US4401499A
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Crosslinked resin of epoxy compound and isocyanate and process for producing same
Assignee: Sumitomo Bakelite Co Ltd
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Filing: 1981-12-01
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Granted: 1983-08-30
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Expires: 2001-12-01
Abstract
Abstract A crosslinked resin excellent in heat resistance, toughness, moisture resistance and adhesiveness can be obtained by the use of an epoxy compound having both alcoholic hydroxyl groups and epoxy groups in its molecule and an isocyanate compound having isocyanate groups in its molecule by first reacting the alcoholic hydroxyl groups of said epoxy compound and the isocyanate groups of said isocyanate compound to produce an epoxy prepolymer having urethane linkages stable at room temperature, followed by dissociating the urethane linkages of the prepolymer to regenerate the isocyanate groups and reacting said isocyanate groups with the epoxy groups of said epoxy compound. By carrying out the above-mentioned reaction between the isocyante groups and the epoxy groups in the presence of at least one member selected from the group consisting of amine compounds, carboxylic acid anhydrides, phenol novolac compounds and polyvinyl-phenol compounds and/or a bisimide compound, a crosslinked resin having higher heat resistance can be produced. Said prepolymer is excellent in storage stability and suitable for use in the production of laminates.
Inventors
- 👤 Shoroku Kaneko
- 👤 Sigenori Yamaoka
- 👤 Masuo Mizuno
- 👤 Yukihiro Okabe
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 12:58
CPC Classifications
C; C08; C08G; C08G18/00; C08G18/06; C08G18/28; C08G18/40; C08G18/58; C08G59/00; C08G59/14; C08G59/1433; C08G59/1477; C08G59/18; C08G59/40; C08G59/4007; C08G59/4014; C08G59/4028
Claims Analysis
Total Claims: 20
Claim 1
Independent Claim
119 words
A crosslinked resin obtained by subjecting to reaction one equivalent of an isocyanate compound having isocyanate groups in the molecule with 0.5 to 10 epoxy equivalents of an epoxy compound having alcoholic hydroxyl groups and epoxy groups in the molecule, to first react the isocyanate groups of the isocyanate compound with the alcoholic hydroxyl groups of the epoxy compound, thereby forming an epoxy prepolymer having urethane linkages stable at room temperature; subsequently heating the resulting prepolymer at a temperature at least 40° C. higher than the reaction temperature for the formation of the prepolymer to dissociate the urethane linkages and regenerate the isocyanate groups; and then reacting the said isocyanate groups with the epoxy groups of the epoxy compound.
Claim 2
Dependent Claim
119 words
A crosslinked resin obtained by subjecting to reaction one equivalent of an isocyanate compound having isocyanate groups in the molecule with 0.5 to 10 epoxy equivalents of an epoxy compound having alcoholic hydroxyl groups and epoxy groups in the molecule, to first react the isocyanate groups of the isocyanate compound with the alcoholic hydroxyl groups of the epoxy compound, thereby forming an epoxy prepolymer having urethane linkages stable at room temperature; subsequently heating the resulting prepolymer at a temperature at least 40° C. higher than the reaction temperature for the formation of the prepolymer to dissociate the urethane linkages and regenerate the isocyanate groups; and then reacting the said isocyanate groups with the epoxy groups of the epoxy compound.
Claim 3
Dependent Claim
52 words
A crosslinked resin according to claim 1, wherein the epoxy compound having both epoxy groups and alcoholic hydroxyl groups is at least one compound selected from glycidyl ethers obtained by reaction between Bisphenol A or F or hydrogenated Bisphenol A and β-methyl-substituted or unsubstituted epichlorohydrin, and brominated products of these epoxy compounds.
Claim 4
Dependent Claim
33 words
A crosslinked resin according to claim 1, wherein the epoxy compound is a diglycidyl ether obtained by reaction between Bisphenol A and epichlorohidrin, and having an average molecular weight of 400 to 1,000.
Claim 5
Dependent Claim
25 words
A crosslinked resin according to claim 1, 2 or 3, wherein the isocyanate compound is an isocyanate compound having an isocyanurate ring in the molecule.
Claim 6
Dependent Claim
43 words
A crosslinked resin according to claim 1, 2 or 3, wherein the isocyanate compound is a trimer of 2,4-tolylene diisocyanate, 2,5-tolylene diisocyanate, 2,6-tolylene diioscyanate or 3,5-tolylene diisocyanate, a trimer of hexane-1,6-diioscyanate or a copolymer of 2,4-tolylene, 2,5-tolylene, 2,6-tolylene or 3,5-tolylene diisocyanate and hexane-1,6-diisocyanate.
Claim 7
Dependent Claim
90 words
A crosslinked resin according to claim 1, wherein the dissociation of the urethane linkages of the epoxy prepolymer to regenerate the isocyanate groups and the reaction between the regenerated isocyanate groups and the epoxy groups are carried out in the presence of at least one compound selected from the group consisting of amine compounds, carboxylic acid anhydrides, phenol-novolac compounds and polyvinyl-phenol compounds in a proportion of 0.1 to 2 equivalents in terms of amine equivalent, acid anhydride equivalent, or hydroxy equivalent per equivalent of the epoxy group of the prepolymer.
Claim 8
Dependent Claim
90 words
A crosslinked resin according to claim 6, wherein the dissociation of the urethane linkages of the prepolymer to regenerate the isocyanate groups and the reaction between the regenerated isocyanate groups and the epoxy groups are carried out in the presence of at least one compound selected from the group consisting of amine compounds, carboxylic acid anhydrides, phenol novolac compounds and polyvinyl-phenol compounds in a proportion of 0.1 to 2 equivalents in terms of amine equivalent, acid anhydride equivalent or hydroxy equivalent per equivalent of the epoxy group of the prepolymer.
Claim 9
Dependent Claim
14 words
A crosslinked resin according to claim 6, wherein the curing agent is an amine.
Claim 10
Dependent Claim
14 words
A crosslinked resin according to claim 8, wherein the amine is an aromatic amine.
Claim 11
Dependent Claim
18 words
A crisslinked resin according to claim 9, wherein the aromatic amine is diaminodiphenyl ether, diaminodiphenylsulfone, diaminodipenylmethane or methylenebis(o-chloroaniline).
Claim 12
Dependent Claim
60 words
A crosslinked resin according to claim 1, wherein the dissociation of the urethane linkages of the epoxy prepolymer to regenerate the isocyanate groups and the reaction between the regenerated isocyanate groups and the epoxy groups are carried out in the presence of 100 parts by weight or less of a bisimide compound per 10 parts by weight of the prepolymer.
Claim 13
Dependent Claim
16 words
A crosslinked resin according to claim 11, wherein the bisimide is N,N'-4,4'-diphenylmethane-bismaleimide, N,N'-4,4'-diphenyl ether-bismaleimide or N,N'-4,4'-diphenylsulfone-bismaleimide.
Claim 14
Dependent Claim
132 words
A process for producing a cross-linked epoxy resin which comprises subjecting to reaction one equivalent of an isocyanate compound having isocyanate groups in the molecule, and an epoxy compound having alcoholic hydroxyl groups and epoxy groups in the molecule in an amount corresponding to 0.5 to 10 epoxy equivalents and 0.2 to 3 alcoholic hydroxy equivalents, to react the alcoholic hydroxyl groups of the epoxy compound with the isocyanate groups of the isocyanate compound, thereby forming an epoxy prepolymer having urethane linkages stable at room temperature; heating the prepolymer at a temperature at least 40° C. higher than the reaction temperature for the formation of the prepolymer, to dissociate the urethane linkages and regenerate the isocyanate groups; and then reacting the said isocyanate groups with the epoxy groups of the epoxy compound.
Claim 15
Dependent Claim
132 words
A process for producing a cross-linked epoxy resin which comprises subjecting to reaction one equivalent of an isocyanate compound having isocyanate groups in the molecule, and an epoxy compound having alcoholic hydroxyl groups and epoxy groups in the molecule in an amount corresponding to 0.5 to 10 epoxy equivalents and 0.2 to 3 alcoholic hydroxy equivalents, to react the alcoholic hydroxyl groups of the epoxy compound with the isocyanate groups of the isocyanate compound, thereby forming an epoxy prepolymer having urethane linkages stable at room temperature; heating the prepolymer at a temperature at least 40° C. higher than the reaction temperature for the formation of the prepolymer, to dissociate the urethane linkages and regenerate the isocyanate groups; and then reacting the said isocyanate groups with the epoxy groups of the epoxy compound.
Claim 16
Dependent Claim
86 words
A process according to claim 13, wherein the dissociation of the urethane linkages to regenerate the isocyanate groups and the reaction between the regenerated isocyanate groups and the epoxy groups are carried out in the presence of at least one compound selected from the group consisting of amine compounds, carboxylic acid anhydrides, phenol novolac compounds and polyvinyl-phenol compound in a proportion of 0.1 to 2 equivalents in terms of amine equivalent, acid anhydride equivalent or hydroxy equivalent per equivalent of the epoxy group of the prepolymer.
Claim 17
Dependent Claim
55 words
A process according to claim 13, wherein the dissociation of the urethane linkages to regenerate the isocyanate groups and the reaction between the regenerated isocyanate groups and the epoxy groups are carried out in the presence of 100 parts by weight or less of a bisimide compound per 10 parts by weight of the prepolymer.
Claim 18
Dependent Claim
108 words
A process according to claim 13, wherein the dissociation of the urethane linkages to regenerate the isocyanate groups and the reaction between the regenerated isocyanate groups and the epoxy groups are carried out in the presence of 100 parts by weight or less of a bisimide per 10 parts by weight of the prepolymer and in the presence of at least one compound selected from the group consisting of amine compounds, carboxylic acid anhydrides, phenol novolac compounds and polyvinyl-phenol compounds in a proportion of 0.1 to 2 equivalents in terms of amine equivalent, acid anhydride equivalent or hydroxy equivalent per equivalent of the epoxy group of the prepolymer.
Claim 19
Dependent Claim
225 words
A process for producing a laminate which comprises subjecting to reaction one equivalent of an isocyanate compound having isocyanate groups in the molecule and an epoxy compound having epoxy groups and alcoholic hydroxyl groups in the molecule in an amount corresponding to 0.5 to 10 epoxy equivalents and 0.2 to 3 alcoholic hydroxy equivalents to first react the alcoholic hydroxyl groups of the epoxy compound with the isocyanate groups of the isocyanate compound, thereby forming an epoxy prepolymer having urethane linkages stable at room temperature; thereafter heating the prepolymer at a temperature at least 40° C. higher than the reaction temperature for the formation of the prepolymer to dissociate the urethane linkages and regenerate the isocyanate groups; reacting the regenerated isocyanate groups with the epoxy groups if necessary in the presence of 100 parts by weight or less, per 10 parts by weight of the prepolymer, of a bisimide and/or 0.1 to 2 equivalents, in terms of amine equivalent, acid anhydride equivalent or hydroxy equivalent, per equivalent of the epoxy group of the prepolymer, of at least one compound selected from the group consisting of amine compounds, carboxylic acid anhydrides, phenol novolac compounds and polyvinyl-phenol compounds; impregnating a fibrous substrate with the resulting resin composition; superposing at least one sheet of the resin-impregnated substrate on a metallic foil; and pressing the resulting assembly with heating.
Claim 20
Dependent Claim
225 words
A process for producing a laminate which comprises subjecting to reaction one equivalent of an isocyanate compound having isocyanate groups in the molecule and an epoxy compound having epoxy groups and alcoholic hydroxyl groups in the molecule in an amount corresponding to 0.5 to 10 epoxy equivalents and 0.2 to 3 alcoholic hydroxy equivalents to first react the alcoholic hydroxyl groups of the epoxy compound with the isocyanate groups of the isocyanate compound, thereby forming an epoxy prepolymer having urethane linkages stable at room temperature; thereafter heating the prepolymer at a temperature at least 40° C. higher than the reaction temperature for the formation of the prepolymer to dissociate the urethane linkages and regenerate the isocyanate groups; reacting the regenerated isocyanate groups with the epoxy groups if necessary in the presence of 100 parts by weight or less, per 10 parts by weight of the prepolymer, of a bisimide and/or 0.1 to 2 equivalents, in terms of amine equivalent, acid anhydride equivalent or hydroxy equivalent, per equivalent of the epoxy group of the prepolymer, of at least one compound selected from the group consisting of amine compounds, carboxylic acid anhydrides, phenol novolac compounds and polyvinyl-phenol compounds; impregnating a fibrous substrate with the resulting resin composition; superposing at least one sheet of the resin-impregnated substrate on a metallic foil; and pressing the resulting assembly with heating.
References Cited (Backward Citations)
US3458527A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1986-08-29 | 1987-02-28 | 1987-08-30 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-08-29 | 1991-02-28 | 1991-08-30 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-08-29 | 1995-02-28 | 1995-08-30 | $7700.00 | Window Closed / Lapsed |