WO1991005002A1 - Polyimide resin laminates - Google Patents
Polyimide resin laminates Download PDFInfo
- Publication number
- WO1991005002A1 WO1991005002A1 PCT/US1990/003361 US9003361W WO9105002A1 WO 1991005002 A1 WO1991005002 A1 WO 1991005002A1 US 9003361 W US9003361 W US 9003361W WO 9105002 A1 WO9105002 A1 WO 9105002A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- bisphenol
- thermosetting resin
- laminate
- dicyandiamide
- resin composition
- Prior art date
Links
- 0 C*([N+](C)[O-])=*[N+]([O-])=* Chemical compound C*([N+](C)[O-])=*[N+]([O-])=* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F22/36—Amides or imides
- C08F22/40—Imides, e.g. cyclic imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/40—Imides, e.g. cyclic imides
- C08F222/404—Imides, e.g. cyclic imides substituted imides comprising oxygen other than the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
- C08G73/123—Unsaturated polyimide precursors the unsaturated precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
- C08G73/124—Unsaturated polyimide precursors the unsaturated precursors containing oxygen in the form of ether bonds in the main chain
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/901—Printed circuit
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31623—Next to polyamide or polyimide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31721—Of polyimide
Definitions
- the invention relates generally to cross-linked, heat resistant, thermosetting polyimide resins, used in the manufacture of laminates for the electronics industry. More particularly, it relates to a novel polyimide resin which avoids the aromatic diamines now in common commercial use.
- Thermosetting resins prepared from bisimides and aromatic diamines are in commercial use. In some instances, such compositions are prepared as prepolymers and combined with epoxy compounds and crossl inked with dicyandiamide or other agents.
- thermosetting resins are produced by reacting
- thermosetting resin suitable for use in laminates for the electronics industry is prepared from (a) a bisimide, preferably a bismaleimide, (b) a polyphenol, preferably a bisphenol, which may be styrene-terminated (i.e. a vinyl benzyl ether of a bisphenol), and (c) dicyandiamide. Additional flame retardant properties are achieved by including octabromodiphenyl oxide in effective amounts while retaining the desirable
- the resin is principally comprised of a bisimide with minor amounts of components (b) and (c).
- the weights of (a), (b), and (c) preferably will be between 80 to 98%/1 to 10X/0.1 to 10%, respectively, most preferably 94 to 98%/l to 236/1.5 to 3%, respectively, based on the total of (a), (b), and (c).
- the octabromodiphenyl oxide will be added in effective amounts up to about 5 weight percent based on the resin.
- thermosetting resins of the invention can replace those made by reacting a bisimide with an aromatic dlamine. Such resins are polymerized and then cross! inked by use of
- Bisimides are compounds having the general formula D(CO) 2 N-A-N(CO) 2 D where D is a divalent radical containing a carbon-carbon double bond and A is a linking group which may be a divalent radical having at least 2 carbon atoms.
- D is a divalent radical containing a carbon-carbon double bond
- A is a linking group which may be a divalent radical having at least 2 carbon atoms.
- BMI bismaleimide
- the bisimide compound will be selected to provide resins having improved toughness, low water absorption, low dielectric constant, and excellent thermal resistance.
- Resins of the invention are usually comprised mainly of the bisimide, preferably from about 80 to 98 weight %, most preferably 94 to 98 weight percent.
- the prepolymers of bisimides and aromatic diamines of the prior art contain smaller amounts of the bisimides than are employed in the present resins.
- the bisimide can react with the diamine through the unsaturated carbon-carbon bond of the imide ring, but it may also react with itself in the same manner.
- a further component of the composition is
- dicyandiamide which is more commonly used in other resin systems as a crosslinking agent once the bisimide and diamine have formed a prepolymer.
- the dicyandiamide here is believed to take an essential, although not fully understood, role in the polymer formation and not to be merely a cross-linking agent.
- the polyphenols used in the resins of the invention preferably are bisphenols, particularly those within the following formula:
- the polyphenols are present in the resin in minor amounts, preferably about 1 to 10 wt.%, most preferably 1 to 2 wt.% Composition of the Resin
- thermosetting resin composition according to the invention may comprise (a) a bisimide having the formula:
- A compri ses at least one of alkylene radical s having
- radicals containing at least one of O, S, and N and phenylene or polycyclic aromatic radicals
- D is a divalent radical containing a carbon-carbon double bond
- the bisimide Is a bismaleimide and the thermosetting resin composition may comprise (a) a bismaleimide having the formula:
- A is -C 6 H 4 -CH 2 -C 6 H 4 -, -C 6 H 4 -C-C 6 H 4 -, -C 6 H 4 -C-C 6 H 4 -, CH 3 3
- R 1 , R 2 , R 3 , R 4 H, CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 , C 5 H 11 and the bisphenol has the formula 2
- Sigma bond refers to a covalent bond between the aromatic rings and corresponds to a bisphenol in which the aromatic rings are directly joined.
- the resin composition may comprise 1-10 mols of (a), greater than zero to 1 mols of (b), and greater than zero to 2 mols of (c).
- Particularly preferred embodiments include those which have bismaleimides where A is 3
- R 1 , R 2 , R 3 , R 4 are each H; and bisphenols where Z is H or
- CH 2 CH-C 6 H 4 -CH 2 -; E is CH 3 -C-CH 3 ; and B is H or Br.
- octabromodiphenyl oxide is capable of providing laminates which meet the UL-94 test for flamrnability while retaining the other physical properties characteristic of the bismaleimide-bisphenol- dicyandiamide resins described above. Sufficient amounts of the octabromodiphenyl oxide are added to the resin formulation to meet the UL-94 test for flamrnability, up to a maximum of about 5 weight percent, after which the other physical properties are adversely affected.
- the improved bismaleimide resins may be prepared by reacting the three components in a solvent at an elevated temperature to form a prepolymer.
- a suitable solvent such as dimethyl formamide (DMF), N- methylpyrrol idone, dimethyl acetamide, acetone, benzene, toluene, and the like to a temperature at which the chosen bismaleimide will be dissolved, say about 90 to 100oC.
- the bismaleimide is added to the solvent and mixed until dissolved.
- the temperature is increased to the desired reaction temperature, about 120 to 140oC, at which time the second and third components are added and mixed.
- the three-component mixture in the solvent will be maintained at the reaction temperature for a sufficient period of time to partially complete the reaction. Polymerization is completed during the manufacture of laminates.
- octabromodiphenyl oxide is added before impregnating the
- the resins of the invention may be used to prepare laminates for the electronics industry by techniques generally in use in the field. Generally, the resins are diluted with a solvent and then used to impregnate a fabric with fibers of glass, high strength organic polymers, and the like familiar to those skilled in the art, and then dried at an elevated temperature. The resulting composite may then be laminated with other layers, such as copper foil, and then baked to fully cure the finished laminate. Such laminates may be used in fabrication of printed circuit boards having improved properties.
- the resins were prepared by this procedure.
- Dimethylformamide (DMF) was added to a glass flask and heated to 100oC.
- the bismaleimide resin (Skybond 3000 supplied by Monsanto) was added to the DMF and the temperature returned to 100oC, when
- Style 108 glass bonding sheet target 62% ⁇ 5% resin; 30% ⁇ 5% flow; 4% maximum volatiles
- Target flammability values are 2.5 seconds average and 5.0 seconds maximum for any one test.
- Style 108 glass bonding sheets targets 62% ⁇ 5% resin; 30% ⁇ 5% flow; 4% maximum volatiles
- Target flammability values are 2.5 seconds average and 5.0 seconds maximum for any one test.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
A thermosetting resin is comprised of (a) a bisimide, particularly a bismaleimide, (b) a polyphenol, particularly a bisphenol, and (c) dicyandiamide. The polyphenol may be styrene-terminated (i.e. a vinyl benzyl ether of a bisphenol). Flame retardance is improved by the addition of octabromodiphenyl oxide.
Description
POLYIMIDE RESIN LAMINATES
Cross-Reference to Related Applications This application is a continuation-in-part of U.S. Serial No. 187,158, filed April 28, 1988
Field of the Invention
The invention relates generally to cross-linked, heat resistant, thermosetting polyimide resins, used in the manufacture of laminates for the electronics industry. More particularly, it relates to a novel polyimide resin which avoids the aromatic diamines now in common commercial use.
Prior Art
Thermosetting resins prepared from bisimides and aromatic diamines are in commercial use. In some instances, such compositions are prepared as prepolymers and combined with epoxy compounds and crossl inked with dicyandiamide or other agents.
While resins derived from bisimides and aromatic diamines perform well in electronic laminates, they have several disadvantages. If substitute materials could be found that had improved performance, contained no free aromatic diamines, were less brittle and met UL flarnmability rating V-0, they should find ready acceptance in the marketplace.
In commonly assigned application Serial No.850,660 now abandoned, thermosetting resins are produced by reacting
bismaleimides (Including a prepolymer chain-extended with an aromatic diamlne) with styrene-terminated bisphenol (and/or the tetrabromo substituted compound). It is characteristic of these compositions to be blended together, combined with reinforcing materials, and cured to prepare laminates. Such compositions are not chemically reacted until the laminates are formed. Such resins are shown to have a desirably low dielectric constant, but they exhibit low peel strength and are too brittle and improved resins have been sought.
In the parent of this application, Serial No. 187,158, an improved thermosetting resins was disclosed which had many desirable properties. It has been found that better flame retardant properties could be obtained for laminates using such resins, but the resin-flame retardant combinations have been found to have unexpected synergistic properties, as well as seen in the discussion which follows.
Summary of the Invention
An improved thermosetting resin suitable for use in laminates for the electronics industry is prepared from (a) a bisimide, preferably a bismaleimide, (b) a polyphenol, preferably a bisphenol, which may be styrene-terminated (i.e. a vinyl benzyl ether of a bisphenol), and (c) dicyandiamide. Additional flame retardant properties are achieved by including octabromodiphenyl oxide in effective amounts while retaining the desirable
properties of the resin.
The resin is principally comprised of a bisimide with minor amounts of components (b) and (c). The weights of (a), (b), and (c) preferably will be between 80 to 98%/1 to 10X/0.1 to 10%, respectively, most preferably 94 to 98%/l to 236/1.5 to 3%, respectively, based on the total of (a), (b), and (c). The octabromodiphenyl oxide will be added in effective amounts up to about 5 weight percent based on the resin.
Description of the Preferred Embodiments
The thermosetting resins of the invention can replace those made by reacting a bisimide with an aromatic dlamine. Such resins are polymerized and then cross! inked by use of
dicyandiamide or related compounds. The present resins, however, introduce dicyandiamide as an intrinsic element of the
composition, and thereby producing a superior laminate, as will be seen.
Bisimides
Bisimides are compounds having the general formula D(CO)2N-A-N(CO)2D where D is a divalent radical containing a carbon-carbon double bond and A is a linking group which may be a divalent radical having at least 2 carbon atoms. Particularly preferred are bismaleimide (BMI) compounds where A comprises an isopropyl radical or an ether linkage between two or more phenyl radicals which are attached to the nitrogen atoms.
For purposes of the present invention, the bisimide compound will be selected to provide resins having improved toughness, low water absorption, low dielectric constant, and excellent thermal resistance.
Resins of the invention are usually comprised mainly of the bisimide, preferably from about 80 to 98 weight %, most preferably 94 to 98 weight percent. Typically, the prepolymers of bisimides and aromatic diamines of the prior art contain smaller amounts of the bisimides than are employed in the present resins. The bisimide can react with the diamine through the unsaturated carbon-carbon bond of the imide ring, but it may also react with itself in the same manner. In the resins of the invention, a further component of the composition is
dicyandiamide, which is more commonly used in other resin systems as a crosslinking agent once the bisimide and diamine have formed a prepolymer. The dicyandiamide here is believed to take an essential, although not fully understood, role in the polymer formation and not to be merely a cross-linking agent.
Dicyandiamide
This compound has the formula
NH
NH2CNHC=N
It i s capable of reacting with the carbon-carbon double bond of the bi smaleimide to extend the polymer chain.
Only relatively small amounts of dicyandiamide are required, broadly about 0.1 to 10 wt.% of the resin may be used. Preferably, about 1.5 to 3 wt.% would be reacted to form the resin.
Polyphenols
The polyphenols used in the resins of the invention preferably are bisphenols, particularly those within the following formula:
B - H, Br, CH3
Of particular interest are the group consisting of bisphenol A, tetrabromobisphenol A, vinyl benzyl ether of bisphenol A, and vinyl benzyl ether of tetrabromobisphenol A.
The polyphenols are present in the resin in minor amounts, preferably about 1 to 10 wt.%, most preferably 1 to 2 wt.% Composition of the Resin
A thermosetting resin composition according to the invention may comprise (a) a bisimide having the formula:
where: A compri ses at least one of alkylene radical s having
1 to 20 carbon atoms, cycloalkylene radicals having 4 to 40 carbon atoms, heterocycl ic
radicals containing at least one of O, S, and N, and phenylene or polycyclic aromatic radicals
D is a divalent radical containing a carbon-carbon double bond
(b) a bi sphenol , and
(c) dicyandiamide.
In a preferred embodiment the bisimide Is a bismaleimide and the thermosetting resin composition may comprise (a) a bismaleimide having the formula:
-C6H4-O-C6H4-O-C6H4-,- C 3 3
B = H, Br, CH3
and (c) dicyandiamide. The term "sigma bond" refers to a covalent bond between the aromatic rings and corresponds to a bisphenol in which the aromatic rings are directly joined.
The resin composition may comprise 1-10 mols of (a), greater than zero to 1 mols of (b), and greater than zero to 2 mols of (c).
Particularly preferred embodiments include those which have bismaleimides where A is
3
CH2 = CH-C6H4-CH2-; E is CH3-C-CH3; and B is H or Br.
Flame Retardants
Use of bisphenols containing bromine improves flame retardant properties of laminates prepared from the above described resins. For some compositions and for some end uses it may be necessary to add additional flame retardants in order to meet required tests. The inventors have discovered that, contrary to experience with epoxy-based laminates, that bismaleimide-based laminates respond differently to the addition of bromine
containing compounds. In particular, certain compounds are not sufficiently effective and/or may adversely affect other
properties of the laminates. Generally, the amount of bromine present in the finished laminate does not predict the results of the usual flamrnability tests. It has been found that
octabromodiphenyl oxide is capable of providing laminates which meet the UL-94 test for flamrnability while retaining the other physical properties characteristic of the bismaleimide-bisphenol- dicyandiamide resins described above. Sufficient amounts of the octabromodiphenyl oxide are added to the resin formulation to meet the UL-94 test for flamrnability, up to a maximum of about 5 weight percent, after which the other physical properties are adversely affected.
Resin Synthesis
The improved bismaleimide resins may be prepared by reacting the three components in a solvent at an elevated temperature to form a prepolymer. One convenient procedure is to warm a suitable solvent, such as dimethyl formamide (DMF), N- methylpyrrol idone, dimethyl acetamide, acetone, benzene, toluene, and the like to a temperature at which the chosen bismaleimide will be dissolved, say about 90 to 100ºC. The bismaleimide is added to the solvent and mixed until dissolved. Then the temperature is increased to the desired reaction temperature, about 120 to 140ºC, at which time the second and third components are added and mixed. The three-component mixture in the solvent will be maintained at the reaction temperature for a sufficient period of time to partially complete the reaction. Polymerization is completed during the manufacture of laminates. The
octabromodiphenyl oxide is added before impregnating the
reinforcing fibers.
Use of the Resins
The resins of the invention may be used to prepare laminates for the electronics industry by techniques generally in use in the field. Generally, the resins are diluted with a solvent and then used to impregnate a fabric with fibers of glass, high strength organic polymers, and the like familiar to those skilled in the art, and then dried at an elevated temperature. The resulting composite may then be laminated with other layers, such as copper foil, and then baked to fully cure the finished laminate. Such laminates may be used in fabrication of printed circuit boards having improved properties.
In the following examples, unless otherwise specified, the resins were prepared by this procedure. Dimethylformamide (DMF) was added to a glass flask and heated to 100ºC. The bismaleimide resin (Skybond 3000 supplied by Monsanto) was added to the DMF and the temperature returned to 100ºC, when
dicyandiamide and the bisphenol ("STTBBPA", a styrene terminated
tetrabromo bisphenol A, i.e., a vinyl benzyl ether of a brominated bisphenol A) were added to the mixture. The flask was heated to 140ºC and maintained at that temperature until the desired degree of reaction is reached. This was determined by sampling the mixture and determining the gel time by stroke cure method on a cure plate. When the resin had a gel time of about 6-7 minutes at 171ºC, the reaction was stopped by cooling the flask. The flame retardent compounds were added and the resin was then ready for use. Example I
A series of laminates were prepared with varying amounts of two bromine flame-retardant compounds, octabromo diphenyl oxide according to the invention (samples 1-3) and for comparison tetrabromobisphenol A (samples 4-6). The composition of each resin, its processing into laminate, and the results of tesss on the laminates are shown in the following tables.
(1) Style 108 glass bonding sheet, target 62% ± 5% resin; 30% ± 5% flow; 4% maximum volatiles
(2) 8 ply style 7628 glass
Target flammability values are 2.5 seconds average and 5.0 seconds maximum for any one test.
(1) Style 108 glass bonding sheets, targets 62% ± 5% resin; 30% ± 5% flow; 4% maximum volatiles
(2) 8 ply style 7628 Glass,
Target flammability values are 2.5 seconds average and 5.0 seconds maximum for any one test.
(3) 5 mil thickness, 2 ply style 108 glass, 1 oz. copper both sides, target 600 seconds
It can be seen from Table A that increasing the amount of octabromodiphenyl oxide reduces the flamrnability test results to within the target range, while the solder blister test apparently is not significantly affected. However, tetrabromobisphenol, even at about the same total bromine content does not reduce the flamrnability results effectively but at the same time reduces the solder blister test and percent volatϋes results to unacceptable values. It is concluded that the octabromo-diphenol oxide is uniquely effective as a flame retardant additive for the bismaleimide-based resins of the invention.
Claims
1. A thermosetting resin composition
(a) said bisimide having the formula:
C
/
D
C C
0 I 0 I where: A comprises at least one of alkylene radicals having 1 to 20 carbon atoms, cycloalkylene radicals having 4 to 40 carbon atoms, heterocyclic radicals containing at least one of O, S, and N,
phenylene or polycyclic aromatic radicals.
D is divalent radicals containing a carbon-carbon double bond
(b) a polyphenol;
(c) dicyandiamide, where the weight of (a), (b), and (c) are 80 to 98%/1 to 10%/ and 0.1 to 10%, respectively, based on the total weight of {a), (b), and (c) and (d) octabromodiphenyl oxide in an effective amount up to about 5 weight percent.
2. A thermosetting resin composition consisting essentially of:
(a) a bismaleimide;
(b) a bisphenol or a vinyl benzyl ether of a bisphenol; (c) dicyandiamide, and
(d) octabromodiphenyl oxide.
3. A thermosetting resin of Claim 1 wherein the weights of (a), (b), and (c) are 94 to 98%/l to 2%/ and 1.5 to 3% respectively.
4. A thermosetting resin composition of Claim 2 wherein
(a) is:
-C6H4-O-C6H4-O-C6H4-, H C
-C6H4-C6H4-, -C6H4-, -C6H3CH3-, 3
-C6G4-O-C6H4-C-C6H4-O-C6H4-, -C6H4-C-C6H4-, 3
R1, R2, R3, R4 = H, CH3, C2H5, C3H7, C4H9, C5H11
B = H, Br, CH3
5. A thermosetting resin composition of Claim 4 wherein
(a) is
and (b) is: 2 3 2
6. A flame resistant laminate comprising a reinforcing fabric and a thermosetting resin composition consisting essentially of:
(a) a bismaleimide;
(b) a bisphenol or a vinyl benzyl ether of a bisphenol; (c) dicyandiamide, and
(d) octabromodiphenyl oxide.
7. The flame retardant laminate of Claim 6 wherein the weight of (a), (b), and (c) are 80-98%/1 to 10%/ and 0.1 to 10% respectively and (d) is present in an effective amount up to about 5 weight percent.
8. The flame retardant laminate of Claim 6 wherein
(a) is:
-C6H4-C6H4-, -C6H4-, -C6H3CH3- ,
R1, R2, R3, R4 = H, CH3, C2H5, C3H7, C4H9 , C5H11
(b) is
B = H, Br, CH3
9. A flame retarding laminate of Claim 8 wherein (a) is
and (b) is:
10. A flame retarding laminate of Claim 6 wherein said reinforcing fabric includes glass fibers.
11. A printed circuit board comprising the flame resi stant laminate of Claims 6-10.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE69017699T DE69017699T2 (en) | 1989-09-28 | 1990-06-13 | POLYIMIDE RESIN LAMINATES. |
EP90913331A EP0493414B1 (en) | 1989-09-28 | 1990-06-13 | Polyimide resin laminates |
KR1019920700675A KR927003690A (en) | 1989-09-28 | 1990-06-13 | Polyimide resin laminate |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/413,883 US5004775A (en) | 1988-04-28 | 1989-09-28 | Polyimide resin laminates |
US413,883 | 1989-09-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1991005002A1 true WO1991005002A1 (en) | 1991-04-18 |
Family
ID=23639065
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1990/003361 WO1991005002A1 (en) | 1989-09-28 | 1990-06-13 | Polyimide resin laminates |
Country Status (7)
Country | Link |
---|---|
US (1) | US5004775A (en) |
EP (1) | EP0493414B1 (en) |
JP (1) | JPH05500525A (en) |
KR (1) | KR927003690A (en) |
AT (1) | ATE119555T1 (en) |
DE (1) | DE69017699T2 (en) |
WO (1) | WO1991005002A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1113459A2 (en) * | 1999-12-28 | 2001-07-04 | TDK Corporation | Composite dielectric material containing ceramic powders and substrate coated with this material |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5334696A (en) * | 1992-12-18 | 1994-08-02 | Allied Signal Inc. | Polyimide resin laminates |
US5393887A (en) * | 1993-10-04 | 1995-02-28 | Monsanto Company | Bisimide compositions |
US5302723A (en) * | 1993-10-04 | 1994-04-12 | Monsanto Company | Process for preparing flame retardant bisimide compositions |
DE102008057921A1 (en) | 2008-11-19 | 2010-05-20 | Döhre, Sven, Dipl.-Inf. | Flashlight holder for bicycle, comprises flexible toothed belt, whose diameter varies continuously over screw, where flashlight mounting and guide rail mounting are arranged to rotate against each other |
JP7056201B2 (en) * | 2018-02-14 | 2022-04-19 | 昭和電工マテリアルズ株式会社 | Thermosetting resin composition, prepreg, laminated board, printed wiring board and high-speed communication compatible module |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0078039A1 (en) * | 1981-10-23 | 1983-05-04 | Hitachi, Ltd. | Thermosetting resin composition, prepolymer thereof and cured article thereof |
EP0269392A2 (en) * | 1986-11-20 | 1988-06-01 | Amoco Corporation | Improved thermoset compositions comprising aromatic cyanate esters and allyl ethers of bisphenols |
US4752641A (en) * | 1984-03-02 | 1988-06-21 | Hitachi, Ltd. | Thermosetting resin composition and prepolymer obtained therefrom |
WO1989010379A1 (en) * | 1988-04-28 | 1989-11-02 | Allied-Signal Inc. | Polyimide resin |
-
1989
- 1989-09-28 US US07/413,883 patent/US5004775A/en not_active Expired - Fee Related
-
1990
- 1990-06-13 KR KR1019920700675A patent/KR927003690A/en not_active Application Discontinuation
- 1990-06-13 DE DE69017699T patent/DE69017699T2/en not_active Expired - Fee Related
- 1990-06-13 AT AT90913331T patent/ATE119555T1/en not_active IP Right Cessation
- 1990-06-13 JP JP2512468A patent/JPH05500525A/en active Pending
- 1990-06-13 WO PCT/US1990/003361 patent/WO1991005002A1/en active IP Right Grant
- 1990-06-13 EP EP90913331A patent/EP0493414B1/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0078039A1 (en) * | 1981-10-23 | 1983-05-04 | Hitachi, Ltd. | Thermosetting resin composition, prepolymer thereof and cured article thereof |
US4752641A (en) * | 1984-03-02 | 1988-06-21 | Hitachi, Ltd. | Thermosetting resin composition and prepolymer obtained therefrom |
EP0269392A2 (en) * | 1986-11-20 | 1988-06-01 | Amoco Corporation | Improved thermoset compositions comprising aromatic cyanate esters and allyl ethers of bisphenols |
WO1989010379A1 (en) * | 1988-04-28 | 1989-11-02 | Allied-Signal Inc. | Polyimide resin |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1113459A2 (en) * | 1999-12-28 | 2001-07-04 | TDK Corporation | Composite dielectric material containing ceramic powders and substrate coated with this material |
EP1113459A3 (en) * | 1999-12-28 | 2001-08-29 | TDK Corporation | Composite dielectric material containing ceramic powders and substrate coated with this material |
US6908960B2 (en) | 1999-12-28 | 2005-06-21 | Tdk Corporation | Composite dielectric material, composite dielectric substrate, prepreg, coated metal foil, molded sheet, composite magnetic substrate, substrate, double side metal foil-clad substrate, flame retardant substrate, polyvinylbenzyl ether resin composition, thermosettin |
Also Published As
Publication number | Publication date |
---|---|
US5004775A (en) | 1991-04-02 |
EP0493414B1 (en) | 1995-03-08 |
JPH05500525A (en) | 1993-02-04 |
ATE119555T1 (en) | 1995-03-15 |
KR927003690A (en) | 1992-12-18 |
DE69017699D1 (en) | 1995-04-13 |
EP0493414A1 (en) | 1992-07-08 |
DE69017699T2 (en) | 1995-09-14 |
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