CA1150444A - Thermosetting resin composition - Google Patents
Thermosetting resin compositionInfo
- Publication number
- CA1150444A CA1150444A CA000355840A CA355840A CA1150444A CA 1150444 A CA1150444 A CA 1150444A CA 000355840 A CA000355840 A CA 000355840A CA 355840 A CA355840 A CA 355840A CA 1150444 A CA1150444 A CA 1150444A
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- CA
- Canada
- Prior art keywords
- group
- radicals
- carbon atoms
- resin composition
- atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
-
- 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
- C08F222/406—Imides, e.g. cyclic imides substituted imides comprising nitrogen other than the imide nitrogen
Abstract
Abstract of the Disclosure:
Disclosed is a thermosetting resin composition comprising (a) a bismaleimide and/or a polymaleimide and (b) at least one member selected from alkenylaniline derivatives, linear dimers thereof, and polymers thereof. In addition to components (a) and (b), this resin composition can contain (c) a polymerizable unsaturated substance.
Disclosed is a thermosetting resin composition comprising (a) a bismaleimide and/or a polymaleimide and (b) at least one member selected from alkenylaniline derivatives, linear dimers thereof, and polymers thereof. In addition to components (a) and (b), this resin composition can contain (c) a polymerizable unsaturated substance.
Description
~ his invention relates to thermosetting resin co~posi-tions having excellent heat resistance and fast-curing properties.
There are a varie-ty of heat-resistant resins which can be used as insulating materials in order to meet the demands for greater capacities, smaller sizes, lighter weights, and higher degrees of reliability of electronic devices and equipments as well as for better heat resistance characteristics, longer service lives, and maintenance-free properties of electrical machinery and apparatus. Among these heat~resistant resins, imide resins of the addition polymerization type, such as bis-maleimide resins and aromatic diamine-modified bismaleimide resins, are well known. Such bismaleimide resins have excellent heat resistance, but are not very satisfactory because of the difficulties in processing. The melting points of bismaleimides are high and their curing rates are very low. Moreover, their poor solubility in organic solvents necessitates the use of polar solvents, such as N-methyl-2-pyrrolidone and dimethylforma-mide, which are undesirable from the viewpoint of environmental polluiion. Furthermore, an organic peroxide such as dicumyl peroxide or benzoyl peroxide is usually added to maleimide resins for the purpose of promoting their cure. ~hen such a resin composition is used as impregnating varnish to make prepregs, the cleavage products of the organic peroxide remaining in the prepregs may lead to a reduc-tion in quality and perform-ance of the finally obtained laminates and, especially in the case of copper-clad laminates, to blistering or peeling-off of the copper foil.
It is well known that bismaleimides form a three-dimensional network when they are heated above their melting points or subjected to the action of free radicals. It is also known that the presence of a catalytic amount of a free-radical initiator is desirable for the purpose of achieving an effective crosslinking
There are a varie-ty of heat-resistant resins which can be used as insulating materials in order to meet the demands for greater capacities, smaller sizes, lighter weights, and higher degrees of reliability of electronic devices and equipments as well as for better heat resistance characteristics, longer service lives, and maintenance-free properties of electrical machinery and apparatus. Among these heat~resistant resins, imide resins of the addition polymerization type, such as bis-maleimide resins and aromatic diamine-modified bismaleimide resins, are well known. Such bismaleimide resins have excellent heat resistance, but are not very satisfactory because of the difficulties in processing. The melting points of bismaleimides are high and their curing rates are very low. Moreover, their poor solubility in organic solvents necessitates the use of polar solvents, such as N-methyl-2-pyrrolidone and dimethylforma-mide, which are undesirable from the viewpoint of environmental polluiion. Furthermore, an organic peroxide such as dicumyl peroxide or benzoyl peroxide is usually added to maleimide resins for the purpose of promoting their cure. ~hen such a resin composition is used as impregnating varnish to make prepregs, the cleavage products of the organic peroxide remaining in the prepregs may lead to a reduc-tion in quality and perform-ance of the finally obtained laminates and, especially in the case of copper-clad laminates, to blistering or peeling-off of the copper foil.
It is well known that bismaleimides form a three-dimensional network when they are heated above their melting points or subjected to the action of free radicals. It is also known that the presence of a catalytic amount of a free-radical initiator is desirable for the purpose of achieving an effective crosslinking
- 2 -~ ~5~
reaction (see, for example, J. Amer. Chem. Soc., Vol. 81, p.
1187, 1959). By nature, many free-radical initiators have a low activation energy for their decomposition and are unstable and easily decomposable even at room temperature, S so that special care must be taken in their storage and handling.
In accordance with the present invention, there is provided: a thermosetting resin composition comprising:
(a) at least one maleimide selected from the group consisting of bismaleimides and polymaleimides; and (b) at least one member selected from the group consisting of alkenylaniline derivatives, linear dimers thereof, and polymers thereof, the weight ratio of the maleimide to said member ranging from 1:1 to 300:1 The thermosetting resin compositions of the invention can provide a cured product having excellent storage stability, heat resistance, and moisture absorption resistance as well as good electrical and mechanical properties.
The thermosetting resin compositions of the invention can be used in the manufacture of impregnating resins~
adhesives, powder paints and coatings, and molding materials~
The thermosetting resin composition of the invention when used in the vulcanization of rubber, can exhibit excellent crosslinking and vulcanization-accelerating ef~ects.
In accordance with one preferred embodilment of this invention, there is provided a thermosetting resin com-position comprising:
:' lSV~
(a) at least one maleimide eYh~ selected from the group jconsisting of bismaleimides having the formula l; R - C - CO ~OC - C - R
i 1 11 ~ N - Z - N . Il 3 . (I) . R2 -C - CO~ ~ OC - C - R4 where Rl, R2, R3; and R4 are hydrogen atoms, halogen atoms, straight-chain or branched alkyl radicals of from 1 to 10 carbon ¦~atoms, phenyl radicals, or substituted phenyl radicals having one ;i , .
or more substituents selected from straight-chain or branched ¦alkyl radicals of from 1 to 10 carbon atoms, halogen atoms, ~13-groups in which R13 is an aliphatic radical of from 1 to 5 carbon atoms and, if there are two or more radicals re~resented by R13, .~,hey may be identical to or different from each other, R13C-'groups in which R13 is as previously defined, hydroxyl groups, and icyano group5, and the radicals represented by Rl, R2, R3, and R4 may be identical to or different from each other, and Z is a aivalent organic radical of at least 2 carbon atomsl and polymalei-des having the formula !' ¦¦1 5 1 1; ~ 7 ~ 8 ~ 9 - I 10 ~.C =C C = C C = C
. ' i l I I I I (II) jOC / O OC /CO OC CO
¢~ ~ C~
~where R5, R6, R7, R8, Rg, and Rlo are hydrogen atoms, halogen atoms, straight-chain or branched alkyl radicals of from 1 to 10 ¦carbon atoms, phenyl radicals, or substituted phenyl radicals having one or more substituents selected from halogen atoms, ! straight-chain or branched alkyl radicals of from 1 to 10 carbon ,I p~v,~us.ly ilatoms, R130- groups in which R13 is as ~}~s~ }~ defined, R13C-!! `
il ~ 4 ~
I, .
groups in which R13 is as previously defined, hydroxyl groups, and cyano groups, and the radicals represented by R , R6, R7, R8, Rg, and Rlo may be identical to or different from each other, and n is zero or a positive numberi and (b) at least one member selected from the group consisting of alkenylaniline having the formula . . .
(R12)ml ~ ~ (X)m2 (III) (Y) m3 where Rll and R12 are hydrogen atoms, halogen atoms, straight-chain or branched alkyl radicals of from 1 to 10 carbon atoms, phenyl radicals, or substituted phe~yl radicals having one or more substituents selected from halogen atoms, straight-chain or branched alkyl radicals of from 1 to 10 carbon atoms, R130- groups in which R13 is as previously defined, R13~-groups in which R13 is as previously defined, hydroxyl groups, and cyano groups, and the radicals represented by Rll and R12 may be identical to or different from each other, X is a hydrogen atom, halogen atom, carboxyl group, R13~- group in which R13 is as previously defined, R13O~ group in which R13 is as previously defined, or cyano group, Y is an amino group, glycidylamino group, diglycidylamino group, R15C-CONH- group R16C- ~OO~I
in which R15 and R16 are hydrogen atoms, halogen atoms, or straight-chain or branched alkyl radicals of from 1 to 10 carbon atoms and the radicals represented by R15 and R16 may be identical to or different from each other, RlS ~ ~ N-group in which R15 and R16 are as previously defined, 15 ~
16 ~O group in which R15 and R16 are as previously defined, R14C-NH- group in which ~a is an aliphatic radical of from 1 to 20 ~ 3 carbon atoms, alkylamino group of from l to 5 carbon atoms, or dialkylamino group in which each alkyl radical has from l to 5 carbon atoms, and m1, m2, and m3 are positive integers and the sum of ml+m2+ m3 has a value of 5; linear dimers thereof;
and polymers thereof.
In addition to the aforesaid components (a)and (b) , this thermosetting resin composition can contain (c) at least one polymerizable unsaturated su~stance. The thermosetting resin compcsitions consisting o~ components (a), (b), and (c) have more l0 excellent performance than those consisting essentially of components (a) and (b).
A particularly preferred thermosetting resin composition of the invention comprises (a) a bismaleimlde of formula (I) in which R1, R2, R3, and R4 are hydrogen atoms, halogen atoms, straight-15 chain or branched alkyl radicals of from l to 5 carbon atoms, orphenyl radicals and the radicals represented by R1, R2, R3, and R4 may be identical to or different from each other, and Z is an organic radical of 2 or more carbon atoms selected from aliphatic, alicyclic, aromatic, and heterocyclic radicals and combinations 20 thereof or a combination of an organic radical as defined above with -O-, -S-, -S-S-, -CO-, -SO-, SO2-, -CO2-, -N=N-, -NH-, or -CONH-; and/or a polymaleimide of formula (II) in which R5, R6, R7, R8, Rg, and R1o are hydrogen atoms, halogen atoms, straight-chain or branched alkyl radicals of from l to 5 carbon atoms~ or 25 phenyl radicals and the radicals represented by R5, R6, R7, R8, Rg, and R10 may be identical to or different from each other, and n has a value of from O.l to lO; and (b) an alkenylaniline derivative of formula (III~ in which R11 and R12 are hydrogen atoms, halogen atoms, straight-chain or branched alkyl radicals of from l to lO
30 carbon atoms, or phenyl radicals and the radicals represented by R11 and R12 may be identical to or different from each other, is a hydrogen or halogen atom, Y is ~n amino group, maleimido group, glycidylamino group, or alkylamino group of from 1 to 5 carbon atoms and ml,m2, and m3 are positive integers and the sum of ml+m2+m3 has a value of 5.
Specific examples o~ the radical represented by Z in formula (I) include two or more phenylene or cyclohexylene radicals interconnected either by a simple valence bond or by an atom or inert radical selected, for example, from -O-, -S-, alkylene radicals of from 1 to 3 carbon atoms, -CO-, -SO2-, NR17-, -N=N-, -CONH-, -P(O)R17-, -CONH-Xl-CONH-, ` ~
~7 ~ N - N
- C - N
N - N
~ N S ; ~ - ~ N - ~ ~ N
and ~ NH ; ~NH
where R17 is a hydrogen atom, alkyl radical of from 1 to 4 carbon atoms, phenyl radical, or cyclohexyl radical, and Xl is an alkylene radical of up to 13 carbon atorns. Each phenylene or cyclohexylene radical may have one or more substituents such as methyl radicals.
The abcve-defined bismaleimides and polymaleimides ar exemplified by the following:
Specific examples of the compounds of formula (I) include N,N'-ethylenebismaleimide, N,U'-ethylenebis(2-methylmaleimice), N,N'--trimethylenebismaleimide, M,N'-tetramethylenebismaleimide, N,N'-hexamethylenebismaleimide, N,N'-1,4-cyclohexylenebismaleimide, - 7a -., , ~50~
N,N'-m-phenylenebismaleimide, N,N'-~-phenylenebismaleimide, IIN,N'-2,4-tolylenebismaleimide, N,N'-2,6-tolylenebismaleimide, ¦iN,N'-(oxydi-~-phenylene)bismaleimide, N,N'-(oxydi-p-phenylene)bis-¦1(2-methylmaleimide~, N,N'-(methylenedi-~-phenylene)bismaleimide, ¦IN,N'-(methylenedi-p-phenylene)bis(2-methylmaleimide), N,N'-11 (methylenedi-~-phenylene)bis(2-phenylmaleimide), N,N'-(sulfonyldi-¦,~-phenylene)bismaleimide, N,N'-(thiodi-p-phenylene)bismaleimide, IlN,N'-(dithiodi-p-phenylene)bismaleimide, N,N'-(sulfonyldi-_-,'phenylene)bismaleimlde, N,N'-(o,~-isopropylidenediphenylene)bis-maleimide, N,N'-(isopropylidenedi-p-phenylene)bismaleimide, N,N'-(o,~-cyclohexylidenediphenylene)bismaleimide, N,N'-(cyclohexylidenedi-~-phenylene)bismaleimide, N,N'-(ethylenedi-p-phenylene)bismaleimide, N,N'-(m-xylylene)bismaleimide, N,N'-(p-. xylylene)bismaleimide, N,N'-(4,4"-p-triphenylene)bismaleimide, i N,N'-(p-phenylenedioxydi-p-phenylene)bismaleimide, N,N'-(methylenedi-1 ~-phenylene~bis(2,3-dichloromaleimide)-, and N,N'-(oxydi-~-¦ phenylene)bis(2-chloromaleimide). They further include maleimide-¦ terminated phenoxy compounds having the general formula I 1 11 \ N- D -COCH2CHCH2 ~ ~ C ~ OH ~R
l, . 'i ~ - 9 - C -D- N ¦¦ (IV) ., O
Il where Rl, R2, R3, and R4 are as previously defined for formula (I), D is a divalent organic radical selected from aliphatic, alicyclic, and aromatic radicals, and Q is a number having a value of from O to 20. Specific examples of the radical ., represented by D in formula (IV) include methylene, dimethylene, trimethylene, hexamethylene, m-phenylene, and p-phenylene radicals.
., po/ rr~/e/,n~ s Specific examples of the co~mpounds of formula (II) include poly(methylenephenylene) polymaleimides having the formula HC = CH HC = CH Hf = CH
N OC\ N ~ O N (V) ~ C112 ~} C~2 ~ "~i where n is a number having an average value of O or greater.
These polymaleimides can be obtained by reacting an aniline-formaldehyde condensation product of the formula NH2 ~ NH2 NH2 ~ 2 ~ ~" } 2 t ~'~ (VI) .~ ~ n : where n is as previously defined, with maleic anhydride according to any conventional procedure. The resulting polymaleimide may contain polyrneric by-products having one or more branched structural units of the formula HC = CH
: I I
OC ,50 N
(VII) . .
_ g ,, ,~ lelm~cle5 The~ 4~ ~de co~u~is of formulas (I) and (II) may be used either alone or in combination.
Specific examples of the alkenylaniline derivatives represented by the formula (III) include aminostyrene (o-, m-, and ~-isomers), isopropenylaniline (o-, m-, and p-isomers), isopropenyltoluidine (for example, 1,3,2-, 1,4,2- and 1,2,3-isomers), vinyltoluidine (for example, l,3,2-, 1,4,2- and 1,2,3-isomers), 4-amino-a-phenylstyrene, N-(_-vinyl)maleanilic acid, N-(p-isopropenylphenyl)maleamic acid, N-(2-chloro-~-isopropenylphenyl)maleamic acid, N-(~-vinylphenyl)maleimide, N-(p-isopropenylphenyl)maleimide, N-~-isopropenylphenyl)-2-methylmaleimide, N-~m-isopropenylphenyl)maleimide, N-~2-methyl-_-isopropenylphenyl)maleimide, N-(p-~-ethylvinylphenyl)maleimide, l-vinyl-3-glycidylaminobenzene, l-vinyl-4-glycidylaminobenzene, l-vinyl-4-diglycidylaminobenzene, l-isopropenyl-3-glycidylaminobenzene, l-isopropenyl-4-glycidylaminobenzene, l-isopropenyl-4-diglycidylaminobenzene, N-~p-isopropenylphenyl )isomaleimide, l-isopropenyl-4-acetylaminobenzene, l-isopropenyl-4-dimethylaminobenzene, and the like.
Specific examples of the linear dimers of the above-defined alkenylaniline derivatives include .
.,, , 4-methyl-2,4-bis(o-aminophenyl)-1-pentene, 4-methyl-2,4-bis(m~aminophenyl)-1-pentene, 4-methyl-2,4-bis(~-aminophenyl)-1-pentene, 4-methyl-2,4-bis(o-aminophenyl)-2-pentene, 4-methyl-2,4-bis(m-aminophenyl)-2-pentene, 4-methyl-2,4-bis(~-aminophenyl)-2-pentene, 4-methyl-2,4-bis[~-~2'-carboxyvinylcarbonylamino)phenyl]-1-pentene 4-methyl-2,4-bis[~-(2'-carboxyvinyIcar~onylamino)phenyl]-2-pentene, 4-methyl-2,4-bis~-N maleimidophenyl)-l-pentene, 1~ 4-methyl-2,4-bis~-N-maleimidophenyl)-2-pentene, 4-methyl-2,4-bis~-N-isomaleimidophenyl)-l-pentene, 4-methyl-2,4-bis~-N-isomaleimidophenyl)-2-pentene, 4-methyl-2,4-bis~3'-methyl-4'-N-maleimidophenyl)-l-pentene, 4-methyl-2,4-bis~3'-methyl-4'-N-maleimidophenyl)-2-pentene, lS 4-methyl-2,4-bis~3', S'-dichloro-4'-N-maleimidophenyl)-l-pentene;, 4-methyl-2,4-bis~3'95'-dichloro-4'-N-maleimidophenyl)-2-pentene,.
and the like.
The chemical makeuP of the thermosetting resin com-position of the invention may vary widely according to the purpose of its use~ The weight ratio of the bismaleimide and/
or polymaleimide to the alkenylaniline derivative and/or its linear dimer and/or its polymer can generally range from 1:1 to 300:1, the preferred range being from 5:1 to 200:1. If the amount of maleimide used is below the aforesaid limits, the resin composition as used in the form of a varnish will h~ve a shortened pot life and the cured product will show a lowering of thermal stability ox heat resistance~ while if it is above the aforesaid limits, the resin composition will show a decrease in curing rate and will have such poor curability that the cured product may fail to achieve sufficient mechanical strength.
The thermosetting resin composition of the invention can contain a polymerizable unsaturated substance in addition to the maleimide and the alkenylaniline derivative and/or dimer and/or polymer thereof. The term "polymerizable unsaturated substance" as used herein denotes vinyl monomers, radical-polymerizable unsaturated polymers, and radical polymerizable unsaturated oligomers. Specific examples of the vinyl monomers include styrene, substituted styrenes having their su~stituent or substituents on the benzene nucleus, acrylonitrile, acrylic acid and its esters, methacrylic acid and its esters, acrylamide, glycidyl acrylate, glycidyl methacrylate, divinylbenzene, divinyltoluene, diallyl phthalate, triallyl cyanurate, tribromopnenyl allyl ether, and the like. Specific examples of the radlcal-polymerizable unsaturated polymers and oligomers include unsaturated polyester, polybutadiene, polychloroprene, polypentadiene, and diallyl phthalate prepolymer; the fore-going polymers and oli~omers modified by the addition of sty ene, maleic acid, or epoxy resin; cyclic oligomers such as dicyclopentadiene and cyclododecatriene; terpenoids; and the like. These polymerizable unsaturated substances may be used either alone or in combination.
The amount of polymerizable unsaturated substances used depends on whether it is a monomer, polymer, or olgiomer.
However, the ratio of the combined weight of the maleimide and the alkenylaniline derivative and/or dimer and/or polymer thereof to the weight of the polymerizable unsaturated sub-stance can generally range from 1:50 to 200:1, the preferred range being from 1:20 to 100:1. If the amount of poly-merizable unsaturated substance used is above the aforesaid limits, the cured product will show a loweriny of heat resistance and storage stability, while if it is below the aforesaid limits, the fluidity of the resin composition will be too low to exhibit good molding properties.
3l~5~4 The thermosetting resin composition of the invention can be cured by application of heat. Although no particular limitation is placed on the curing temperature, the preferred range is from 30 to 300C. It can also be cured by exposure to radiation such as ultraviolet rays, X rays, alpha rays, beta rays, and gamma rays.
Depending on the purpose of its use, the thermosetting resin composition of the invention can be either mixed with one or more additional components or dissolved in an organic solvent. More specifically, if the resin composition is to be used as a molding material, one or more inorganic fillers such as silica, silica glass, clay, aluminum hydroxide, asbestos, glass fiber, mica, gypsum, kaolin, cement, talc, zinc white, graphite, magnesite, molybdenum disulfide, titanium white, silica sand, carbon black, barium sulfate, and calcium carbonate can be incorporated thereinto. Moreover, a conventional flame retarder such as brominated organic compounds, antimony compounds, and phosphorus compounds can be added to the resin composition for the purpose of imparting flame-retardant properties thereto.
If the resin composition is to be used in ~he form of a solutioII, it can be dissolved in an organic solvent such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, dioxane, acetone, methyl ethyl ketone, tetrahydro-uran, cellosolve, methyl acetate, ethyi acetate, chloroform, benzene, toluene, xylene, and chlorobenzene.
The thermosetting resin composition of the invention can give a cured product having excellent heat resistance, storage stability, and moisture absorption resistance as well as good electrical and mechanical properties, and can bring about an improvement in operating efficiency owing to its good molding I
~
I - 13 - ~
i and fast-curing properties. Accordingly, it has a wide variety , of industrial applications and can be used, for example, in the manufacture of impregnating resins, adhesives, powdeT paints and coatings, and molding materials. Moreover, when used in the vulcanization of rubber, it can exhibit excellent crosslink-ing and vulcanization-accelerating e-ffects, thereby imparting improved characteristics, such as very high resistance to heat deterioration, to the vulcanized rubber. Thus, it will be apparent to those skilled in the art that the thermosetting resin composition of the invention is an exceptionally good material having a wide spectrum of functionality.
The present invention is further illustrated by the following examples. In these examples, all parts and percentages are by weight unless otherwise nDted.
Examples 1-5 To 53.7g of N,N'-(methylenedi-p-phenylene)bismaleimide were added 10.5g, 3.5g9 2.5g 1.5g and 0.8g, respectively, of N-j(p-isopropenylphenyl)maleimide. These ingredients were thoroughly mixed to form a total of S resin compositions. Each resin composition was melted on an iron plate preheated to and kept at 180C, and the~ stirred well with a spatula to measure the time required for gelation. In addition, the resulting gel was measured by thermogravimetry to measure its loss in weight due to thermal decomposition, the loss in weight being regarded as a measure of its thermal decomposition. The results thus obtained are summarized in Table 1.
I
.1 Table 1 N,N'-~Methylenedi- N-(p-Isopro- Gelation Temperature -phenylene)- penylphenyl)- Time at 1% loss Example bismaleimidemaleimide in Weight (g) (g) (sec) (C) I . .
I 53.7 10.5 2n 476 53.7 3.5 37 500
reaction (see, for example, J. Amer. Chem. Soc., Vol. 81, p.
1187, 1959). By nature, many free-radical initiators have a low activation energy for their decomposition and are unstable and easily decomposable even at room temperature, S so that special care must be taken in their storage and handling.
In accordance with the present invention, there is provided: a thermosetting resin composition comprising:
(a) at least one maleimide selected from the group consisting of bismaleimides and polymaleimides; and (b) at least one member selected from the group consisting of alkenylaniline derivatives, linear dimers thereof, and polymers thereof, the weight ratio of the maleimide to said member ranging from 1:1 to 300:1 The thermosetting resin compositions of the invention can provide a cured product having excellent storage stability, heat resistance, and moisture absorption resistance as well as good electrical and mechanical properties.
The thermosetting resin compositions of the invention can be used in the manufacture of impregnating resins~
adhesives, powder paints and coatings, and molding materials~
The thermosetting resin composition of the invention when used in the vulcanization of rubber, can exhibit excellent crosslinking and vulcanization-accelerating ef~ects.
In accordance with one preferred embodilment of this invention, there is provided a thermosetting resin com-position comprising:
:' lSV~
(a) at least one maleimide eYh~ selected from the group jconsisting of bismaleimides having the formula l; R - C - CO ~OC - C - R
i 1 11 ~ N - Z - N . Il 3 . (I) . R2 -C - CO~ ~ OC - C - R4 where Rl, R2, R3; and R4 are hydrogen atoms, halogen atoms, straight-chain or branched alkyl radicals of from 1 to 10 carbon ¦~atoms, phenyl radicals, or substituted phenyl radicals having one ;i , .
or more substituents selected from straight-chain or branched ¦alkyl radicals of from 1 to 10 carbon atoms, halogen atoms, ~13-groups in which R13 is an aliphatic radical of from 1 to 5 carbon atoms and, if there are two or more radicals re~resented by R13, .~,hey may be identical to or different from each other, R13C-'groups in which R13 is as previously defined, hydroxyl groups, and icyano group5, and the radicals represented by Rl, R2, R3, and R4 may be identical to or different from each other, and Z is a aivalent organic radical of at least 2 carbon atomsl and polymalei-des having the formula !' ¦¦1 5 1 1; ~ 7 ~ 8 ~ 9 - I 10 ~.C =C C = C C = C
. ' i l I I I I (II) jOC / O OC /CO OC CO
¢~ ~ C~
~where R5, R6, R7, R8, Rg, and Rlo are hydrogen atoms, halogen atoms, straight-chain or branched alkyl radicals of from 1 to 10 ¦carbon atoms, phenyl radicals, or substituted phenyl radicals having one or more substituents selected from halogen atoms, ! straight-chain or branched alkyl radicals of from 1 to 10 carbon ,I p~v,~us.ly ilatoms, R130- groups in which R13 is as ~}~s~ }~ defined, R13C-!! `
il ~ 4 ~
I, .
groups in which R13 is as previously defined, hydroxyl groups, and cyano groups, and the radicals represented by R , R6, R7, R8, Rg, and Rlo may be identical to or different from each other, and n is zero or a positive numberi and (b) at least one member selected from the group consisting of alkenylaniline having the formula . . .
(R12)ml ~ ~ (X)m2 (III) (Y) m3 where Rll and R12 are hydrogen atoms, halogen atoms, straight-chain or branched alkyl radicals of from 1 to 10 carbon atoms, phenyl radicals, or substituted phe~yl radicals having one or more substituents selected from halogen atoms, straight-chain or branched alkyl radicals of from 1 to 10 carbon atoms, R130- groups in which R13 is as previously defined, R13~-groups in which R13 is as previously defined, hydroxyl groups, and cyano groups, and the radicals represented by Rll and R12 may be identical to or different from each other, X is a hydrogen atom, halogen atom, carboxyl group, R13~- group in which R13 is as previously defined, R13O~ group in which R13 is as previously defined, or cyano group, Y is an amino group, glycidylamino group, diglycidylamino group, R15C-CONH- group R16C- ~OO~I
in which R15 and R16 are hydrogen atoms, halogen atoms, or straight-chain or branched alkyl radicals of from 1 to 10 carbon atoms and the radicals represented by R15 and R16 may be identical to or different from each other, RlS ~ ~ N-group in which R15 and R16 are as previously defined, 15 ~
16 ~O group in which R15 and R16 are as previously defined, R14C-NH- group in which ~a is an aliphatic radical of from 1 to 20 ~ 3 carbon atoms, alkylamino group of from l to 5 carbon atoms, or dialkylamino group in which each alkyl radical has from l to 5 carbon atoms, and m1, m2, and m3 are positive integers and the sum of ml+m2+ m3 has a value of 5; linear dimers thereof;
and polymers thereof.
In addition to the aforesaid components (a)and (b) , this thermosetting resin composition can contain (c) at least one polymerizable unsaturated su~stance. The thermosetting resin compcsitions consisting o~ components (a), (b), and (c) have more l0 excellent performance than those consisting essentially of components (a) and (b).
A particularly preferred thermosetting resin composition of the invention comprises (a) a bismaleimlde of formula (I) in which R1, R2, R3, and R4 are hydrogen atoms, halogen atoms, straight-15 chain or branched alkyl radicals of from l to 5 carbon atoms, orphenyl radicals and the radicals represented by R1, R2, R3, and R4 may be identical to or different from each other, and Z is an organic radical of 2 or more carbon atoms selected from aliphatic, alicyclic, aromatic, and heterocyclic radicals and combinations 20 thereof or a combination of an organic radical as defined above with -O-, -S-, -S-S-, -CO-, -SO-, SO2-, -CO2-, -N=N-, -NH-, or -CONH-; and/or a polymaleimide of formula (II) in which R5, R6, R7, R8, Rg, and R1o are hydrogen atoms, halogen atoms, straight-chain or branched alkyl radicals of from l to 5 carbon atoms~ or 25 phenyl radicals and the radicals represented by R5, R6, R7, R8, Rg, and R10 may be identical to or different from each other, and n has a value of from O.l to lO; and (b) an alkenylaniline derivative of formula (III~ in which R11 and R12 are hydrogen atoms, halogen atoms, straight-chain or branched alkyl radicals of from l to lO
30 carbon atoms, or phenyl radicals and the radicals represented by R11 and R12 may be identical to or different from each other, is a hydrogen or halogen atom, Y is ~n amino group, maleimido group, glycidylamino group, or alkylamino group of from 1 to 5 carbon atoms and ml,m2, and m3 are positive integers and the sum of ml+m2+m3 has a value of 5.
Specific examples o~ the radical represented by Z in formula (I) include two or more phenylene or cyclohexylene radicals interconnected either by a simple valence bond or by an atom or inert radical selected, for example, from -O-, -S-, alkylene radicals of from 1 to 3 carbon atoms, -CO-, -SO2-, NR17-, -N=N-, -CONH-, -P(O)R17-, -CONH-Xl-CONH-, ` ~
~7 ~ N - N
- C - N
N - N
~ N S ; ~ - ~ N - ~ ~ N
and ~ NH ; ~NH
where R17 is a hydrogen atom, alkyl radical of from 1 to 4 carbon atoms, phenyl radical, or cyclohexyl radical, and Xl is an alkylene radical of up to 13 carbon atorns. Each phenylene or cyclohexylene radical may have one or more substituents such as methyl radicals.
The abcve-defined bismaleimides and polymaleimides ar exemplified by the following:
Specific examples of the compounds of formula (I) include N,N'-ethylenebismaleimide, N,U'-ethylenebis(2-methylmaleimice), N,N'--trimethylenebismaleimide, M,N'-tetramethylenebismaleimide, N,N'-hexamethylenebismaleimide, N,N'-1,4-cyclohexylenebismaleimide, - 7a -., , ~50~
N,N'-m-phenylenebismaleimide, N,N'-~-phenylenebismaleimide, IIN,N'-2,4-tolylenebismaleimide, N,N'-2,6-tolylenebismaleimide, ¦iN,N'-(oxydi-~-phenylene)bismaleimide, N,N'-(oxydi-p-phenylene)bis-¦1(2-methylmaleimide~, N,N'-(methylenedi-~-phenylene)bismaleimide, ¦IN,N'-(methylenedi-p-phenylene)bis(2-methylmaleimide), N,N'-11 (methylenedi-~-phenylene)bis(2-phenylmaleimide), N,N'-(sulfonyldi-¦,~-phenylene)bismaleimide, N,N'-(thiodi-p-phenylene)bismaleimide, IlN,N'-(dithiodi-p-phenylene)bismaleimide, N,N'-(sulfonyldi-_-,'phenylene)bismaleimlde, N,N'-(o,~-isopropylidenediphenylene)bis-maleimide, N,N'-(isopropylidenedi-p-phenylene)bismaleimide, N,N'-(o,~-cyclohexylidenediphenylene)bismaleimide, N,N'-(cyclohexylidenedi-~-phenylene)bismaleimide, N,N'-(ethylenedi-p-phenylene)bismaleimide, N,N'-(m-xylylene)bismaleimide, N,N'-(p-. xylylene)bismaleimide, N,N'-(4,4"-p-triphenylene)bismaleimide, i N,N'-(p-phenylenedioxydi-p-phenylene)bismaleimide, N,N'-(methylenedi-1 ~-phenylene~bis(2,3-dichloromaleimide)-, and N,N'-(oxydi-~-¦ phenylene)bis(2-chloromaleimide). They further include maleimide-¦ terminated phenoxy compounds having the general formula I 1 11 \ N- D -COCH2CHCH2 ~ ~ C ~ OH ~R
l, . 'i ~ - 9 - C -D- N ¦¦ (IV) ., O
Il where Rl, R2, R3, and R4 are as previously defined for formula (I), D is a divalent organic radical selected from aliphatic, alicyclic, and aromatic radicals, and Q is a number having a value of from O to 20. Specific examples of the radical ., represented by D in formula (IV) include methylene, dimethylene, trimethylene, hexamethylene, m-phenylene, and p-phenylene radicals.
., po/ rr~/e/,n~ s Specific examples of the co~mpounds of formula (II) include poly(methylenephenylene) polymaleimides having the formula HC = CH HC = CH Hf = CH
N OC\ N ~ O N (V) ~ C112 ~} C~2 ~ "~i where n is a number having an average value of O or greater.
These polymaleimides can be obtained by reacting an aniline-formaldehyde condensation product of the formula NH2 ~ NH2 NH2 ~ 2 ~ ~" } 2 t ~'~ (VI) .~ ~ n : where n is as previously defined, with maleic anhydride according to any conventional procedure. The resulting polymaleimide may contain polyrneric by-products having one or more branched structural units of the formula HC = CH
: I I
OC ,50 N
(VII) . .
_ g ,, ,~ lelm~cle5 The~ 4~ ~de co~u~is of formulas (I) and (II) may be used either alone or in combination.
Specific examples of the alkenylaniline derivatives represented by the formula (III) include aminostyrene (o-, m-, and ~-isomers), isopropenylaniline (o-, m-, and p-isomers), isopropenyltoluidine (for example, 1,3,2-, 1,4,2- and 1,2,3-isomers), vinyltoluidine (for example, l,3,2-, 1,4,2- and 1,2,3-isomers), 4-amino-a-phenylstyrene, N-(_-vinyl)maleanilic acid, N-(p-isopropenylphenyl)maleamic acid, N-(2-chloro-~-isopropenylphenyl)maleamic acid, N-(~-vinylphenyl)maleimide, N-(p-isopropenylphenyl)maleimide, N-~-isopropenylphenyl)-2-methylmaleimide, N-~m-isopropenylphenyl)maleimide, N-~2-methyl-_-isopropenylphenyl)maleimide, N-(p-~-ethylvinylphenyl)maleimide, l-vinyl-3-glycidylaminobenzene, l-vinyl-4-glycidylaminobenzene, l-vinyl-4-diglycidylaminobenzene, l-isopropenyl-3-glycidylaminobenzene, l-isopropenyl-4-glycidylaminobenzene, l-isopropenyl-4-diglycidylaminobenzene, N-~p-isopropenylphenyl )isomaleimide, l-isopropenyl-4-acetylaminobenzene, l-isopropenyl-4-dimethylaminobenzene, and the like.
Specific examples of the linear dimers of the above-defined alkenylaniline derivatives include .
.,, , 4-methyl-2,4-bis(o-aminophenyl)-1-pentene, 4-methyl-2,4-bis(m~aminophenyl)-1-pentene, 4-methyl-2,4-bis(~-aminophenyl)-1-pentene, 4-methyl-2,4-bis(o-aminophenyl)-2-pentene, 4-methyl-2,4-bis(m-aminophenyl)-2-pentene, 4-methyl-2,4-bis(~-aminophenyl)-2-pentene, 4-methyl-2,4-bis[~-~2'-carboxyvinylcarbonylamino)phenyl]-1-pentene 4-methyl-2,4-bis[~-(2'-carboxyvinyIcar~onylamino)phenyl]-2-pentene, 4-methyl-2,4-bis~-N maleimidophenyl)-l-pentene, 1~ 4-methyl-2,4-bis~-N-maleimidophenyl)-2-pentene, 4-methyl-2,4-bis~-N-isomaleimidophenyl)-l-pentene, 4-methyl-2,4-bis~-N-isomaleimidophenyl)-2-pentene, 4-methyl-2,4-bis~3'-methyl-4'-N-maleimidophenyl)-l-pentene, 4-methyl-2,4-bis~3'-methyl-4'-N-maleimidophenyl)-2-pentene, lS 4-methyl-2,4-bis~3', S'-dichloro-4'-N-maleimidophenyl)-l-pentene;, 4-methyl-2,4-bis~3'95'-dichloro-4'-N-maleimidophenyl)-2-pentene,.
and the like.
The chemical makeuP of the thermosetting resin com-position of the invention may vary widely according to the purpose of its use~ The weight ratio of the bismaleimide and/
or polymaleimide to the alkenylaniline derivative and/or its linear dimer and/or its polymer can generally range from 1:1 to 300:1, the preferred range being from 5:1 to 200:1. If the amount of maleimide used is below the aforesaid limits, the resin composition as used in the form of a varnish will h~ve a shortened pot life and the cured product will show a lowering of thermal stability ox heat resistance~ while if it is above the aforesaid limits, the resin composition will show a decrease in curing rate and will have such poor curability that the cured product may fail to achieve sufficient mechanical strength.
The thermosetting resin composition of the invention can contain a polymerizable unsaturated substance in addition to the maleimide and the alkenylaniline derivative and/or dimer and/or polymer thereof. The term "polymerizable unsaturated substance" as used herein denotes vinyl monomers, radical-polymerizable unsaturated polymers, and radical polymerizable unsaturated oligomers. Specific examples of the vinyl monomers include styrene, substituted styrenes having their su~stituent or substituents on the benzene nucleus, acrylonitrile, acrylic acid and its esters, methacrylic acid and its esters, acrylamide, glycidyl acrylate, glycidyl methacrylate, divinylbenzene, divinyltoluene, diallyl phthalate, triallyl cyanurate, tribromopnenyl allyl ether, and the like. Specific examples of the radlcal-polymerizable unsaturated polymers and oligomers include unsaturated polyester, polybutadiene, polychloroprene, polypentadiene, and diallyl phthalate prepolymer; the fore-going polymers and oli~omers modified by the addition of sty ene, maleic acid, or epoxy resin; cyclic oligomers such as dicyclopentadiene and cyclododecatriene; terpenoids; and the like. These polymerizable unsaturated substances may be used either alone or in combination.
The amount of polymerizable unsaturated substances used depends on whether it is a monomer, polymer, or olgiomer.
However, the ratio of the combined weight of the maleimide and the alkenylaniline derivative and/or dimer and/or polymer thereof to the weight of the polymerizable unsaturated sub-stance can generally range from 1:50 to 200:1, the preferred range being from 1:20 to 100:1. If the amount of poly-merizable unsaturated substance used is above the aforesaid limits, the cured product will show a loweriny of heat resistance and storage stability, while if it is below the aforesaid limits, the fluidity of the resin composition will be too low to exhibit good molding properties.
3l~5~4 The thermosetting resin composition of the invention can be cured by application of heat. Although no particular limitation is placed on the curing temperature, the preferred range is from 30 to 300C. It can also be cured by exposure to radiation such as ultraviolet rays, X rays, alpha rays, beta rays, and gamma rays.
Depending on the purpose of its use, the thermosetting resin composition of the invention can be either mixed with one or more additional components or dissolved in an organic solvent. More specifically, if the resin composition is to be used as a molding material, one or more inorganic fillers such as silica, silica glass, clay, aluminum hydroxide, asbestos, glass fiber, mica, gypsum, kaolin, cement, talc, zinc white, graphite, magnesite, molybdenum disulfide, titanium white, silica sand, carbon black, barium sulfate, and calcium carbonate can be incorporated thereinto. Moreover, a conventional flame retarder such as brominated organic compounds, antimony compounds, and phosphorus compounds can be added to the resin composition for the purpose of imparting flame-retardant properties thereto.
If the resin composition is to be used in ~he form of a solutioII, it can be dissolved in an organic solvent such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, dioxane, acetone, methyl ethyl ketone, tetrahydro-uran, cellosolve, methyl acetate, ethyi acetate, chloroform, benzene, toluene, xylene, and chlorobenzene.
The thermosetting resin composition of the invention can give a cured product having excellent heat resistance, storage stability, and moisture absorption resistance as well as good electrical and mechanical properties, and can bring about an improvement in operating efficiency owing to its good molding I
~
I - 13 - ~
i and fast-curing properties. Accordingly, it has a wide variety , of industrial applications and can be used, for example, in the manufacture of impregnating resins, adhesives, powdeT paints and coatings, and molding materials. Moreover, when used in the vulcanization of rubber, it can exhibit excellent crosslink-ing and vulcanization-accelerating e-ffects, thereby imparting improved characteristics, such as very high resistance to heat deterioration, to the vulcanized rubber. Thus, it will be apparent to those skilled in the art that the thermosetting resin composition of the invention is an exceptionally good material having a wide spectrum of functionality.
The present invention is further illustrated by the following examples. In these examples, all parts and percentages are by weight unless otherwise nDted.
Examples 1-5 To 53.7g of N,N'-(methylenedi-p-phenylene)bismaleimide were added 10.5g, 3.5g9 2.5g 1.5g and 0.8g, respectively, of N-j(p-isopropenylphenyl)maleimide. These ingredients were thoroughly mixed to form a total of S resin compositions. Each resin composition was melted on an iron plate preheated to and kept at 180C, and the~ stirred well with a spatula to measure the time required for gelation. In addition, the resulting gel was measured by thermogravimetry to measure its loss in weight due to thermal decomposition, the loss in weight being regarded as a measure of its thermal decomposition. The results thus obtained are summarized in Table 1.
I
.1 Table 1 N,N'-~Methylenedi- N-(p-Isopro- Gelation Temperature -phenylene)- penylphenyl)- Time at 1% loss Example bismaleimidemaleimide in Weight (g) (g) (sec) (C) I . .
I 53.7 10.5 2n 476 53.7 3.5 37 500
3 53.7 2.5 41 496 53.7 1.5 77 496 53.7 0 8 188 496 I
Examples 6-11 To 53.9g of N,N'-(methylenedi-p-phenylene)bismaleimide were;
added lO.Og, 6.7g, 3.3g, 2.4g, 1.3g and 0.5g, respectively, of an equimolar mixture of 4-methyl-2,4-bis(~-aminophenyl)-1-pentene and 4-methyl-2,4-bis(_-aminophenyl)-2-pentene. These ingredients were thoroughly mixed to form a total of 6 resin compositions.
The gelation time of each resin composition and its loss in weight due to thermal decomposi-tion were measured in the same manner as described in Example ~ . The results thus ob~ained are summarized in Table 2.
¦ Table 2 _ , _ . _ _ i N'N'-(Methylenedi- 1 Temperature p-phenylene)- Diamine ) Gelation at 1~ Loss Example bi smaleimide Time in Weight (g) (g) ~sec) ( C) _ _, _, , . j 53.7 10.0 57 418 53.7 6.7 74 438 53.7 3.3 12$ 460 53.7 2.4 134 468 ~/ 53.7 1.3 214 47~
" 53.7 _ _ 0.5 2~9 490 ,~
~ 34~
¦ 1) An equimolar mixture of 4-methyl-2,4-bis~_-aminophenyl)-l l-pentene and 4-methyl-2,4-bis~-aminophenyl)-2-pentene ¦ Example 12 To 53.7g of N,N'-~methylenedi-p-phenylene)bismaleimide was ¦ added 2.4g of an alkenylaniline derivati~e composition consisting of 7.5~ of p-isopropenylaniline, 63~ of 4-methyl-2,4-bis(_-aminophenyl)-l-pentene, 20.7~ of 4-methyl-2,4-bis~p-aminophenyl)-2-pentene, and 8.8% of _-isopropenylaniline trimer.
¦ These ingredients were thoroughly mixed to form a resin ¦ composition. When measured in the same manner as described in Il Example 11, the gelation time of this resin composition was ¦' found to be 124 seconds and the temperature at 1% loss in weight ¦I was found to be 472C.
¦ Comparative Example N,N'-(Methylenedi-p-phenylene3b-ismaleimide alone was melted on an iron plate preheated to and kept at 180C, and then stirred well with a spatula to measure the time required for gelation. As a result, the gelation time was found to be 1,307 seconds.
¦~ Example 13 An intimate mixture of lOg of styrene, 7g of N,N'-~methyl- , enedi-p-phenylene)bismaleimide, and 1.5g of N-~p-isopropenyl-¦ phenyl)~aleimide was prepared. Upon heating at 120C, it cured ¦ in 28 minutes~ When styrene was used alone~ little polymeri7a-¦ tion product was noted even after 3 hours 7 heating at that I temperature. Moreover, a mixture of styrene and the aforesaid ; bismaleimide showed similar unsuccessful results.
1.
L~
, i Example 14 An intimate mixture of 7.0g of a resin composition f (commercially available under the trade name of ESTAR ~E7472 from Mitsui Toatsu Chemicals, Inc.), 1.0g of N,N'-(methylenedi-¦ ~-phenylene)bismaleimide, and 0.2g o:E N-(~-isopropenylphenyl)-maleimide was prepared. The aforesaid resin composition consisted of about 55% of unsaturated polyester, about ~5% of styrene, and 0.02% of hydroquinone. Upon heating at 120C, this mixture cured in 13 minutes. When ESTAR XE7472 was used alone, little polymerization product was noted even after 200 minutes' heating at that temperature.
Example_15 An intimate mixture of 10g of liquid polybutadiene (commercially available under the trade name of NISSO-PB G-1000 I from Nippon Soda Company, Limited)~ lOg of styrene, 7g of ¦ N,N'-(methylenedi-p-phenylene)bismaleimide, and 2.0g of
Examples 6-11 To 53.9g of N,N'-(methylenedi-p-phenylene)bismaleimide were;
added lO.Og, 6.7g, 3.3g, 2.4g, 1.3g and 0.5g, respectively, of an equimolar mixture of 4-methyl-2,4-bis(~-aminophenyl)-1-pentene and 4-methyl-2,4-bis(_-aminophenyl)-2-pentene. These ingredients were thoroughly mixed to form a total of 6 resin compositions.
The gelation time of each resin composition and its loss in weight due to thermal decomposi-tion were measured in the same manner as described in Example ~ . The results thus ob~ained are summarized in Table 2.
¦ Table 2 _ , _ . _ _ i N'N'-(Methylenedi- 1 Temperature p-phenylene)- Diamine ) Gelation at 1~ Loss Example bi smaleimide Time in Weight (g) (g) ~sec) ( C) _ _, _, , . j 53.7 10.0 57 418 53.7 6.7 74 438 53.7 3.3 12$ 460 53.7 2.4 134 468 ~/ 53.7 1.3 214 47~
" 53.7 _ _ 0.5 2~9 490 ,~
~ 34~
¦ 1) An equimolar mixture of 4-methyl-2,4-bis~_-aminophenyl)-l l-pentene and 4-methyl-2,4-bis~-aminophenyl)-2-pentene ¦ Example 12 To 53.7g of N,N'-~methylenedi-p-phenylene)bismaleimide was ¦ added 2.4g of an alkenylaniline derivati~e composition consisting of 7.5~ of p-isopropenylaniline, 63~ of 4-methyl-2,4-bis(_-aminophenyl)-l-pentene, 20.7~ of 4-methyl-2,4-bis~p-aminophenyl)-2-pentene, and 8.8% of _-isopropenylaniline trimer.
¦ These ingredients were thoroughly mixed to form a resin ¦ composition. When measured in the same manner as described in Il Example 11, the gelation time of this resin composition was ¦' found to be 124 seconds and the temperature at 1% loss in weight ¦I was found to be 472C.
¦ Comparative Example N,N'-(Methylenedi-p-phenylene3b-ismaleimide alone was melted on an iron plate preheated to and kept at 180C, and then stirred well with a spatula to measure the time required for gelation. As a result, the gelation time was found to be 1,307 seconds.
¦~ Example 13 An intimate mixture of lOg of styrene, 7g of N,N'-~methyl- , enedi-p-phenylene)bismaleimide, and 1.5g of N-~p-isopropenyl-¦ phenyl)~aleimide was prepared. Upon heating at 120C, it cured ¦ in 28 minutes~ When styrene was used alone~ little polymeri7a-¦ tion product was noted even after 3 hours 7 heating at that I temperature. Moreover, a mixture of styrene and the aforesaid ; bismaleimide showed similar unsuccessful results.
1.
L~
, i Example 14 An intimate mixture of 7.0g of a resin composition f (commercially available under the trade name of ESTAR ~E7472 from Mitsui Toatsu Chemicals, Inc.), 1.0g of N,N'-(methylenedi-¦ ~-phenylene)bismaleimide, and 0.2g o:E N-(~-isopropenylphenyl)-maleimide was prepared. The aforesaid resin composition consisted of about 55% of unsaturated polyester, about ~5% of styrene, and 0.02% of hydroquinone. Upon heating at 120C, this mixture cured in 13 minutes. When ESTAR XE7472 was used alone, little polymerization product was noted even after 200 minutes' heating at that temperature.
Example_15 An intimate mixture of 10g of liquid polybutadiene (commercially available under the trade name of NISSO-PB G-1000 I from Nippon Soda Company, Limited)~ lOg of styrene, 7g of ¦ N,N'-(methylenedi-p-phenylene)bismaleimide, and 2.0g of
4-methyl-2,4-bis(_-aminophenyl)-1-pentene was prepared. Upon i heating at 120C, it cured in 21 minutes.
I .
Example 16 ¦ An intimate mixture of 10g of liquid polybutadiene lll (commercially available under the trade name of NEW POLYOIL
jl NX-5 from Nippon Zeon Co., Ltd.), 10g of styrene, and 7g of a polymethylene polyphenylene polymaleimide of formula (V) in which n had an average value of 0.~ was prepared. Thus, the aforesaid polymaleimide is represented by the formula HC = CH HC = CIH HC = CH
`N/CO ~N/ OC~N/CO (V) 1, ~ Hz- ~ ~ ~ ~ CH2 , , Upon heating at 120C, this mixture cured in 27 minutes.
Example 17 An in~imate mixture of 7.0g of a resin composition ~commercially available under the trade name of ESTAR XE7472 from Mitsui Toatsu Chemicals, Inc.), l.Og of N,N'-(methylenedi-p-phenylene)bismaleimide, and 0.2g of an alkenylaniline derivative composition was prepared. The aforesaid resin composition consisted of about 55% of unsaturated polyester, about 45% of styrene, and 0.02% of hydroquinone, and the aforesaid alkenylaniline derivative composition consisted of 7.5% of p-isopropenylaniline, 42.0% of 4-methyl-2,4-bis(p-aminophenyl)-l-pentene, 30.2% of 4-methyl-2,4-bis(p-aminophenyl)-pentene, 30.2% of 4-methyl-2,4-bis(p-aminophenyl)-2-pentene, and 20.3% of _-isopropenylaniline trimer. Upon heating at l20C, this mixture cured i~ 1l.5 minutes.
j ,
I .
Example 16 ¦ An intimate mixture of 10g of liquid polybutadiene lll (commercially available under the trade name of NEW POLYOIL
jl NX-5 from Nippon Zeon Co., Ltd.), 10g of styrene, and 7g of a polymethylene polyphenylene polymaleimide of formula (V) in which n had an average value of 0.~ was prepared. Thus, the aforesaid polymaleimide is represented by the formula HC = CH HC = CIH HC = CH
`N/CO ~N/ OC~N/CO (V) 1, ~ Hz- ~ ~ ~ ~ CH2 , , Upon heating at 120C, this mixture cured in 27 minutes.
Example 17 An in~imate mixture of 7.0g of a resin composition ~commercially available under the trade name of ESTAR XE7472 from Mitsui Toatsu Chemicals, Inc.), l.Og of N,N'-(methylenedi-p-phenylene)bismaleimide, and 0.2g of an alkenylaniline derivative composition was prepared. The aforesaid resin composition consisted of about 55% of unsaturated polyester, about 45% of styrene, and 0.02% of hydroquinone, and the aforesaid alkenylaniline derivative composition consisted of 7.5% of p-isopropenylaniline, 42.0% of 4-methyl-2,4-bis(p-aminophenyl)-l-pentene, 30.2% of 4-methyl-2,4-bis(p-aminophenyl)-pentene, 30.2% of 4-methyl-2,4-bis(p-aminophenyl)-2-pentene, and 20.3% of _-isopropenylaniline trimer. Upon heating at l20C, this mixture cured i~ 1l.5 minutes.
j ,
Claims (9)
The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A thermosetting resin composition comprising:
(a) at least one maleimide selected from the group consisting of bismaleimides and polymaleimides; and (b) at least one member selected from the group con-sisting of alkenylaniline derivatives, linear dimers thereof, and polymers thereof, the weight ratio of the maleimide to said member ranging from 1:1 to 300:1.
(a) at least one maleimide selected from the group consisting of bismaleimides and polymaleimides; and (b) at least one member selected from the group con-sisting of alkenylaniline derivatives, linear dimers thereof, and polymers thereof, the weight ratio of the maleimide to said member ranging from 1:1 to 300:1.
2, A thermosetting resin composition comprising:
(a) at least one maleimide selected from the group consisting of bismaleimides having the formula (I) where R1, R2, R3, and R4 are hydrogen atoms, halogen atoms, straight-chain or branched alkyl radicals of from 1 to 10 carbon atoms, phenyl radicals, or substituted phenyl radicals having one or more substituents selected from straight-chain or branched alkyl radicals of from 1 to 10 carbon atoms, halogen atoms, R13O-groups in which R13 is an aliphatic radical of from 1 to 5 carbon atoms and, if there are two or more radicals represented by R13, they may be identical to or different from each other, R C - groups in which R13 is as previously defined, hydroxyl groups, and cyano groups, and the radicals represented by R1, R2, R3, and R4 may be identical to or different from each other, and Z is a divalent organic radical of at least 2 carbon atoms; and polymaleimides having the formula (II) where R5, R6, R7, R8, R9, and R10 are hydrogen atoms, halogen atoms, straight-chain or branched alkyl radicals of from 1 to 10 carbon atoms, phenyl radicals, or substituted phenyl radicals having one or more substituents selected from halogen atoms, straight-chain or branched alkyl radicals of from 1 to 10 carbon atoms R13O- groups in which R13 is as previously defined, R13?- groups in which R13 is as previously defined, hydroxyl groups, and cyano groups, and the radicals represented by R5, R6, R7, R8, R9, and R10 may be identical to or different from each other, and n is zero or a positive number; and (b) at least one member selected from the group con-sisting of alkenylaniline derivatives having the formula (III) where R11 and R12 are hydrogen atoms, halogen atoms, straight-chain or branched alkyl radicals of from 1 to 10 carbon atoms, phenyl radicals, or substituted phenyl radicals having one or more substituents selected from halogen atoms, straight-chain or branched alkyl radicals of from 1 to 10 carbon atoms, R13 O-groups in which R13 is as previously defined, and cyano groups, and the radicals represented by R11 and R12 may be identical to or different from each other, X is a hydrogen atom, halogen atom, carboxyl group, R13?-group in which R13 is as previously defined, Rl3O- group in which R13 is as previously defined, or cyano group, Y is an amino group, glycidylamino group, diglycidylamino group, group in which R15 and R16 are hydrogen atoms, halogen atoms or straight-chain or branched alkyl radicals of from 1 to 10 carbon atoms and the radicals represented by R15 and R16 may be identical to or different from each other, group in which R15 and R16 are as previously defined, group in which R15 and R16 are as previously defined, R14?-NH- group in which R14 is an aliphatic radical of from 1 to 20 carbon atoms, an alkylamino group of from 1 to 5 carbon atoms, or a dialkylamino group in which each alkyl radical has from 1 to 5 carbon atoms, and m1, m2, and m3 are positive integers and the sum of m1+m2+m3 has a value of 5, linear dimers thereof, and polymers thereof, the weight ratio of said maleimide to said member ranging from 1:1 to 300:1.
(a) at least one maleimide selected from the group consisting of bismaleimides having the formula (I) where R1, R2, R3, and R4 are hydrogen atoms, halogen atoms, straight-chain or branched alkyl radicals of from 1 to 10 carbon atoms, phenyl radicals, or substituted phenyl radicals having one or more substituents selected from straight-chain or branched alkyl radicals of from 1 to 10 carbon atoms, halogen atoms, R13O-groups in which R13 is an aliphatic radical of from 1 to 5 carbon atoms and, if there are two or more radicals represented by R13, they may be identical to or different from each other, R C - groups in which R13 is as previously defined, hydroxyl groups, and cyano groups, and the radicals represented by R1, R2, R3, and R4 may be identical to or different from each other, and Z is a divalent organic radical of at least 2 carbon atoms; and polymaleimides having the formula (II) where R5, R6, R7, R8, R9, and R10 are hydrogen atoms, halogen atoms, straight-chain or branched alkyl radicals of from 1 to 10 carbon atoms, phenyl radicals, or substituted phenyl radicals having one or more substituents selected from halogen atoms, straight-chain or branched alkyl radicals of from 1 to 10 carbon atoms R13O- groups in which R13 is as previously defined, R13?- groups in which R13 is as previously defined, hydroxyl groups, and cyano groups, and the radicals represented by R5, R6, R7, R8, R9, and R10 may be identical to or different from each other, and n is zero or a positive number; and (b) at least one member selected from the group con-sisting of alkenylaniline derivatives having the formula (III) where R11 and R12 are hydrogen atoms, halogen atoms, straight-chain or branched alkyl radicals of from 1 to 10 carbon atoms, phenyl radicals, or substituted phenyl radicals having one or more substituents selected from halogen atoms, straight-chain or branched alkyl radicals of from 1 to 10 carbon atoms, R13 O-groups in which R13 is as previously defined, and cyano groups, and the radicals represented by R11 and R12 may be identical to or different from each other, X is a hydrogen atom, halogen atom, carboxyl group, R13?-group in which R13 is as previously defined, Rl3O- group in which R13 is as previously defined, or cyano group, Y is an amino group, glycidylamino group, diglycidylamino group, group in which R15 and R16 are hydrogen atoms, halogen atoms or straight-chain or branched alkyl radicals of from 1 to 10 carbon atoms and the radicals represented by R15 and R16 may be identical to or different from each other, group in which R15 and R16 are as previously defined, group in which R15 and R16 are as previously defined, R14?-NH- group in which R14 is an aliphatic radical of from 1 to 20 carbon atoms, an alkylamino group of from 1 to 5 carbon atoms, or a dialkylamino group in which each alkyl radical has from 1 to 5 carbon atoms, and m1, m2, and m3 are positive integers and the sum of m1+m2+m3 has a value of 5, linear dimers thereof, and polymers thereof, the weight ratio of said maleimide to said member ranging from 1:1 to 300:1.
3. The thermosetting resin composition according to claim 2 wherein, in formula (I), R1, R2, R3, and R4 are hydrogen atoms, halogen atoms, straight-chain or branched alkyl radicals of from 1 to 5 carbon atoms, or phenyl radicals and the radicals represented by R1, R2, R3, and R4 may be identical to or different from each other, and Z is an organic radical of 2 or more carbon atoms selected from aliphatic, alicyclic, aromatic, and hetercyclic radicals and combinations thereof or a combination of an organic radical as defined above with -O-, -S-, -S-S-, -CO-, -SO-, -SO2-, -CO2-, -N=N-, -NH-, or -CONH-; in formula (II), R5, R6, R7, R8, R9, and R10 are hydrogen atoms, halogen atoms, straight-chain or branched alkyl radicals of from 1 to 5 carbon atoms, or phenyl radicals and the radicals represented by R5, R6, R7, R8, R9, and R10 may be identical to or different from each other, and n has a value of from 0.1 to 10; and in formula (III), R11 and R12 are hydrogen atoms, halogen atoms, straight-chain or branched alkyl radicals of from 1 to 10 carbon atoms or phenyl radicals and the radicals represented by R11 and R12 may be identical to or different from each other, X is a hydrogen or halogen atom, and Y is an amino group, maleimido group, glycidylamino group, or alkylamino group of from 1 to 5 carbon atoms.
4. The thermosetting resin composition according to claim 2 wherein the maleimide is N,N'-(methylenedi-p-phenylene)bismaleimide.
5. The thermosetting resin composition according to claim 2 wherein the maleimide is a polymaleimide of formula (II) in which n has a value of from 0.1 to 10.
6. The thermosetting resin composition according to claim 2 which contains at least one polymerizable unsaturated substance in addition to said maleimide and said member, the ratio of combined weight of said maleimide and said member to said polymerizable unsaturated substance ranging from 1:50 to 200:1.
7. The thermosetting resin composition according to claim 6 wherein the polymerizable unsaturated substance is at least one substance selected from the group consisting of vinyl monomers, radical-polymerizable unsaturated polymers, and radical-polymerizable unsaturated oligomers.
8. The thermosetting resin composition according to claim 6 wherein the polymerizable unsaturated substance is at least one vinyl monomer selected from the group consisting of styrene, substituted styrenes, acrylonitrile, acrylic acid, acrylic esters, methacrylic acid, methacrylic esters, acrylamide, glycidyl acrylate, divinylbenzene, divinyltoluene, diallyl phthalate, triallyl cyanurate, tribromophenyl allyl ether and glycidyl methacrylate.
9. The thermosetting resin composition according to claim 6 wherein the polymerizable unsaturated substance is an unsaturated polyester, cyclized polybutadiene, or poly-butadiene having a 1, 2-double bond.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP86429/1979 | 1979-07-10 | ||
| JP8642979A JPS5611917A (en) | 1979-07-10 | 1979-07-10 | Thermosetting resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1150444A true CA1150444A (en) | 1983-07-19 |
Family
ID=13886652
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000355840A Expired CA1150444A (en) | 1979-07-10 | 1980-07-09 | Thermosetting resin composition |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US4323662A (en) |
| JP (1) | JPS5611917A (en) |
| CA (1) | CA1150444A (en) |
Families Citing this family (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5521014A (en) | 1981-11-13 | 1996-05-28 | The Boeing Company | Extended multidimensional ether or ester oligomers |
| US5512676A (en) | 1987-09-03 | 1996-04-30 | The Boeing Company | Extended amideimide hub for multidimensional oligomers |
| US5516876A (en) | 1983-09-27 | 1996-05-14 | The Boeing Company | Polyimide oligomers and blends |
| US5210213A (en) | 1983-06-17 | 1993-05-11 | The Boeing Company | Dimensional, crosslinkable oligomers |
| US5969079A (en) | 1985-09-05 | 1999-10-19 | The Boeing Company | Oligomers with multiple chemically functional end caps |
| US5693741A (en) | 1988-03-15 | 1997-12-02 | The Boeing Company | Liquid molding compounds |
| US5705598A (en) | 1985-04-23 | 1998-01-06 | The Boeing Company | Polyester sulfone oligomers and blends |
| PT77595B (en) * | 1982-11-06 | 1986-03-18 | Dsm Resins Bv | Bismaleimide-containing thermosetting compositions and polymers |
| NL8303229A (en) * | 1983-09-20 | 1985-04-16 | Dsm Resins Bv | NEW MALEIMIDE-AMIDE COMPOUNDS AND COMPOSITIONS INCLUDING THESE, PREPARATION AND APPLICATION THEREOF. |
| US4609705A (en) * | 1983-07-18 | 1986-09-02 | General Electric Company | Polyimide molding compositions |
| US4541489A (en) * | 1984-03-19 | 1985-09-17 | Phillips Petroleum Company | Method of removing flow-restricting materials from wells |
| JPS6128545A (en) * | 1984-07-18 | 1986-02-08 | Hitachi Ltd | Resin composition, laminate, and their preparation |
| US4564663A (en) * | 1985-02-21 | 1986-01-14 | The United States Of America As Represented By The Secretary Of The Navy | Free radical cure of the bismaleimide of dimer diamine |
| US4568733A (en) * | 1985-04-04 | 1986-02-04 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | High performance mixed bisimide resins and composites based thereon |
| US5618907A (en) | 1985-04-23 | 1997-04-08 | The Boeing Company | Thallium catalyzed multidimensional ester oligomers |
| US5610317A (en) | 1985-09-05 | 1997-03-11 | The Boeing Company | Multiple chemically functional end cap monomers |
| FR2589868B1 (en) * | 1985-11-13 | 1988-05-13 | Rhone Poulenc Spec Chim | POLYMERS WITH IMIDED GROUPS AND PROCESS FOR THEIR PREPARATION |
| US5364700A (en) * | 1985-12-27 | 1994-11-15 | Amoco Corporation | Prepregable resin composition and composite |
| US4714726A (en) * | 1986-06-04 | 1987-12-22 | W. R. Grace & Co. | Low temperature single step curing polyimide adhesive |
| US4740830A (en) * | 1986-06-04 | 1988-04-26 | W. R. Grace & Co. | Low temperature single step curing polyimide adhesive |
| US4851454A (en) * | 1986-07-17 | 1989-07-25 | The Dow Chemical Company | Photolytically crosslinkable thermally stable composition |
| US5817744A (en) | 1988-03-14 | 1998-10-06 | The Boeing Company | Phenylethynyl capped imides |
| US5260411A (en) * | 1988-04-20 | 1993-11-09 | Polytechnic University | Polyimide resins |
| AU617206B2 (en) * | 1988-08-15 | 1991-11-21 | Mitsubishi Rayon Company Limited | Maleimide copolymer and a process for producing the same |
| FR2664605A1 (en) * | 1990-07-16 | 1992-01-17 | Rhone Poulenc Chimie | IMIDA GROUPED POLYMERS AND PROCESS FOR PREPARATION. |
| TW209231B (en) * | 1990-10-29 | 1993-07-11 | Akzo Nv | |
| US6960636B2 (en) | 1994-09-02 | 2005-11-01 | Henkel Corporation | Thermosetting resin compositions containing maleimide and/or vinyl compounds |
| US7645899B1 (en) | 1994-09-02 | 2010-01-12 | Henkel Corporation | Vinyl compounds |
| US6852814B2 (en) * | 1994-09-02 | 2005-02-08 | Henkel Corporation | Thermosetting resin compositions containing maleimide and/or vinyl compounds |
| US20030055121A1 (en) * | 1996-09-10 | 2003-03-20 | Dershem Stephen M. | Thermosetting resin compositions containing maleimide and/or vinyl compounds |
| ES2215860T3 (en) * | 2000-10-19 | 2004-10-16 | Bridgestone Corporation | A BLEND OF RUBBER AND OTHER MISCELLANEOUS INGREDIENTS CONTAINING POLIMALEIMIDE AND A COVER. |
| GB2435262B (en) | 2006-02-16 | 2011-08-31 | Ngf Europ Ltd | Method, composition and articles |
| US7691475B2 (en) * | 2006-07-21 | 2010-04-06 | 3M Innovative Properties Company | Anisotropic conductive adhesives |
| JP2010539293A (en) * | 2007-09-13 | 2010-12-16 | スリーエム イノベイティブ プロパティズ カンパニー | Low temperature bonding electronic adhesive |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2989504A (en) * | 1960-05-18 | 1961-06-20 | Us Rubber Co | Vulcanization of polymer with nu, nu'-bismaleimides and compositions thereof |
| SE316011B (en) * | 1964-11-13 | 1969-10-13 | Rhodiaceta | |
| US3651012A (en) * | 1969-04-25 | 1972-03-21 | Gen Electric | Novel bis-imide compositions and polymers therefrom |
| US3929713A (en) * | 1973-05-25 | 1975-12-30 | Du Pont | Polymerizing bis-maleimides and polyimides therefrom |
| US3890272A (en) * | 1973-05-25 | 1975-06-17 | Univ Notre Dame Du Lac | Polymerizing bis-maleimides |
| NL7500119A (en) * | 1974-01-16 | 1975-07-18 | Ciba Geigy | MIXTURES CONTAINING MIXTURES CONTAINING POLYIMIDES CONTAINING TO THE HEAT STABLE FOAMED MATERIALS. |
| SE7506026L (en) * | 1974-07-02 | 1976-01-05 | Ciba Geigy Ag | STOCK-STABLE, MATERTABLE MIXTURES. |
| CH620938A5 (en) * | 1976-04-08 | 1980-12-31 | Ciba Geigy Ag | |
| US4179551A (en) * | 1977-10-25 | 1979-12-18 | Trw, Inc. | Low temperature curable compliant bismaleimide compositions |
| JPS54100488A (en) * | 1978-01-25 | 1979-08-08 | Toshiba Corp | Heat-resistant impregnation resin composition |
| JPS5827806B2 (en) * | 1978-01-31 | 1983-06-11 | 三井東圧化学株式会社 | Curable resin composition |
| US4216297A (en) * | 1978-02-13 | 1980-08-05 | Trw Inc. | Vinyl polybutadiene bisimide copolymers |
| US4229550A (en) * | 1978-12-11 | 1980-10-21 | Trw Inc. | Flexibilized vinyl polybutadiene maleimide resins |
-
1979
- 1979-07-10 JP JP8642979A patent/JPS5611917A/en active Granted
-
1980
- 1980-07-08 US US06/167,145 patent/US4323662A/en not_active Expired - Lifetime
- 1980-07-09 CA CA000355840A patent/CA1150444A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6221006B2 (en) | 1987-05-11 |
| JPS5611917A (en) | 1981-02-05 |
| US4323662A (en) | 1982-04-06 |
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