, preferably having from 1 to ~ carbon atoms, halogen atoms, i.e., fluorine, chlorine, bromine and iodine, or alkoxy radicals, preferably having from 1 to 4 carbon atoms, x and y are integers having a value 0 to a maximum value corresponding to the number of hy-drogen atoms on the aromatic radical (Ar) which can be replaced by substituents and Rl is a bond bet~een adjacent carbon atoms as in dihydroxydiphenyl or is a divalent radical including, for example, --C ~ 0--,--S--,--SG~ SO2--and--S--S--Il , and divalent hydrocarbon radicals, such as alkylene, alkylidene, cycloaliphatic, e.g., cycloalkylene and cycloalkylidene, halogenated, alkoxy or aryloxy sub-stituted alkylene, alkylidene and cycloaliphatic rad-icals as well as alkarylene and aromatic radicals in-cluding halogenated, alkyl, alkoxy or aryloxy substi-tuted aromatic radicals and a ring fused to an Argroup; or Rl can be polyalkoxy, or polysiloxy, or two or more alkylidene radicals separated by an aromatic ring, a tertiary amino group, an ether linkage, a carbonyl group or a sulfur containing group such as sulfoxide~
Examples of specific dihydric polynuclear phenols are the bis-(hydroxyphenyl)alkanes such as 2,2-bis-(4-hy-:~Z(~l:?64~:) droxyphenol)propane, 2,4'-dihydroxydiphenylmethane, bis-(2-hydroxyphenyl~methane, bis-l4-hydroxyphenyl) methane, bis-(4-hydroxy-2,~-dimethyl-3-methoxyphenyl) methane, l,l-bis-(4-hydroxyphenyl)ethane, 1,2-bis-(4-S hydroxyphenyl)ethane, 1,1-bis-(4-hydroxy-2-chlorphen-yl)ethane, l,l-bis-(3-methyl-4-hydroxyphenyl)ethane, 1,3-bis-(3-methyl-4-hydroxyphenyl)propane, 2,2-bis-(2-isopropyl 4-hydroxyphenyl)propane, 2,Z-bis-(4-hy-droxynaphthyl)propane, 2,2-bis-(4-hydroxyphenyl)pen-tane, 3,3-bis-(4-hydroxyphenyl)pentane, 2,2-bis-(4-hydroxyphenyl)heptane, bis-(4-hydroxyphenyl)phenyl-methane, bis-(4-hydroxyphenyl)cyclohexylmethane, 1,2-bis-(4-hydroxyphenyl)-1,2-bis-(phenyl)propane and 2,
BISMALEIMIDE TRIAZINE POLYMER COMPOSITIONS
FOR MAKING CIRCUIT BOARDS
Description of Invention Technical Field The present invention is concerned with a composition containing a bismaleimide triazine polymer. The com-positions of the present invention are especially ` suitable as the matrix material for printed circuit boards. In particular, the present invention is con-cerned with a solution containing a bismaleimide tri-azine polymer and solvent which exhibits extraordi-nary stability characteristics.
Background Art Cir,cuit boards find a wide variety of uses in the electxical industry such as for radios, televisions, appliances, and various electrical apparatus. A
widely employed technique or preparins circuit boards is to impregnate a ~oven fiberglass sheet with a resin composition and then laminate a copper sheet to one or both sides of the resin impregnated fiber-glass sheet. Next, an electrical circuit is etchedinto the copper to form the circuit board and then electrical connections can be soldered to the board when it is used.
~Z~.3()~
. dlO23 - 2 -Various resins have been suggested for the purpose ofimpregnating the fiberglass to prepare the circuit boards. For instance, polyimide resins have been used for such purpose. The use of the polyimide res-ins provides good quality circuit boards which pos-sess high resis~ance to elevated temperatures, low thermal expansion, and good electrical prsperties in-cluding high electrical resistivity. However, cir-cuit boards prepared from polyimide resins are rela-tively expensive when compared to circuit boards pre-pared from epoxy resin impregnated fiberslass sheets.
Circuit boards of epoxy resin impregnated fiberglass sheets, although much less e~pensive than those preC
pared using polyimide resins, are not especially re-sistant to high temperatures, have reduced electricalproperties and higher thermal expansion when compared to circuit boards of polyimide resin impregnated fi-berglass sheets. In addition, other types of resin systems have been suggested for this purpose. For instance, a combination of certain epoxy resins and certain specific bismaleimide materials are suggested in U.S. Patent Nos. 4,294,877 and 4,294,743.
Moreover, bismaleimide triazine resins have bee~ sug-gested as a possible binder or matrix material for printed circuit boards. However, such materials do not form a stable solution in various low boiling point solvents. It is desirable to use low boiling solvents to assist in the rapid application of the resin when attempting to employ such for the purposes of preparing printed circuit boards. One suggestion to prevent such resins from coming out of the solu-tion is to include a solvent such as dimethyl forma-mide or N-methyl pyrrolidone. Along these lines see page 11 of High Heat Resistant Polyimide Resin BT
Resin Bismaleimide Triazine (the third edition), Mitsubishi Gas Chemical Company, Inc.
r ~810~3 Resin composi~ion when cured should desirably e~hibit a relatlvely high gLass transition temperature and possess high resistance ~o elevated temperatures. Ac cordlngly, compositions to be suitable as the matri:~
material for integrated circuit boards must possess a - number of diverse characteristics including relative-ly high glass transition temperature when cured, solu-bility and s~ability in low boiling point solvents, adhesion to the fiberglass sheets, low thermal expan--10 sion and high electrical resistivity.
Summary of Invention The present invention provides a composition which ex-hibits extraordinary stability characteristics in low boiling point solvents. In addition, the composi-tions of the present invention have very high resis-tance to elevated temperatures and have very low thermal expansion characteristics when cured.
The composition of the present invention comprises about 70 to about 80% by weight of a bismaleimide tria-zine polymer, and about 20 to about 30~ by weight ofa brominated epoxy polymer. The above amounts are based upon the total amount of bismaleimide triazine an~ brominated epoxy pol~mer present in the composi-tion. The composition also includes a solvent in an amount of about 10 to about 70~ by weight based upon - the total weight of the bismaleimide triazine and epoxy polymer and solvent present in the composition.
The brominated epoxy polymer contains at least about 45~ by weight of bromine and is a tetrabrominated di-glycidyl ether of a phenol. The present invention is also concerned with a product comprising a fibrous substrate impregnated with the composition discussed above and a curing agent.
12~(~6~L~
~' Best and Various Modes for Carrying out the Invention The compositions of the present invention contain a bismaleimide triazine polymer as tile major solid com-ponent of the composition. Blsmaleimide triazine polymers are commercially available such as under the trade deslgnation BT resin*from Mitsubishi Gas Chemi~
cal Company, Inc., Tokyo, Japan. Discussions of bis-maleimide tria~ine resins can be found in the follow-10 ing:
High Heat Resistant Resin BT Resin (Bismaleimide Triazine), Mitsubishi Gas Chemical Company, Inc.
High Heat Resistant Resin BT Resin (Bismaleimide Triazine)(the second edition), Mitsubishi Gas Chemical Company, Inc.
High Heat Resistant Polyimide Resin BT Resin (Bismaleimide Triazine) (the third edition), Mitsubishi Gas Chemi-cal Company, Inc.
Chemical Economy and Engineering Re-view, March 1978, volume 10, number 3 (no. 115), Triazine Chemistry and Its Application Development-Triazine and BT
Resins as High Performance Materials~
Ayano.
Technical Bulletin BT Resin *(Bismaleimide Triazine Resin) BT 2420, Mitsubishi Gas Chemical Company, Inc.
Technical Bulletin BT Resin (Bismaleimide Triazine Resin) BT 212OA, Mitsubishi Gas Chemical Company, Inc.
The disclosures in the above-iden-ti~ied materials The bismaleimide triazine polymers employed according to the present invention are thermosetting polyimide resins of additional polymerization type containing * Trade mark r~
EN981023 _ 5 ~ 064~
triazine and bismaleimide moieties. Bismaleimide-tri zine is a polymer of bisphenol A-dicyanate and the bis-imide of 4, 4' diaminodiphenyl methane and maleic anhy-dride. The following is a representative model of bis-maleimide-triazine polymer.
C - C ~ ~ C ~_ ~ n + N C - O ~ C ~
A r ~ r Ar.
O ~.
- A r. - O - C C - O - Ar, - O - C C - C ~ , C ` C' C ~ N
`N'~ I I N-Ar,-~N
C', ' C~ "C ~ ` N ~
Ar. Ar, O\~ H . , ~ ,,0 0 1~ 0 -Ar--Ni C-N N C'' ~ ,`c~c-c~
~C,C~C~0-Ar--O-~ C~c' ~ C . C~ ,C~ ~
H H O O H
Il C--N
(1111 0 ~r.
11-'1 ~
The preferred resins employed according to the pres-ent invention are solid and are available under the trade designation BT 2000*Series and most preferably BT 2170*and BT 2120*A from Mitsubishi Gas Chemical Company, Inc. The preferred resins are obtained from mixturescontaininq at least about 50% by weight of the bisphenol-A-dicyanate.
The other essential polymeric material present in the compositions of the present invention is a brominated epoxy polymer. The brominated epoxy polymer must have at least 45% by weight and preferably at least about 50% by weight of bromine and must be a tetra-* Trade mark ~Z~6~D
r ~81023 - 6 -brominated diglycidyl 0ther of a phenol. The phenols are polynuclear dihydric phenols and are xepresented by the formula:
- (A)x (Al)y ~
HO Ar - Rl lr OH
wherein Ar ls an aromatic divalent hydrocarbon such as naphthylene and, preferably, phenylene, A and ~1 which can be the sa~e or different are alkyl radicals, preferably having from 1 to ~ carbon atoms, halogen atoms, i.e., fluorine, chlorine, bromine and iodine, or alkoxy radicals, preferably having from 1 to 4 carbon atoms, x and y are integers having a value 0 to a maximum value corresponding to the number of hy-drogen atoms on the aromatic radical (Ar) which can be replaced by substituents and Rl is a bond bet~een adjacent carbon atoms as in dihydroxydiphenyl or is a divalent radical including, for example, --C ~ 0--,--S--,--SG~ SO2--and--S--S--Il , and divalent hydrocarbon radicals, such as alkylene, alkylidene, cycloaliphatic, e.g., cycloalkylene and cycloalkylidene, halogenated, alkoxy or aryloxy sub-stituted alkylene, alkylidene and cycloaliphatic rad-icals as well as alkarylene and aromatic radicals in-cluding halogenated, alkyl, alkoxy or aryloxy substi-tuted aromatic radicals and a ring fused to an Argroup; or Rl can be polyalkoxy, or polysiloxy, or two or more alkylidene radicals separated by an aromatic ring, a tertiary amino group, an ether linkage, a carbonyl group or a sulfur containing group such as sulfoxide~
Examples of specific dihydric polynuclear phenols are the bis-(hydroxyphenyl)alkanes such as 2,2-bis-(4-hy-:~Z(~l:?64~:) droxyphenol)propane, 2,4'-dihydroxydiphenylmethane, bis-(2-hydroxyphenyl~methane, bis-l4-hydroxyphenyl) methane, bis-(4-hydroxy-2,~-dimethyl-3-methoxyphenyl) methane, l,l-bis-(4-hydroxyphenyl)ethane, 1,2-bis-(4-S hydroxyphenyl)ethane, 1,1-bis-(4-hydroxy-2-chlorphen-yl)ethane, l,l-bis-(3-methyl-4-hydroxyphenyl)ethane, 1,3-bis-(3-methyl-4-hydroxyphenyl)propane, 2,2-bis-(2-isopropyl 4-hydroxyphenyl)propane, 2,Z-bis-(4-hy-droxynaphthyl)propane, 2,2-bis-(4-hydroxyphenyl)pen-tane, 3,3-bis-(4-hydroxyphenyl)pentane, 2,2-bis-(4-hydroxyphenyl)heptane, bis-(4-hydroxyphenyl)phenyl-methane, bis-(4-hydroxyphenyl)cyclohexylmethane, 1,2-bis-(4-hydroxyphenyl)-1,2-bis-(phenyl)propane and 2,
2-bis-(4-hydroxyphenyl)-1-phenyl-propane; di(hydroxy-phenyl)sulfones such as bis-(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenyl sulfone, 5'-chloro-2,4'-dihy-droxydiphenyl sulfo~e, and 5'-chloro-4,4'-dihydroxy-diphenyl sulfone; di(hydroxyphenyl)ethers such as bis-(4-hydroxyphenyl)ether, the 4,3'-,4,2'-,2,2'-,2,3'-, dihydroxydiphenyl ethers, 4,4'-dihydroxy-2,6-dimethy-ldiphenyl ether, bis-(4-hydroxy-3-isobutylphenyl) ether, bi~-(4-hydroxy-3-isopropylphenyl)ether, bis~(4 -hydroxy-3-chlorophenyl)ether, bis-(4-hydroxy-3-fluo-rophenyl)ether, bis-(4-hydroxy-3-bromophenyl)ether, bis-(4-hydroxynaphthyl)ether, bis-(4-hydroxy-3-chloro-naphthyl)ether, bis-(2-hydroxydiphenyl)ether, 4,4'-di-hydroxy-2,5-diethoxydiphenyl ether.
The preferred dihydric polynuclear phenols are repre-` sented by the formula:
(A)x (Al)y ~( ~ \\O /
r~
)06~0 wherein A and A are as previously deflned, x and y have values from O to 4 inclusive and R is a divalent saturated aliphatic hydrocarbon radical, particularly alkylene and alkylidene radicals having from 1 to 3 carbon atoms, and cycloalkylene radicals having up to and including 10 carbon atoms. The most preferred di-hydric phenol is bisphenol A, l.e., 2,2-bis-(p-hydrox-yphenyl)propane.
The preferred bromina~ed epoxy polymers employed ac-cording to the present invention have a bromine con-tent of at least about 4s% by weight and are commer~
cially available such as under the trade designation Araldite*LT a 049 from Ciba-Geigy Corporation. This brominated epoxy polymer has a melting point o about 55C, an epoxy value (eq/lOOg) of 0.26 and weight per epoxide of about 385.
In addition, in order to achieve all of the necessary properties obtained by the compositions of the pres-ent invention, the relative amounts of the bismalei-mide triazine poly~er and bro~inated epoxy polymermust be about 70 to about 80~ by weight of the tria-zine polymer and correspondingly about 20 to about 30%
by weight o the ~rominated epoxy polymer. The above reLative amcunts are based upon the total of the bis-maleimide triazine polymer and brominated epoxy poly-mer present in the composition. Use of greater amounts of the ~rominated epoxy polymer than employed ` according to the present invention tends to result in significantly lower glass transition temperatures of the cured products. This is detrimental to the intended use-as an impregnant for preparing printed circuit boards. Moreover, as will be demonstrated hereinbelow, use of epoxy polymers with less than 45%
by weight o~ bromine does not provide the combination * Trade mark ,'i.~
~)a6~0 ~81023 of properties crucial to the present invention. In addition, the preferred compositions of the present invention are substantially free from other polymeric materials such as non-brominated epo~y pol~mers, since such adversely lower the glass transition tem ~ ature of the cured ~ositions, ~hich preferably should be at least about 175C.
Furthermore, it has been noted that the stability problem of the bismaleimide ~riazine resin is parti-cularly pronounced when over about 65% by weight of the solids of the compositio~ is the bismaleimide tri-azine resin. At low percentages of the bismaleimide triazine resin, the solubility properties are not noticeable to any significant extent.
The compositions of the present invention also contain an organic solvent. The solvent is preferably a low boiling point solvent and most preferably is a ketone such as acetone or methylethyl l~etone. In the pre~
ferred aspects of the present invention, the solvent is substantially free, if not entirely free, Lrom 501vent5 other than ketones. The solvent is present in amounts of about 10 to about 70~ by weight based upon the total weight of the bismaleimide triazine, the brominated epoxy polymer, and the solvent present in the composition. During storage prior to use, the composition generally contains about 10 to about 60%
by weight of solvent. ~hen the composition is to be employed, the amount of solvent is generally about 20 to about 70~ by weight. Most preferably, during - storage, the relative amount of solvent is about 30 by weight and then the composition is diluted to about 45~ by weight of solvent shortly before use.
In addition, just prior to use, a catalyst is general-ly added to the compositions of the present invention to facilitate curing of the compositions. ~he cata-64~
~1023 - 10 -lysts employed are of the type that initiate oxidation types of reactions. Examples of suitable catal~sts include metal salts of carboxylic acids such as salts of octylic acid and naphthenic acid, including zinc octoate, stannic octoate, zinc naphthenic and cobalt naphthenate; metallic salts of acetylacetone such as ferriacetylacetone and copper acetylacetone; butyl-titanate; propylaluminum; metallic powders such as zinc powder and iron powder; peroxides such as dicu-myl peroxide, benzoyl peroxide, cyclohexanone perox~ide, t-butyl hydroperoxide, decanoyl peroxide, and di-isopropylperoxydicarbonate; amines such as triethy-lene diamine, N,N-dimethylbenzylamine, N-methylmor~
pholine, tri-N-butylamine, and N,N,~l, Nl-tetramethyl-butanediamine; imidazoles such as 2-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, and 2-ethyl-4-methylimidazole; and chlorides such as stannic chlor- -ide, aluminum chloride, ferric chloride, and ferrous chloride. In addition, when desired, mixtures of curing agents can be employed. ~he catalyst employed generally in amounts of about 0.01 to about 5 parts per hundred parts of resin in the composition. The preferred catalyst employed according to the present invention is zinc octoate.
The compositions of the present invention are pref-erably employed to prepare printed circuit boards.
In preparing the boards, a fibrous substrate is coat-ed and impregnated with the composition of the pres-ent invention. Conventional coating equipment can be employed. Subsequent to coatinq, the impregnated substrate is cured at a temperature of about lO0 to about 200C for about 1 to about 10 minutes to form a rigid substrate. The compositions can be used to coat and/or impregnate fibrous substrates such as fiberglass, polyimides, graphite, and the like.
lZ~306940 ~ 381023 ....
After the rigid substrate is formed, a sheet of cop-per or other conductive material can then be laminat-ed to the rigid substrate using laminating conditions such as about 50 to about 400 pounds per square inch, about 50 to 300C for about 30 to about 300 minutes~
Then, a circuit can be etched to the conductive layer using technlques well-known to form circuit boards.
The following non-limiting examples are presented to further illustrate the present invention.
Example 1 About 345.6 parts by weight of a bismaleimide-triazine composition available under the trade designation 3T-2120A and containing about 280 parts by weight of solid polymer and about 65.6 parts by weight methyl-ethyl ketone; about 120 parts by weight of brominated epoxy resin available under the trade designation Araldite LT 8049 having a bromine content of about 50%; about 98.4 parts by weight of additional methyl-e.thyl ketone and about 164 parts by weight of acetone are admixed. The above composition is stable at room temperature for at least 9 months. In addition, the above composition is mixed with about 0.2~ by weight of,a solution.of 8% zinc octoate in mineral spirits.
The composition is then used to impregnate glass fibers and is cured at about 175C using about 200 psi. The results provide good flammability, and an excellent glass transition temperature of about 200C.
Comparison ~:xample 2 About 280 parts by weight of bismaleimide triazine ~0 composition available under the trade designation 3Q~
I '81023 1 ~ --BT-2120A containing about 176 parts by weight bisma-leimide triazine resin and about 44 parts by weight of methylethyl ketone; about 76 parts by weight of brominated epoxide containing about 37 to 38% by 5 weight of bromine and available under the trade des-ignation Araldite I.T-8052; about 49 parts by weight of additional methylethyl ketone; and about 82 parts by weight o~ acetone are admixed. Although the com-~osition upon curing had sufficient glass transition 10 temperature because of the lower amount of bromine present, such was flammable. Also it was not very stable. Precipitation occurred within about 1 month This e~ample illustrates the criticality of the present invention of employing the specific types of 15 brominated epoxy polymers as required by the present invention e~en when the relative amounts of epoxy and ; bismaleimide triazine resin are the same.
Comparison Example 3 Comparison Example 2 is repeated except that the rel-20 ative amount of the bismaleimide triazine resin and brominated epoxide is adjusted to provide a bromine content based on the total solids of about 15~ as in Example 1. The composition contains about 199 parts by ~eight of BT 2120A, about 93 parts by weight of 25 Araldite LT-8052, about 52 parts of additional methyl-ethyl ketone and about 82 parts by weight of acetone.
The composition of this example when cured does not provide sufficient glass transition temperature. The glass transition temperature is about 160C.
3a Comparison Example 3 About 220 parts by ~eight of bismaleimide triazine composition containing about 176 parts by weight of ~IZ~(~6~
~1023 - 13 -bismaleimide triazine resin and about 44 parts by weight methylethyl ke~one available under the trade designation BT~2120A; about 76 parts by weight of brominated epoxy containing about 20~ by weight of bromine and available under the trade designation - Araldite LT-8047 from Ciba-Geigy; about 49 parts by weight of additional methylethyl ketone; and about 82 parts by',weight of acetone are admixed. The com-position contains the same relative amounts of bis-maleimide triazine resin and brominated epoxy as in Example 1. However, the percent of bromine based on the solids is about 6~ and the cured composition is not flameproof as is that of Example l.
Comparison Exa~ple 5 Comparison Example 4 is repeated except that the rela-tive amount of the bismaleimide resin and brominated epoxide is adjusted to provide a bromine content based upon the solids of about 15% as in Example l.
The composition contains about 81 parts by weight of BT-2120A; about 187 parts by weight of'Araldite LT-8047; about 71 parts by weight or additional methyl-ethyl ketone; and about 82 parts by weight of acetone.
The composition contains about 26% by weight of bis-maleimide triazine resin. The glass transition temp-erature of the cured composition is only about 140C.
Accordingly, as demonstrated by the above examples, it is necessary to employ the relative amounts of materials and type of brominated epoxide in order to - achieve the combination of properties obtained by the compositions of the present invention. In particular, . the present invention provides for the combination of flameproof characteristics, storage stability, and upon curing, a high glass transition temperature.
When practicing outside of the range of the composi-6~0 F-`'81023 ~ . . .
tion of the presen~ invention it is not possible to obtain a combination of all of these pxoperties.
~2(~ 0 ~ !
''' . , SUPPLEMENTARY DISCLOSURE~
Bismaleimide triazine polymeric materials employed according to the present invention are thermosetting polyimide resins of additional polymerization type containing triazine and bismaleimide moieties.
Bismaleimide triazine polymeric materials are from the polymerization of bisphenol A-dicyanate and the bisimide of 4,4' diaminodiphenyl methane and maleic anhydride. The following is a representative model of a bismaleimide triazine polymeric material reported by Mitsubishi Gas Chemical Company, Inc., the manufacturer of BT resins.
C - C ~ ~ "C ,H CH~- IJ - C I X
C H C _ C
O ' o I l ,:
Ar2 Ar Ar~
O A~.
o 1. c-O-Ar.-O-C; C ~ c-O-Ar,-Ar, Ar. ; ' O H \ H ~ O H
--A~ - N ~ ~ ;' C ~y ~ C ` C ' C~
,C ~C -O-Ar~-O-1.:, ~, C- C' ~ C -C 1, ~ ;O
~I t) O H ' `
Il l:-N
lilll , O A;
Any particular bismaleimide triazine polymeric component may include one or more of the segments I, II, III, and IV. Moreover, as reported on pages 4 and ~ of High- Heat Resistant Resin BT Resin (Blsmaleimide o~
~, EN9-Rl-023 16 ..;
Triazine) ~the third edition), Mitsubishi Gas Chemical Company, Inc., the bismaleimide triazine polymeric material can include as triazine moiety .,~
- Ar,-O- C - N - Ar.-O-C ~C-O-Ar, . N N
.. ~ C
Ar, and/or as bismaleimide moiety / ~O ~ H H H H H H
I ~IC' \ -jC-C~ -jC-C~ /C-C--r~~ n Oc~\ /C~ ~ \ / ~o Ar~ Ar. Ar2 I I I
. .... . . ..
The preferred bismaleimide triazine polymeric materials employed according to the present invention are solid and are available under the trade designation BT 2000 Series and most preferably, BT 2170 and BT 2120A from Mitsubishi Gas Chemical Company, Inc. The pref~erred resins bismaleimide triazine polymeric materials are~
obtained from mixtures containing at least about 50% by weight of the bisphenol-A-dicyanate. The relative amounts of triazine moieties to bismaleimide moieties are such that the triazine bismaleimide polymeric component is soluble in the organic solvent employed and when combined with the epoxy polymeric material, the cured composition exhibits high resistance to elevated temperatures. Preferably, the relative amount of triazine moieties to bismaleimide moieties is about 5~5:1 to about 9:1.
The preferred dihydric polynuclear phenols are repre-` sented by the formula:
(A)x (Al)y ~( ~ \\O /
r~
)06~0 wherein A and A are as previously deflned, x and y have values from O to 4 inclusive and R is a divalent saturated aliphatic hydrocarbon radical, particularly alkylene and alkylidene radicals having from 1 to 3 carbon atoms, and cycloalkylene radicals having up to and including 10 carbon atoms. The most preferred di-hydric phenol is bisphenol A, l.e., 2,2-bis-(p-hydrox-yphenyl)propane.
The preferred bromina~ed epoxy polymers employed ac-cording to the present invention have a bromine con-tent of at least about 4s% by weight and are commer~
cially available such as under the trade designation Araldite*LT a 049 from Ciba-Geigy Corporation. This brominated epoxy polymer has a melting point o about 55C, an epoxy value (eq/lOOg) of 0.26 and weight per epoxide of about 385.
In addition, in order to achieve all of the necessary properties obtained by the compositions of the pres-ent invention, the relative amounts of the bismalei-mide triazine poly~er and bro~inated epoxy polymermust be about 70 to about 80~ by weight of the tria-zine polymer and correspondingly about 20 to about 30%
by weight o the ~rominated epoxy polymer. The above reLative amcunts are based upon the total of the bis-maleimide triazine polymer and brominated epoxy poly-mer present in the composition. Use of greater amounts of the ~rominated epoxy polymer than employed ` according to the present invention tends to result in significantly lower glass transition temperatures of the cured products. This is detrimental to the intended use-as an impregnant for preparing printed circuit boards. Moreover, as will be demonstrated hereinbelow, use of epoxy polymers with less than 45%
by weight o~ bromine does not provide the combination * Trade mark ,'i.~
~)a6~0 ~81023 of properties crucial to the present invention. In addition, the preferred compositions of the present invention are substantially free from other polymeric materials such as non-brominated epo~y pol~mers, since such adversely lower the glass transition tem ~ ature of the cured ~ositions, ~hich preferably should be at least about 175C.
Furthermore, it has been noted that the stability problem of the bismaleimide ~riazine resin is parti-cularly pronounced when over about 65% by weight of the solids of the compositio~ is the bismaleimide tri-azine resin. At low percentages of the bismaleimide triazine resin, the solubility properties are not noticeable to any significant extent.
The compositions of the present invention also contain an organic solvent. The solvent is preferably a low boiling point solvent and most preferably is a ketone such as acetone or methylethyl l~etone. In the pre~
ferred aspects of the present invention, the solvent is substantially free, if not entirely free, Lrom 501vent5 other than ketones. The solvent is present in amounts of about 10 to about 70~ by weight based upon the total weight of the bismaleimide triazine, the brominated epoxy polymer, and the solvent present in the composition. During storage prior to use, the composition generally contains about 10 to about 60%
by weight of solvent. ~hen the composition is to be employed, the amount of solvent is generally about 20 to about 70~ by weight. Most preferably, during - storage, the relative amount of solvent is about 30 by weight and then the composition is diluted to about 45~ by weight of solvent shortly before use.
In addition, just prior to use, a catalyst is general-ly added to the compositions of the present invention to facilitate curing of the compositions. ~he cata-64~
~1023 - 10 -lysts employed are of the type that initiate oxidation types of reactions. Examples of suitable catal~sts include metal salts of carboxylic acids such as salts of octylic acid and naphthenic acid, including zinc octoate, stannic octoate, zinc naphthenic and cobalt naphthenate; metallic salts of acetylacetone such as ferriacetylacetone and copper acetylacetone; butyl-titanate; propylaluminum; metallic powders such as zinc powder and iron powder; peroxides such as dicu-myl peroxide, benzoyl peroxide, cyclohexanone perox~ide, t-butyl hydroperoxide, decanoyl peroxide, and di-isopropylperoxydicarbonate; amines such as triethy-lene diamine, N,N-dimethylbenzylamine, N-methylmor~
pholine, tri-N-butylamine, and N,N,~l, Nl-tetramethyl-butanediamine; imidazoles such as 2-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, and 2-ethyl-4-methylimidazole; and chlorides such as stannic chlor- -ide, aluminum chloride, ferric chloride, and ferrous chloride. In addition, when desired, mixtures of curing agents can be employed. ~he catalyst employed generally in amounts of about 0.01 to about 5 parts per hundred parts of resin in the composition. The preferred catalyst employed according to the present invention is zinc octoate.
The compositions of the present invention are pref-erably employed to prepare printed circuit boards.
In preparing the boards, a fibrous substrate is coat-ed and impregnated with the composition of the pres-ent invention. Conventional coating equipment can be employed. Subsequent to coatinq, the impregnated substrate is cured at a temperature of about lO0 to about 200C for about 1 to about 10 minutes to form a rigid substrate. The compositions can be used to coat and/or impregnate fibrous substrates such as fiberglass, polyimides, graphite, and the like.
lZ~306940 ~ 381023 ....
After the rigid substrate is formed, a sheet of cop-per or other conductive material can then be laminat-ed to the rigid substrate using laminating conditions such as about 50 to about 400 pounds per square inch, about 50 to 300C for about 30 to about 300 minutes~
Then, a circuit can be etched to the conductive layer using technlques well-known to form circuit boards.
The following non-limiting examples are presented to further illustrate the present invention.
Example 1 About 345.6 parts by weight of a bismaleimide-triazine composition available under the trade designation 3T-2120A and containing about 280 parts by weight of solid polymer and about 65.6 parts by weight methyl-ethyl ketone; about 120 parts by weight of brominated epoxy resin available under the trade designation Araldite LT 8049 having a bromine content of about 50%; about 98.4 parts by weight of additional methyl-e.thyl ketone and about 164 parts by weight of acetone are admixed. The above composition is stable at room temperature for at least 9 months. In addition, the above composition is mixed with about 0.2~ by weight of,a solution.of 8% zinc octoate in mineral spirits.
The composition is then used to impregnate glass fibers and is cured at about 175C using about 200 psi. The results provide good flammability, and an excellent glass transition temperature of about 200C.
Comparison ~:xample 2 About 280 parts by weight of bismaleimide triazine ~0 composition available under the trade designation 3Q~
I '81023 1 ~ --BT-2120A containing about 176 parts by weight bisma-leimide triazine resin and about 44 parts by weight of methylethyl ketone; about 76 parts by weight of brominated epoxide containing about 37 to 38% by 5 weight of bromine and available under the trade des-ignation Araldite I.T-8052; about 49 parts by weight of additional methylethyl ketone; and about 82 parts by weight o~ acetone are admixed. Although the com-~osition upon curing had sufficient glass transition 10 temperature because of the lower amount of bromine present, such was flammable. Also it was not very stable. Precipitation occurred within about 1 month This e~ample illustrates the criticality of the present invention of employing the specific types of 15 brominated epoxy polymers as required by the present invention e~en when the relative amounts of epoxy and ; bismaleimide triazine resin are the same.
Comparison Example 3 Comparison Example 2 is repeated except that the rel-20 ative amount of the bismaleimide triazine resin and brominated epoxide is adjusted to provide a bromine content based on the total solids of about 15~ as in Example 1. The composition contains about 199 parts by ~eight of BT 2120A, about 93 parts by weight of 25 Araldite LT-8052, about 52 parts of additional methyl-ethyl ketone and about 82 parts by weight of acetone.
The composition of this example when cured does not provide sufficient glass transition temperature. The glass transition temperature is about 160C.
3a Comparison Example 3 About 220 parts by ~eight of bismaleimide triazine composition containing about 176 parts by weight of ~IZ~(~6~
~1023 - 13 -bismaleimide triazine resin and about 44 parts by weight methylethyl ke~one available under the trade designation BT~2120A; about 76 parts by weight of brominated epoxy containing about 20~ by weight of bromine and available under the trade designation - Araldite LT-8047 from Ciba-Geigy; about 49 parts by weight of additional methylethyl ketone; and about 82 parts by',weight of acetone are admixed. The com-position contains the same relative amounts of bis-maleimide triazine resin and brominated epoxy as in Example 1. However, the percent of bromine based on the solids is about 6~ and the cured composition is not flameproof as is that of Example l.
Comparison Exa~ple 5 Comparison Example 4 is repeated except that the rela-tive amount of the bismaleimide resin and brominated epoxide is adjusted to provide a bromine content based upon the solids of about 15% as in Example l.
The composition contains about 81 parts by weight of BT-2120A; about 187 parts by weight of'Araldite LT-8047; about 71 parts by weight or additional methyl-ethyl ketone; and about 82 parts by weight of acetone.
The composition contains about 26% by weight of bis-maleimide triazine resin. The glass transition temp-erature of the cured composition is only about 140C.
Accordingly, as demonstrated by the above examples, it is necessary to employ the relative amounts of materials and type of brominated epoxide in order to - achieve the combination of properties obtained by the compositions of the present invention. In particular, . the present invention provides for the combination of flameproof characteristics, storage stability, and upon curing, a high glass transition temperature.
When practicing outside of the range of the composi-6~0 F-`'81023 ~ . . .
tion of the presen~ invention it is not possible to obtain a combination of all of these pxoperties.
~2(~ 0 ~ !
''' . , SUPPLEMENTARY DISCLOSURE~
Bismaleimide triazine polymeric materials employed according to the present invention are thermosetting polyimide resins of additional polymerization type containing triazine and bismaleimide moieties.
Bismaleimide triazine polymeric materials are from the polymerization of bisphenol A-dicyanate and the bisimide of 4,4' diaminodiphenyl methane and maleic anhydride. The following is a representative model of a bismaleimide triazine polymeric material reported by Mitsubishi Gas Chemical Company, Inc., the manufacturer of BT resins.
C - C ~ ~ "C ,H CH~- IJ - C I X
C H C _ C
O ' o I l ,:
Ar2 Ar Ar~
O A~.
o 1. c-O-Ar.-O-C; C ~ c-O-Ar,-Ar, Ar. ; ' O H \ H ~ O H
--A~ - N ~ ~ ;' C ~y ~ C ` C ' C~
,C ~C -O-Ar~-O-1.:, ~, C- C' ~ C -C 1, ~ ;O
~I t) O H ' `
Il l:-N
lilll , O A;
Any particular bismaleimide triazine polymeric component may include one or more of the segments I, II, III, and IV. Moreover, as reported on pages 4 and ~ of High- Heat Resistant Resin BT Resin (Blsmaleimide o~
~, EN9-Rl-023 16 ..;
Triazine) ~the third edition), Mitsubishi Gas Chemical Company, Inc., the bismaleimide triazine polymeric material can include as triazine moiety .,~
- Ar,-O- C - N - Ar.-O-C ~C-O-Ar, . N N
.. ~ C
Ar, and/or as bismaleimide moiety / ~O ~ H H H H H H
I ~IC' \ -jC-C~ -jC-C~ /C-C--r~~ n Oc~\ /C~ ~ \ / ~o Ar~ Ar. Ar2 I I I
. .... . . ..
The preferred bismaleimide triazine polymeric materials employed according to the present invention are solid and are available under the trade designation BT 2000 Series and most preferably, BT 2170 and BT 2120A from Mitsubishi Gas Chemical Company, Inc. The pref~erred resins bismaleimide triazine polymeric materials are~
obtained from mixtures containing at least about 50% by weight of the bisphenol-A-dicyanate. The relative amounts of triazine moieties to bismaleimide moieties are such that the triazine bismaleimide polymeric component is soluble in the organic solvent employed and when combined with the epoxy polymeric material, the cured composition exhibits high resistance to elevated temperatures. Preferably, the relative amount of triazine moieties to bismaleimide moieties is about 5~5:1 to about 9:1.
Claims (11)
1. A composition consisting essentially of:
(a) about 70 to about 80% by weight of bismaleimide triazine polymeric component;
(b) about 20 to about 30% by weight of a brominated epoxy polymeric component wherein said brominated epoxy polymeric component is a tetrabrominated diglycidyl ether of a phenol and contains at least 45% by weight of bromine; and (c) solvent comprising a ketone selected from the group comprising acetone and methylethyl ketone, or mixtures thereof, in an amount of about 10 to 70% by weight based upon the total weight of (a), (b), and (c) in the composition.
(a) about 70 to about 80% by weight of bismaleimide triazine polymeric component;
(b) about 20 to about 30% by weight of a brominated epoxy polymeric component wherein said brominated epoxy polymeric component is a tetrabrominated diglycidyl ether of a phenol and contains at least 45% by weight of bromine; and (c) solvent comprising a ketone selected from the group comprising acetone and methylethyl ketone, or mixtures thereof, in an amount of about 10 to 70% by weight based upon the total weight of (a), (b), and (c) in the composition.
2. The composition of claim 1 wherein said bismaleimide triazine polymeric component is from bisphenol-A-dicyanate and the bis-imide of 4, 4'-diaminodiphenyl methane and maleic anhydride.
3. The composition of claim 1 wherein said brominated epoxy polymeric compound is tetrabrominated diglycidyl ether of bisphenol-A.
4. The composition of claim l wherein said brominated epoxy polymeric component contains at least about 50% by weight bromine.
5. The composition of claim 1 wherein said solvent is substantially free from solvents other than said ketone.
6. The composition of claim 1 which is substantially free from polymeric materials other than said bismaleimide triazine polymeric component and said brominated epoxy polymeric component.
7. A product comprising a fibrous substrate impregnated with the composition of claim 1 and a curing agent of said composition.
8. The product of claim 7 wherein said substrate is fiberglass.
9. The product of claim 7 wherein said curing agent is zinc octoate.
10. The product of claim 1 or claim 7 having a glass transition temperature of at least about 175° C when cured.
CLAIM SUPPORTED BY SUPPLEMENTARY DISCLOSURE
CLAIM SUPPORTED BY SUPPLEMENTARY DISCLOSURE
11. The composition of claim 1 wherein the relative amount of triazine to bismaleimide moieties in the polymeric component is about 5.5:1 to about 9:1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US38831682A | 1982-06-14 | 1982-06-14 | |
| US388,316 | 1982-06-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1200640A true CA1200640A (en) | 1986-02-11 |
Family
ID=23533612
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000425433A Expired CA1200640A (en) | 1982-06-14 | 1983-04-07 | Bismaleimide triazine polymer compositions for making circuit boards |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS58219257A (en) |
| CA (1) | CA1200640A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60118799A (en) * | 1983-11-29 | 1985-06-26 | Nippon Oil Co Ltd | Lubricant for working metal |
-
1983
- 1983-04-07 CA CA000425433A patent/CA1200640A/en not_active Expired
- 1983-04-20 JP JP6851383A patent/JPS58219257A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6410020B2 (en) | 1989-02-21 |
| JPS58219257A (en) | 1983-12-20 |
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