GB2093847A - Epoxy imide compositions - Google Patents

Epoxy imide compositions Download PDF

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Publication number
GB2093847A
GB2093847A GB8106776A GB8106776A GB2093847A GB 2093847 A GB2093847 A GB 2093847A GB 8106776 A GB8106776 A GB 8106776A GB 8106776 A GB8106776 A GB 8106776A GB 2093847 A GB2093847 A GB 2093847A
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product
reaction product
composition
formula
resin
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GB2093847B (en
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

A composition useful for making circuit boards which is the reaction product of (a) an epoxy resin or an epoxy novalac resin and optionally, a brominated epoxy resin and (b) a bismaleimide; wherein the product of (a) and (b) is subsequently reacted with a curing agent such as a diamine of the formula H2N-R<1>-NH2 wherein R<1> is an aromatic, aliphatic or cycloaliphatic group. The composition is used to impregnate a fibrous substrate of fiberglass, high temperature polyamides or graphite fibers which is laminated to a copper sheet; the resulting laminate is used for form a circuit boards that have good electrical and physical properties.

Description

SPECIFICATION Epoxy Imide Compositions Background of the Invention This invention is related to a composition that is useful for making circuit boards.
Circuit boards are widely used in the electrical industry for radio, television, appliances, industrial and electrical equipment. In general, circuit boards are made by impregnating a woven fiberglass sheet with a resin and laminating copper sheet to one or both sides of the resin impregnated fiberglass sheet; then an electrical circuit is etched into the copper to form the circuit board. Electrical connections are usually soldered to the board when the board is utilized.
Polyimide resins have been used to impregnate these fiberglass sheets and form excellent quality circuit boards which have resistance to high temperatures, low thermal expansion and good electrical properties, such as a high level of resistivity. However, these boards are of a relatively high cost in comparison to circuit boards made from an epoxy resin impregnated fiberglass sheets. Circuit boards of epoxy resin impregnated fiberglass sheets are not resistant to high temperatures and have poorer electrical properties and a higher level of thermal expansion in comparison to circuit boards of polyimide resin impregnated fiberglass sheets.
There is a need for a composition that has a cost that is comparable to epoxy resins but that will form a circuit board having physical and electrical properties close to polyimide circuit boards but substantially better than epoxy resin circuit boards. The novel composition of this invention will form circuit boards that have such properties.
Summary of the Invention The composition comprises 20~80% by weight of a reaction product and 20~80% of a nonamide solvent for the reaction product having a dispersion solubility parameter of 7.2~10.5, a polar solubility parameter of 3-9.5 and a hydrogen bonding solubility parameter of 0--5.5; wherein the reaction product consists essentially of (a) an epoxy resin of the formula
wherein R is an alkylene group of 14 carbon atoms, n is a positive integer and the resin has an epoxide equivalent of about 150~1000; or an epoxy novolac resin of the formula
where n is a positive integer and the resin has an epoxide equivalent of about 150~300;; and optionally, a brominated epoxy resin having the above epoxy resin formula except each aromatic group contains 2-4 bromine atoms that are substituted for hydrogen atoms of the aromatic group can be used with the above epoxy resin or epoxy novolac resin, (b) a bismaleimide of the formula
wherein (a) and (b) are reacted at 1 5-1 350C for about 0.5-2 hours and subsequently contacting the product of (a) and (b) with (c) a curing agent such as a diamine of the formula H2N-F(1-NH2 to form the reaction product, where R' of the bismaleimide and diamine is an aromatic, aliphatic or cycloaliphatic group and wherein the molar ratio of bismaleimide to diamine is less than 1.
Decription of the Invention The composition contains about 20~80% by weight of the reaction product and 20~80% by weight of a nonamide solvent or a blend of nonamide solvents for the reaction product. For most uses of the composition, the composition contains about 50~70% by weight of the reaction product.
The combination of epoxy resin or epoxy novolac resin and the optional brominated epoxy resin comprises about 10~96% by weight of the reaction product. The bismaleimide comprises about 260% by weight of the reaction product and the curing agent comprises about 2~30% by weight of the reaction product.
A process for forming the reaction product comprises the following steps: (1) the epoxy resin or epoxy novolac resin and the optional brominated epoxy resin are reacted with the bismaleimide at about 1 5-1 35CC for about 0.5-2 hours to form a product soluble in nonamide solvents; preferred reaction conditions are 1 5-1 250 C for about 0.75-1.25 hours.
(2) a curing agent, such as a diamine is added to the product of Step (1).
The reaction product may be diluted with an appropriate nonamide solvent. These nonamide solvents have dispersion solubility parameter of 7.2-10.5, a polar solubility parameter of 3-9.5 and a hydrogen bonding solubility parameter of 0--5.5. These solubility parameters are measured at 250C.
A discussion of solubility parameters is in The Encyclopedia of Chemical Technology, Supplement Vol., 2nd Edition (1971), pages 889-910, which is hereby incorporated by reference. Typically useful solvents are as follows: Dispersion Polar Sol. Hydrogen Bonding Solvent Sol. Parameter Parameter Sol.Parameter acetone 7.6 5.1 3.4 methylethyl ketone 7.8 4.4 2.5 cyclohexanone 8.7 3.1 2.5 diethyl ketone 7.7 3.7 2.3 methylisobutyl ketone 7.5 3.0 2.0 methylisoamyl ketone 7.8 2.8 2.0 methylene dichloride 8.9 3.1 3.0 nitrobenzene 9.8 4.2 2.0 acetonitrile 7.5 8.8 3.0 proprionitrile 7.5 7.0 2.7 dichloroethane 8.1 4.0 0.2 ethylformate 7.6 4.1 4.1 2,4-pentanedione 7.8 3.9 2.8 Mixtures of the above solvents can be used and mixtures of the above solvents with other solvents that are not within the above solubility parameters can be used provided that the resulting mixture is within the above solubility parameters.Typically useful mixtures are cyclohexanol/methylethyl ketone, acetonitrile/methylisobutyl carbinol, diisobutyl ketone/propionitrile, cyclohexane/acetonitrile, proprionitrile/toluene or xylene, acetonitrile/aliphatic hydrocarbon solvent and the like.
One preferred epoxy resin used to form the reaction product which forms a good quality circuit board has the formula
wherein n is a positive integer sufficient to provide a viscosity of 16000-25,000 centipoises measured at 250C and has an epoxide equivalent of about 180-300.
Epoxide equivalent means the grams of resin that contain one-gram equivalent of epoxide.
One preferred epoxy novolac resin has the aforementioned formula for an epoxy novolac resin where n is a positive integer sufficiently large to provide a viscosity of about 1400-2000 centipoises measured at 250C and has an epoxide equivalent of about 1 70-180.
The brominated epoxy resin has the same formula as the above epoxy resin except each aromatic group contains 2-4 bromine atoms that are substituted for hydrogen atoms of the aromatic group.
Preferably, the brominated epoxy resin has the formula
wherein n is a positive integer sufficient to provide a viscosity of about 250-4,000 centipoises measured at 250C and has an epoxide equivalent of about 300-800.
One particularly preferred brominated epoxy resin having the above formula has an epoxide equivalent of about 305-355 and contains about 44~48% by weight bromine.
Another preferred brominated epoxy resin having the above formula has an epoxide equivalent of about 460 and contains about 47~51% by weight bromine.
The bismaleimide used to form the reaction product is of the formula
wherein R' is an aromatic, aliphatic, or a cycloaliphatic group.
Preferably a bismaleimide is used in which R1 is an alkylene group having 1-6 carbon atoms, phenylene, cyclohexylene,
where R2 is an alkylene group having 1-4 carbon atoms, SO2 or 0.
Examples of typical bismaleimides are as follows: N,N'-ethylene-bis-maleimide N,N'-butylene-bis-maleimide N,N'-hexamethylene-bis-maleimide N,N'-phenylene-bis-maleimide N,N'-4,4'-diphenylmethane-bis-maleimide N,N'-4,4'-diphenyl ether-bis-maleimide N,N'-4,4'-diphenyl sulfone-bis-maleimide N,N'-4,4'-dicyclohexyl methane-bis-maleimide N,N'-xylylene-bis-maleimide N,N'-diphenyl cyclohexane-bis-maleimide and the like.
The curing agent used to form the reaction product can be a diamine of the formula H2N-R1- NH2 where R' is an aromatic, aliphatic or a cycloaliphatic group, an amide, a primary, secondary or tertiary monoamine, such as N,N'-dim#thyl amino benzaldehyde or benzyl dimethylamine, diethanol amine, triethanoiamine, diethyl amino propylamine; polyamines, melamines, Lewis acids, such as boron trifluoride, boron trifluoride monoethylamine and the like.
Preferably, diamines are used as curing agents in which R1 is an alkylene group that has 1-6 carbon atoms, phenylene, cyclohexylene,
where R2 is an alkylene group having 1-4 carbon atoms, SO2 or 0.
Examples of typically useful diamines are as follows: ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, 2-ethylhexylene diamine, nonamethylene diamine, decamethylene diamine, 2,1 1-diamino-dodecane and the like; meta-phenylene diamine, para-phenylene diamine, 2,2'-naphthalene diamine, 4,4'-biphenylene diamine, methylene dianiline-(4,4'-diaminodiphenyl methane), ethylene dianiline(4,4'-diaminodiphenyl ethane), propylene dianiline(4,4'-diaminodiphenyl propane), and the like;; oxydianiline(4,4'-diaminodiphenylether), ketodianiline, 4,4'-diamino-diphenyl sulfide, 3,3'-diamino diphenyl sulfide, 4,4'-diamino diphenyl sulfone, 3,3'-diamino-diphenyl sulfone, bis-(para-amino-cyclohexyl)methane, bis-(para-amino-cyclohexyl)ethane, bis-(para-amino-cyclohexyl)propane, bis-(para-amino-cyclohexyl)sulfide, bis-(para-amino-cyclohexyl)sulfone, bis-(para-amino-cyclohexyl)ether, bis-(para-amino-cyclohexyl)diethyl silane, bis-(para-amino-cyclohexyl)diphenyl silane, bis-(para-amino-cyclohexyl)ethyl phosphine oxide, bis-(para-amino-cyclohexyl)phenyl phosphine oxide, bis-(para-amino-cyclohexyl)-N-phenyl amine, bis-(para-amino -cyclohexyl)-N-methyl amine, hexafluoroisopropylidene-bis-(4-phenyl amine), 4,4'-diamino-diphenyl methane, 4,4'-diamino-diphenyl ethane, 4,4'-diamino-diphenyl propane, 4,4'-diamino-diphenyl butane, 2,6-diamino-pyridine, bis-(4-amino-phenyl)diethyl silane, bis-(4-amino-phenyl)diphenyl silane, bis-(4-amino-phenyl)ethyl phosphine oxide, bis-(4-amino-phenyl)phenyl phosphine oxide, bis-(4-am ino-phenyl)-N-phenyla mine, bis-(4-amino-phenyl)-N-methylamine, 3,3'-dimethyl-4,4'-diamino-biphenyl, 3,3'-dimethoxy-benzidine, 2,4-bis-(b-amino-t-butyl)toluene, bis-(para-b-ami no-t-butyl-phenyl)ether, para-bis-(2-methyl-4-amino-phenyl)benzene, para-bis-( 1,1 -dimethyl-5-amino-pentyl)benzene, m-xylylene diamine, p-xylylene diamine, 1 ,2-bis-(3-amino-propoxy)ethane, 2,2-dimethyl propylene diamine, 3-methoxy-hexamethylene diamine, 2,5-dimethylheptamethylene diamine, 5-methylnonamethylene diamine, 1 ,4-diamino-cyclohexane, 1 ,2-diamino-octadecane, 2,5-diamino-1 ,3,4-oxadiazole.
Preferred diamines are the above diamino diphenyl sulfones which form a high quality reaction product that has good electrical and physical properties.
The molar ratio of bismaleimide to diamine used in the reaction product is less than 1 and preferably is about 0.6-0.8. The most preferred ratio is 0.7 which forms a reaction product with good electrical and physical properties.
The following reaction products are preferred since these products are used for circuit boards that have good electrical and physical properties: (1) a reaction product of about 30~60% by weight of the aforementioned epoxy resin, 10~30% by weight of the aforementioned brominated epoxy resin,10~30% by weight of a bismaleimide and 10~30% by weight of a diamine; (2) a reaction product of about 40% by weight of the aforementioned preferred epoxy resin, 20% by weight of the aforementioned preferred brominated epoxy resin, 20% by weight N,N'-4,4'-diphenyl methane bismaleimide and, 20% by weight of diamino diphenyl sulfone;; (3) a reaction product of about 1 5--35% by weight of the aforementioned brominated epoxy resin, 40~60% by weight of the aforementioned epoxy novolac resin, 1 5--35% by weight of a bismaleimide and 15~35% by weight of a diamine; (4) a reaction product of about 20% by weight of the aforementioned preferred brominated epoxy resin; 40% by weight of the aforementioned preferred epoxy novolac resin, 20% by weight of N,N'4,4'-diphenyl methane bismaleimide and 20% by weight of diamino diphenyl sulfone.
The reaction product is used in making bases for circuit boards. In preparing these bases, a fibrous substrate is coated and impregnated with the reaction product using conventional coating equipment and then the resulting impregnated substrate is cured at about 50 to 2000C for about 1 to 30 minutes to form a rigid sheet. A sheet of copper or another conductive material is then laminated to the rigid sheet using the following laminating conditions: 50 to 1000 pounds per square inch, 50 to 300cm for 30 to 300 minutes.
A circuit can then be etched into the conductive layer using conventional techniques to form a circuit board.
The reaction product can be used to coat and/or impregnate fibrous substrates, in particular high temperature resistant substrates, such as substrates of fiberglass, high temperature polyamides, graphite, and the like.
The following examples illustrate the invention. All parts and percentages are on a weight basis unless otherwise indicated.
Example 1 The following constituents are charged into a reaction vessel equipped with a stirrer, a heating unit and a reflux condenser: Portion 1 Parts by Weight Epoxy resin (having the formula 40
where n is a positive integer sufficiently large to provide a viscosity of 16,000-25,000 centipoises measured at 250C and has an epoxide equivalent* of about 192~203) Brominated epoxy resin (having the 20 above formula except the resin contains 44~ 48% by weight bromine and bromine atoms are substituted for hydrogen atoms of the aromatic groups and the resin has an epoxide equivalent* of 305-355) Portion 2 Bismaleimide (having the formula 20
Portion 3 Diamino diphenyl sulfone 20 Methyl ethyl ketone 53 Total 153 *Epoxide Equivalent-grams of resin containing one-gram equivalent of epoxide.
Portion 1 is added to the vessel and heated to a temperature of 1 25 C. Portion 2 is then slowly added to the vessel while maintaining the temperature at 1 250C. When Portion 2 is added, the temperature is increased to 1 300C and held at this temperature for 1 hour and cooled to 1 O00C.
Portion 3 is premixed and then slowly added to the vessel while maintaining a temperature of 1 000C.
The resulting resin solution is cooled to 700C and held at this temperature for 30 minutes and then filtered.
About 0.5 parts by weight of boron fluoride monoethyl amine complex dissolved in methyl ethyl ketone per 100 parts by weight of resin solids are added to the above prepared resin solution. The resulting resin solution is then coated onto a fiberglass fabric using a conventional coating tower.
The following fiberglass fabrics are coated in the tower: 108 glass fabric~1.5 ounces per square yard 11 6 glass fabric~3.5 ounces per square yard 7628 glass fabric~5.8 ounces per square yard.
The coating tower is operated at a speed of about 5-7 yards per minute and a heater temperature of about 120-1 350C is used. About 1.5 ounces of resin per square yard of fabric is applied to both sides of the fabric providing a resin impregnated and coated glass fabric.
A copper sheet is then laminated to the top and bottom of each of the resin impregnated and coated glass fabric by placing the copper sheets and the resin impregnated glass fabric in a press for about 60 minutes at 400 pounds per square inch and at a temperature of about 1 750C. The resulting laiminates are formed into circuit boards using conventional techniques.
The expansion of each of the circuit boards from 250C to 2500C is measured. Each of the boards expanded only about 3.0% under these conditions.
Example 2 The following constituents are charged into a reaction vessel equipped as in Example 1: Parts by Weight Portion 1 Composition A Epoxy novolac resin (having the formula 50
where n is a positive integer sufficiently large to provide a viscosity of 1400- 2000 centipoises measured at 250C and the resin has an epoxide equivalent weight of 172~179) Brominated epoxy resin (described in 25 Example 1) Portion 2 Bismaleimide (described in Example 1) 25 Portion 3 Diamino diphenyl sulfone 25 Methyl ethyl ketone 165 Total 290 Portions 1,2 and 3 are added and reacted using the identical conditions and procedures as used in Example 1 to form a resin solution. Boron fluoride mono methyl amine in the same amount as used in Example 1 is added to the resin solution.
The glass fabrics described in Example 1 are coated in a conventional coating tower with the above resin solution using the same coating speed and temperature conditions and the same amount of resin is applied to the fabric. A copper sheet is then laminated to the top and bottom of each of the resin impregnated and coated glass fabrics using the same time, temperature and pressure conditions used in Example 1. The resulting laminates are used for circuit boards.
The expansion of each of these circuit boards from 250C to 2500C is measured. Each of the boards expanded about 3.0% under these conditions.
Example 3 The following constituents are charged into a reaction vessel equipped with a stirrer, a heating unit and a reflux condenser: Portion 1 Parts by Weight Epoxy resin (having the formula 40
where n is a positive integer sufficiently large to provide a viscosity of 1 6,000-25,000 centipoises measured at 250C and has an epoxide equivalent* of about 192-203) Brominated epoxy resin (having the 20 above formula except the resin contains 47 51% by weight bromine and bromine atoms are substituted for hydrogen atoms of the aromatic groups and the resin has an epoxide equivalent* of 460) Portion 2 Bismaleimide (having the formula 20
Portion 3 Diamino diphenyl sulfone 20 Methyl ethyl ketone 53 Total 1 53 *oxide Equivalent-grams of resin containing one-gram equivalent of epoxide.
Portion 1 is added to the vessel and heated to a temperature of 1 50C. Portion 2 is then slowly added to the vessel while maintaining the temperature at about 1 5#1250 C. After Portion 2 is added, the temperature is held at 1 5-1 250C for 1 hour and then the methylethyl ketone is added and the solution is cooled to 60#700 C. The diaminodiphenyl sulfone is added and the temperature is held at about 60-700C for about 1 hour and then the solution is cooled to the ambient temperature and then filtered.
About 0.5 parts by weight of boron fluoride monoethyl amine complex dissolved in methylethyl ketone per 100 parts by weight of resin solids are added to the above prepared resin solution. The resulting resin solution is then coated onto a fiberglass fabric using a conventional coating tower.
The following fiberglass fabrics are coated in the tower: 108 glass fabric~1.5 ounces per square yard 1 6 glass fabric~3.5 ounces per square yard 7628 glass fabric~5.8 ounces per square yard.
The coating tower is operated at a speed of about 5-7 yards per minute and a heater temperature of about 120-1 350C is used. About 1.5 ounces of resin per square yard of fabric is applied to both sides of the fabric providing a resin impregnated and coated glass fabric.
A copper sheet is then laminated to the top and bottom of each of the resin impregnated and coated glass fabric by placing the copper sheets and the resin impregnated glass fabric in a press for about 60 minutes at 400 pounds per square inch and at a temperature of about 1750 C. The resulting laminates are formed into circuit boards using conventional techniques.
The expansion of each of the circuit boards from 250C to 2500C is measured. Each of the boards expanded only about 3.0% under these conditions.
Example 4 Example 2 is duplicated using the identical constituents in the same amounts except the following procedure is used to make the resin solution: Portion 1 is added to the vessel and heated to a temperature of 11 50C. Portion 2 is then slowly added to the vessel while maintaining the temperature at about 1 5-1 250 C. After Portion 2 is added, the temperature is held at 1 5-1 250C for 1 hour and then the methylethyl ketone is added and the solution is cooled to 60~70 C. The diaminodiphenyl sulfone is added and the temperature is held at about 60-700C for about 1 hour and then the solution is cooled to the ambient temperature and then filtered. Boron fluoride mono methyl amine in the same amount as used in Example 1 is added to the resin solution.
The glass fabrics described in Example 1 are coated in a conventional coating tower with the above resin solution using the same coating speed and temperature conditions and the same amount of resin is applied to the fabric. A copper sheet is then laminated to the top and bottom of each of the resin impregnated and coated glass fabrics using the same time, temperature and pressure conditions used in Example 1. The resulting laminates are used for circuit boards.
The expansion of each of these circuit boards from 250C to 2500C is measured. Each of the boards expanded about 3.0% under these conditions.

Claims (28)

Claims
1. A composition comprising 20~80% by weight of a reaction product and 20~80% of a nonamide solvent for the reaction product having a dispersion solubility parameter of 7.2-10.5, a polar solubility parameter of 3-9.5 and a hydrogen bonding solubility parameter of 0--5.5; wherein the reaction product consists essentially of (a) an epoxy resin of the formula
wherein R is an alkylene group of 1 ti carbon atoms, n is a positive integer; and the resin having an epoxide equivalent of about 150~1000; or an epoxy novolac resin as hereinbefore defined; and (b) a bismaleimide of the formula
wherein (a) and (b) are reacted at 1 5-1 350C for about 0.5-2 hours and subsequently contacting the product of (a) and (b) with (c) a curing agent such as a diamine of the formula H2N-R1-NH2 to form the reaction product; where R1 is an aromatic, aliphatic or cycloaliphatic group; wherein the molar ratio of bismaleimide to diamine is less than 1.
2. The composition of Claim 1 in which R1 is an alkylene group having 1-6 carbon atoms, phenylene, cyclohexylene,
where R2 is an alkylene group having 1 4 carbon atoms, SO2 or 0.
3. The composition of Claim 1 or Claim 2 in which R is
4. The composition of any one of Claims 1 to 3 in which R' is an aromatic group.
5. The composition of Claim 4 in which R1 is
6. The composition of Claim 4 in which R1 is
7. A composition comprising 50~70% by weight of a reaction product and 30~50% by weight of a solvent selected from the group consisting of acetone, methylene dichloride, cyclohexanone, pentanedione, methyl-N-amyl keton, methylisobutyl ketone, methylethyl ketone; and mixtures thereof; wherein the reaction product consists essentially of (a) an epoxy resin of the formula
wherein n is a positive integer sufficient to provide a viscosity of 1 6,000-25,000 centipoises measured at 250C and having an epoxide equivalent of about 180-300; (b) a brominated epoxy resin of the formula
wherein n is a positive integer sufficiently large to provide a viscosity of 250~4,000 centipoises measured at 250 C, and the resin having an epoxide equivalent of about 300-800;; (c) a bismaleimide of the formula
wherein (a), (b) and (c) are reacted for about 0.75-1.25 hours at about 1 5-1 250C and subsequently the product of (a), (b) and (c) with (d) a curing agent such as a diamine of the formula
to form the reaction product; wherein the molar ratio of bismaleimide to diamine is about 0.6-0.8.
8. A product comprising a fibrous substrate impregnated with the composition of any one of Claims 1 to 7.
9. The product of Claim 8 in which the fibrous substrate is of fiberglass, a high temperature resistant polyamide fiber or a graphite fiber.
10. The product of Claim 9 in which the substrate is of fiberglass and has a copper electrical circuit firmly adhered thereto.
1 1. A process for forming the reaction product of any one of Claims 1 to 7 which comprises the following steps.
(1) contacting the epoxy resin with the bismaleimide at about 1 1 5~1 350C for about 0.5-2 hours to form a product and (2) adding the diamine to the product of Step 1.
12. A composition comprising 20~80% by weight of a reaction product and 20~80% of a nonamide solvent for the reaction product having a dispersion solubility parameter of 7.2-10, a polar solubility parameter of 3-9.5 and a hydrogen bonding solubility parameter of 0--5.5; wherein the reaction product consists essentially of (a) an epoxy novolac resin of the formula
where n is a positive integer and the resin has an epoxide equivalent of about 1 50-300.
(b) a bismaleimide of the formula
wherein (a) and (b) are reacted at about 1 15--135 C for about 0.5-2 hours and subsequently reacting the product of (a) and (b) with (c) a curing agent such as a diamine of the formula H2N-R1-NH2 to form the reaction product, where R1 is an aromatic, aliphatic or cycloaliphatic group; wherein the molar ratio of bismaleimide to diamine is less than 1.
13. The composition of Claim 12 in which R' is an alkylene group having 1-6 carbon atoms, phenylene, cyclohexylene,
where R2 is an alkylene group having 1 1--4 carbon atoms, SO2 or 0.
14. The composition of Claim 12 or Claim 13 in which R' is an aromatic group.
15. The composition of Claim 14 in which R1 is
16. The composition of Claim 14 in which R1 is
17. A composition comprising 50~70% by weight of a reaction product and 30~50% by weight of a solvent selected from the group consisting of acetone, methylene dichloride, cyclohexanone, pentanedione, methyl-N-amyl ketone, methyl isobutyl ketone, methyethyl ketone and mixtures thereof; wherein the reaction product consists essentially of (a) an epoxy novolac resin of the formula
where n is a positive integer and the resin has an epoxide equivalent of about 170~180 and a viscosity of about 1400-2000 centipoises measured at 250C; (b) a brominated epoxy resin of the formula
wherein n is a positive integer sufficiently large to provide a viscosity of 250-4,000 centipoises measured at 250C, and the resin having an epoxide equivalent of about 300-800;; (c) a bismaleimide of the formula
and wherein (a), (b) and (c) are reacted at about 1 5-1 350C for about 0.5-2.0 and subsequently reacting the product of (a), (b) and (c) with (d) a curing agent such as a diamine of the formula
to form the reaction product; wherein the molar ratio of bismaleimide to diamine is about 0.6~0.8.
18. A product comprising a substrate of fiberglass, a high temperature polyamide or a graphite fiber impregnated with the composition of any one of Claims 12 to 16.
1 9. The product of Claim 18 in which the substrate is fiberglass.
20. The product of Claim 1 9 having a copper electrical circuit firmly adhered thereto.
21. A product comprising a substrate of fiberglass, a high temperature polyamide or a graphite fiber impregnated with the composition of Claim 17.
22. The product of Claim 21 in which the substrate is fiberglass.
23. The product of Claim 22 having a copper electrical circuit firmly adhered thereto.
24. A process for forming the reaction product of any one of Claims 12 to 1 6 which comprises the following steps.
(1) contacting the epoxy novolac resin with the bismaleimide at about 1 5-1 35C for about 0.5-2 hours to form a product and (2) adding the diamine to the product of Step (1).
25. A process for forming the reaction product of Claim 17 which comprises the following steps (1) contacting the epoxy novolac resin and the brominated epoxy resin with the bismaleimide at about 1 5-1 350C for about 0.2-2 hours to form a product and (2) adding the diamine to the product of Step (1).
26. A composition comprising a reaction product and a solvent substantially as hereinbefore described in any one of the foregoing Examples.
27. A process for forming a reaction product substantially as hereinbefore described in any one of the foregoing Examples.
28. A product comprising an impregnated fibrous substrate substantially as hereinbefore described in any one of the foregoing Examples.
GB8106776A 1981-03-04 1981-03-04 Epoxy imide compositions Expired GB2093847B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
GB8106776A GB2093847B (en) 1981-03-04 1981-03-04 Epoxy imide compositions
HK108/85A HK10885A (en) 1981-03-04 1985-02-07 Epoxy imide compositions

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB8106776A GB2093847B (en) 1981-03-04 1981-03-04 Epoxy imide compositions

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Publication Number Publication Date
GB2093847A true GB2093847A (en) 1982-09-08
GB2093847B GB2093847B (en) 1984-09-05

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2543394A1 (en) * 1983-03-22 1984-09-28 Thomson Csf Printed board having a low coefficient of expansion and high thermal conductivity
GB2139628A (en) * 1983-03-16 1984-11-14 Avco Corp Bis-maleimide-epoxy compositions and pre-pregs
FR2653130A1 (en) * 1989-10-16 1991-04-19 Rhone Poulenc Chimie POLYMERS WITH IMIDE GROUPINGS MADE FROM CONCEALED DIAMINES.

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2139628A (en) * 1983-03-16 1984-11-14 Avco Corp Bis-maleimide-epoxy compositions and pre-pregs
FR2543394A1 (en) * 1983-03-22 1984-09-28 Thomson Csf Printed board having a low coefficient of expansion and high thermal conductivity
FR2653130A1 (en) * 1989-10-16 1991-04-19 Rhone Poulenc Chimie POLYMERS WITH IMIDE GROUPINGS MADE FROM CONCEALED DIAMINES.
EP0424286A1 (en) * 1989-10-16 1991-04-24 Ciba-Geigy Ag Imide group-containing polymers from sterically hindered diamines

Also Published As

Publication number Publication date
GB2093847B (en) 1984-09-05
HK10885A (en) 1985-02-15

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