US4975319A
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US
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Printed circuit board from fibers impregnated with epoxy resin mixture, halogenated bisphenol and polyphenylene ether
Assignee: Polyclad Laminates Inc
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Filing: 1989-04-03
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Granted: 1990-12-04
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Expires: 2009-04-03
Abstract
Abstract Curable compositions containing a reaction product of at least one bisphenol polyglycidyl ether, at least one epoxidized novolak and at least one brominated bisphenol, in combination with a polyphenylene ether and further components including specific catalysts and hardeners, may be used in the preparation of laminates useful as printed circuit boards and having excellent physical and electrical properties.
Inventors
- 👤 Erik W. Walles
- 👤 John H. Lupinski
- 👤 Mark Markovitz
- 👤 Robert E. Colborn
- 👤 James R. Presley
- 👤 Michael J. Davis
- 👤 Michael G. Minnick
- 👤 Steven J. Kubisen, Jr.
- 👤 John E. Hallgren
- 👤 Donald A. Bolon
- 👤 Victoria J. Eddy
- 👤 Patricia C. Irwin
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 15:22
CPC Classifications
H; H05; H05K; H05K1/00; H05K1/02; H05K1/03; H05K1/0313; H05K1/0353; H05K1/0373; C; C08; C08G; C08G59/00; C08G59/02; C08G59/04; C08G59/06; C08G59/063; C08G59/18; C08G59/20; C08G59/32; C08G59/38; C08L; C08L63/00; C08L71/00; C08L71/08; C08L71/10; C08L71/12; C08L71/123; H05K2201/00; H05K2201/01; H05K2201/0104; H05K2201/012; H05K2203/00; H05K2203/12; H05K2203/121; Y; Y10; Y10S; Y10S428/00; Y10S428/901; Y10S428/92; Y10T; Y10T428/00; Y10T428/31504; Y10T428/31511; Y10T428/31515; Y10T428/31518; Y10T428/31522; Y10T428/31678; Y10T442/00; Y10T442/20; Y10T442/2549; Y10T442/2566; Y10T442/2631; Y10T442/2713
Claims Analysis
Total Claims: 18
Claim 1
Independent Claim
270 words
A printed circuit board blank comprising an article clad with a conductive metal, said article being prepared by curing an article comprising a fibrous substrate impregnated with a curable composition containing chemically combined bromine in an amount effective to impart flame retardancy, said curable composition comprising: (I) about 25-50% of a resinous composition containing 15-20% chemically combined bromine and comprising the reaction product obtained by heating at a temperature in the range of about 125°-225° C., in the presence of a catalytic amount of at least one basic reagent, a mixture comprising: (A) at least one halogen-free bisphenol polyglycidyl ether having an average of at most one aliphatic hydroxy group per molecule; (B) about 15-25% of at least one halogen-free epoxidized novolak; and (C) about 15-25% of at least one bisphenol containing bromine as aryl substituents; the percentages of components B and C being based on total reagents A, B and C; (II) about 35-55% of at least one polyphenylene ether; (III) about 4-15% of at least one halogen-free novolak, substantially all oxygen therein being in the form of phenolic hydroxy groups; (IV) an amount of at least one of imidazoles and arylene polyamines to provide a total of at least 2 milliequivalents of basic nitrogen per 100 parts of said curable composition; (V) about 0.1-1.0% of zinc in the form of a zinc salt which is soluble or stably dispersible in said curable composition; and (VI) about 1-4% of antimony pentoxide stably dispersed in said curable composition; said percentages being by weight and based on the total of components I-VI and any other resinous materials and brominated materials present.
Claim 2
Dependent Claim
270 words
A printed circuit board blank comprising an article clad with a conductive metal, said article being prepared by curing an article comprising a fibrous substrate impregnated with a curable composition containing chemically combined bromine in an amount effective to impart flame retardancy, said curable composition comprising: (I) about 25-50% of a resinous composition containing 15-20% chemically combined bromine and comprising the reaction product obtained by heating at a temperature in the range of about 125°-225° C., in the presence of a catalytic amount of at least one basic reagent, a mixture comprising: (A) at least one halogen-free bisphenol polyglycidyl ether having an average of at most one aliphatic hydroxy group per molecule; (B) about 15-25% of at least one halogen-free epoxidized novolak; and (C) about 15-25% of at least one bisphenol containing bromine as aryl substituents; the percentages of components B and C being based on total reagents A, B and C; (II) about 35-55% of at least one polyphenylene ether; (III) about 4-15% of at least one halogen-free novolak, substantially all oxygen therein being in the form of phenolic hydroxy groups; (IV) an amount of at least one of imidazoles and arylene polyamines to provide a total of at least 2 milliequivalents of basic nitrogen per 100 parts of said curable composition; (V) about 0.1-1.0% of zinc in the form of a zinc salt which is soluble or stably dispersible in said curable composition; and (VI) about 1-4% of antimony pentoxide stably dispersed in said curable composition; said percentages being by weight and based on the total of components I-VI and any other resinous materials and brominated materials present.
Claim 3
Dependent Claim
91 words
A printed circuit board blank according to claim 2 wherein reagent A has the formula ##STR7## wherein n has an average value up to 1; reagent B is a novolak prepared from formaldehyde, phenol and epichlorohydrin and reagent C is 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane; said curable composition also containing (VII) an amount up to about 10% of at least one polyepoxy compound selected from halogen-free bisphenol polyglycidyl ethers having an average of at most one aliphatic hydroxy group per molecule other than polyglycidyl ether (A) and halogen-free epoxidized novolaks other than epoxidized novolak (B).
Claim 4
Dependent Claim
47 words
A printed circuit board blank according to claim 2 wherein n is 0, component II is a poly(2,6-dimethyl-1,4-phenylene ether) having a number average molecular weight within the range of about 12,000-40,000 and component VII is an epoxidized novolak and is present in the amount of about 4-8%.
Claim 5
Dependent Claim
14 words
A printed circuit board blank according to claim 3 wherein the metal is copper.
Claim 6
Dependent Claim
23 words
A printed circuit board blank according to claim 4 wherein component VII is a halogen-free epoxidized novolak prepared from phenol, formaldehyde and epichlorohydrin.
Claim 7
Dependent Claim
36 words
A printed circuit board blank according to claim 4 wherein component IV is at least one imidazole and provides a total of at least 4.5 milliequivalents of basic nitrogen per 100 parts of said curable composition.
Claim 8
Dependent Claim
45 words
A printed circuit board blank according to claim 4 wherein component IV is a mixture of at least one imidazole with at least one arylene polyamine and provides a total of at least 4.5 milliequivalents of basic nitrogen per 100 parts of said curable composition.
Claim 9
Dependent Claim
18 words
A printed circuit board blank according to claim 4 wherein component V is zinc acetylacetonate or zinc stearate.
Claim 10
Dependent Claim
50 words
A printed circuit board blank according to claim 8 wherein the proportions of components in the curable composition are: Bromine--6-9%; Component I--about 30-40%; Component II--about 40-50%; Component III--about 4-8%; Component IV--about 5-10 milliequivalents of basic nitrogen; Component V--about 0.1-0.6% of zinc; Component VI--about 1-3% of antimony pentoxide; Component VII--about 4.2-4.8%.
Claim 11
Dependent Claim
67 words
A printed circuit board blank according to claim 9 wherein the polyphenylene ether comprises molecules having end groups of the formula ##STR8## wherein each R 2 is independently hydrogen or a C 1-6 primary alkyl radical and each Q 2 is independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy or a halohydrocarbonoxy wherein at least two carbon atoms separate the halogen and oxygen atoms.
Claim 12
Dependent Claim
15 words
A printed circuit board blank according to claim 10 wherein each R 2 is n-butyl.
Claim 13
Dependent Claim
84 words
A printed circuit board blank according to claim 4 wherein the curable composition also contains at least one aliphatic tris(dialkylphosphato)titanate of the formula ##STR9## wherein R 3 is C 2-6 primary of secondary alkyl or alkenyl, R 4 is C 1-3 alkylene, R 5 is C 1-5 primary or secondary alkyl, R 6 is C 5-12 primary or secondary alkyl and x is from 0 to about 3, in the amount of about 0.1-1.0 part by weight per 100 parts of the resinous composition.
Claim 14
Dependent Claim
32 words
A printed circuit board blank according to claim 12 wherein R 3 is alkyl, R 4 is methylene, R 5 is ethyl, R 6 is octyl and x is 0 or 1.
Claim 15
Dependent Claim
257 words
A printed circuit board blank comprising an article clad with a conductive metal, said article being prepared by curing an article comprising a fibrous substrate impregnated with a curable composition containing chemically combined bromine in an amount effective to impart flame retardancy, said curable composition comprising: (I) about 25-50% of a resinous composition containing 15-20% chemically combined bromine and comprising the product obtained by the reaction, in the presence of a catalytic amount of at least one basic reagent, of: (A) at least one halogen-free bisphenol polyglycidyl ether having an average of at most one aliphatic hydroxy group per molecule; (B) about 15-25% of at least one halogen-free epoxidized novolak; and (C) 25-35% of at least one bisphenol containing bromine as aryl substituents; the percentages of components B and C being based on total reagents A, B and C; (II) about 35-55% of at least one polyphenylene ether; (III) about 4-15% of at least one halogen-free novolak, substantially all oxygen therein being in the form of phenolic hydroxy groups; (IV) an amount of at least one of imidazoles and arylene polyamines to provide a total of at least 2 milliequivalents of basic nitrogen per 100 parts of said curable composition; (V) about 0.1-1.0% of zinc in the form of a zinc salt which is soluble or stably dispersible in said curable composition; and (VI) about 1-4% of antimony pentoxide stably dispersed in said curable composition; said percentages being by weight and based on the total of components I-VI and any other resinous materials and brominated materials present.
Claim 16
Dependent Claim
257 words
A printed circuit board blank comprising an article clad with a conductive metal, said article being prepared by curing an article comprising a fibrous substrate impregnated with a curable composition containing chemically combined bromine in an amount effective to impart flame retardancy, said curable composition comprising: (I) about 25-50% of a resinous composition containing 15-20% chemically combined bromine and comprising the product obtained by the reaction, in the presence of a catalytic amount of at least one basic reagent, of: (A) at least one halogen-free bisphenol polyglycidyl ether having an average of at most one aliphatic hydroxy group per molecule; (B) about 15-25% of at least one halogen-free epoxidized novolak; and (C) 25-35% of at least one bisphenol containing bromine as aryl substituents; the percentages of components B and C being based on total reagents A, B and C; (II) about 35-55% of at least one polyphenylene ether; (III) about 4-15% of at least one halogen-free novolak, substantially all oxygen therein being in the form of phenolic hydroxy groups; (IV) an amount of at least one of imidazoles and arylene polyamines to provide a total of at least 2 milliequivalents of basic nitrogen per 100 parts of said curable composition; (V) about 0.1-1.0% of zinc in the form of a zinc salt which is soluble or stably dispersible in said curable composition; and (VI) about 1-4% of antimony pentoxide stably dispersed in said curable composition; said percentages being by weight and based on the total of components I-VI and any other resinous materials and brominated materials present.
Claim 17
Dependent Claim
60 words
A printed circuit board blank according to claim 14 wherein the curable composition also contains (VII) an amount up to about 10% of at least one polyepoxy compound selected from halogen-free bisphenol polyglycidyl ethers having an average of at most one aliphatic hydroxy group per molecule other than polyglycidyl ether (A) and halogen-free epoxidized novolaks other than epoxidized novolak (B).
Claim 18
Dependent Claim
84 words
A printed circuit board blank according to claim 15 wherein the curable composition also contains at least one aliphatic tris(dialkylphosphato)titanate of the formula ##STR10## wherein R 3 is C 2-6 primary or secondary alkyl or alkenyl, R 4 is C 1-3 alkylene, R 5 is C 1-5 primary or secondary alkyl, R 6 is C 5-12 primary or secondary alkyl and x is from 0 to about 3, in the amount of about 0.1-1.0 part by weight per 100 parts of the resinous composition.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1993-12-03 | 1994-06-04 | 1994-12-04 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1997-12-03 | 1998-06-04 | 1998-12-04 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2001-12-03 | 2002-06-04 | 2002-12-04 | $7700.00 | Window Closed / Lapsed |