CA2081000A1 - Epoxy novolaks stabilised with organic phosphorus compounds - Google Patents
Epoxy novolaks stabilised with organic phosphorus compoundsInfo
- Publication number
- CA2081000A1 CA2081000A1 CA002081000A CA2081000A CA2081000A1 CA 2081000 A1 CA2081000 A1 CA 2081000A1 CA 002081000 A CA002081000 A CA 002081000A CA 2081000 A CA2081000 A CA 2081000A CA 2081000 A1 CA2081000 A1 CA 2081000A1
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- Prior art keywords
- formula
- composition according
- bromo
- group
- methyl
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
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- 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
- H05K1/0326—Organic insulating material consisting of one material containing O
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Medicines Containing Plant Substances (AREA)
Abstract
Epoxy novolaks stabilised with organic phosphorus compounds Abstract of the Disclosure Compositions comprising a) an epoxidised novolak, and b) 0.1 to 100 parts by weight, based on 100 parts by weight of component a), of at least one compound of formula I
(I), wherein X1 is chloro or bromo, X2 is chloro, bromo or hydrogen, and Y is O or S,and R1 and R2 are each independently of the other C1-C4alkyl, and R3 and R4 are a group of formula II
(II), wherein R1, R2. X1 and X2 are as defined above, which group carries identical or different substituents, or R3 and R4, when taken together, form a group of formula III
(I), wherein X1 is chloro or bromo, X2 is chloro, bromo or hydrogen, and Y is O or S,and R1 and R2 are each independently of the other C1-C4alkyl, and R3 and R4 are a group of formula II
(II), wherein R1, R2. X1 and X2 are as defined above, which group carries identical or different substituents, or R3 and R4, when taken together, form a group of formula III
Description
2~V.~
Epoxv novolaks stabilised with or~anic phosphorus compounds The present invention relates to novel compositions comprising an epoxidised novolak and at least one speci~lc organic phosphorus compound as flame retardant, and to the use of said compositions in encapsulating systems and laminating resins.
The flame resistance of polymers can be enhanced in different ways, for example by reducing the organic polymer component by adding fillers of low flammability such as quartz flour, glass or wollastonite, and also by the addition of flame retardants such as boron compounds, metal hydroxides, brominated compounds, halogenated phosphoric acid esters or specific organic phosphorus compounds as disclosed in European patent application 0 456 605.
The flame retardants currently added to the epoxy novolaks which are used in encapsulating systems and in laminating resins and which have to be made flame resistant are usually combinations of brominated organic compounds in admixture with antimony trioxide, the brominated organic compound normally being a brominated and glycidylised novolak.
For some time there have been ongoing efforts to develop replacement products for antimony trioxide for ecological and industrial health reasons, all the more so as antimony trioxide is preferably used in the ~me (dust) form in which it has the best flame retardant effect. If the antimony trioxide component is eliminated, then it is observed that the thermostability of encapsulating compositions is markedly impaired.
Surprisingly, it has now been found that specific combinations of epoxidised novolaks and specific sterically hindered organic (thio)phosphates, without the use of antimony trioxide and with a low halogen concentration in the encapsulating and laminating systems, ensure excellent flame resistance without the other performance properties such as thermal resistance, mechanical strength, dielectric constant or water absorption, being materially influenced.
2~8~f3 Specifically, the invention relates to compositions comprising a) an epoxidised novolak, and b) 0.1 to 100 parts by weight, based on 100 parts by weight of component a), of at least one compound of formula I
X1~0- 1 -Y (I), wherein ~1 is chloro or bromo, X2 is chloro, bromo or hydrogen, and Y is OorS, and Rl and R2 are each independently of the other Cl-C4alkyl, and R3 and R4 are a group of formula II
R,l _o~X1 (II), R2 x2 wherein Rl, R2, Xl and X2 are as defined above, which group calTies identical or different substituents, or R3 and R4, when taken together, forrn a group of formula m R2~R1 ~o~
CH2 (III), C~' 208~0~
wherein Rl and R2 are as defined above.
Xl and X2 are chloro and, preferably, bromo. X2 is preferably hydrogen. Y is preferably oxygen.
Rl and R2 as aLkyl substituents may each independently of the other typically be methyl, ethyl, propyl, isopropyl, butyl or tert-butyl. Rl in ~ormulae I and Il is preferably methyl or tert-butyl and, in formula III, is preferably tert-butyl. The preferred meaning of 1~2 is methyl.
In preferred compounds of formula I, Xl is bromo, X2 is hydrogen and Y is oxygen.
In particularly preferred compounds of formula I, Xl is bromo, X2 is hydrogen, Y is oxygen, Rl is methyl or tert-butyl, R2 is methyl, and R3 and R4 are each an identically substituted group of -formula I~, and Xl, X2, Rl and R2 are as defined above.
Further preferred compounds of forrnula I are those wherein R3 and R4, when taken together, form a group of formula III, and Xl is bromo, X2 is hydrogen, Y is oxygen, Rl and R2 in formula I are rnethyl, and Rl in formula UI is tert-butyl, and R2 in formula III is methyl.
The compounds of forrnula I and the preparation thereof are known and disclosed in European patent application 0 456 605 referred to above.
Suitable epoxidised novolaks are typically epoxy phenol novolak and epoxy cresolnovolak resins which may be obtained by condensing phenolic compounds with aldehydes. Owing to their high functionality - usually 2 to 6 epoxy groups per molecule -they are capable, in conjunction with the customary crosslinking agents, preferably at elevated temperature, of constructing a very compact macromolecular ne~work.
Exemplary of phenolic compounds are phenol, alkylphenols containing up to 9 carbon atoms in the alkyl moiety, typically cresols, xylenols, ethyl-, propyl- and butylphenols, and also phenylphenols, resorcinol, pyrocatechol, hydroquinone, bisphenol A and pyro-gallol.
Exemplary of aldehydes are formaldehyde, acetaldehyde, benzaldehyde and 2 ~ g ~
teraphthalaldehyde .
It is preferred to use phenol-foremaldehyde resins and, more particularly, cresol-formaldehyde resins, for the preparation of which o-, m- or p-cresol or mixtures of these isomers have been used in any or in given rados. The preparation of such resins is known.
It is preferred to use 0.5 to 30 parts by weight and, more particularly, 2 to 20 parts by weight, of a sompound of formula I, based on 100 parts by weight of component a). The optimum amount will depend on the nature of component a) and on the type of compound of formula I, and can be easily computed by simple experimentation.
As the compounds of ~ormula I are ordinarily effective in minor amounts and, in addition, are of low halogen content, they give rise to virtually no undesirable effects in the novolak compared with other known flame retardants.
The compounds of formula I may be used in different physical forms, depending on the type of epoxidised novolak used and on the desired properties. Thus they may be milled to a finely particulate form to enable better dispersion throughout the novolak. Mixtures of different compounds of formula I may also be used.
The novel compositions are suitable for fabricating cured products, typically for encapsulations, for exarnple of electronic components, as of integrated circuits, or for making laminates, in which case a hardener is used for component a).
Mixtures of different novel compositions andlor hardeners may be used. Suitable hardeners are any epoxy resin hardeners, typically cyanamide, dicyandiamide, polycarboxylic acids, polycarboxylic anhydrides, polyamines, polyaminoamides, adducts of amines and polyepoxides, and polyols.
Suitable polycarboxylic acids and their anhydrides are typically phthalic anhydride or tetrahydro- and hexahydrophthalic anhydride, and the acids from which these anhydrides are derived.
Exemplary of polyamines which may suitably be used as hardeners are aliphatic, cycloaliphatic, aromatic and heterocyclic polyamines, such as hexamethylenediarnine, 2 ~ 3 diethylenetriamine, m-xylylenediamine, bis(4-aminocyclohexyl)methane, m- and p-phen-ylenediamine, bis(4-aminophenyl)methane, bis(4-aminophenyl)sulfone and aniline-formaldehyde resins. Suitable polyaminoamides are typically those which are prepared from aliphatic polyamines and dimerised or trimerised unsaturated fatty acids.
Particularly suitable polyol hardeners are mononuclear or polynuclear aromatic polyols, including novolaks, typically resorcinol~ hydroquinone, 2,6-dihydroxytoluene, pyrogallol, 1,1,3-tris(hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxy-phenyl)propane, bis(4-hydroxyphenyl)sulfone and 4,4'-dihydroxybiphenyl, as well as novolaks from formaldehyde or acetaldehyde and phenol, chlorophenol or aLtcylphenols containing up to ~ carbon atoms in the alkyl moiety, preferably phenol and cresol novolaks.
PrefeIred hardeners are polycarboxylic anhydrides, such as tetrahydro- and hexahydrophthalic anhydride, as well as aromatic polyainines, preferably bis(4-aminophenyl)methane, bis(4-aminophenyl)sulfone and m- or p-phenylenediamine, and also, most preferably, polyol hardeners based on novolaks, more particularlycresol-novolaks or phenol-novolaks.
The novel compositions may also contain further conventional modifiers, typically an accelerator and/or other modifiers.
Per se known compounds can also be used as accelerators. Typical examples are:
complexes of amines, preferably tertiary amines such as monoethylamine with boron trifluoride or boron trichloride, tertiary amines such as benzyldimethylamine, urea derivatives such as N-4-chlorophenyl-N',N'-dimethylurea (monuron), unsubstituted or substituted imidazoles such às imidazole or 2-phenylimidazole, and sulfonium salts and tertiary phosphines.
The hardeners are used in the usual effective amounts, i.e. in the amounts suff1cient to cure the novel compositions. The ratio of component a) to the hardener will depend on the type of compounds used, on the requisite curing rate, and on the desired properties of ;he final product, and can be easily determined by those skilled in the art of curing epoxy resins. lf the hardener is an amine, then it will be expedient to use 0.75 to 1.25 equivalents of active hydrogen bound to amino nitrogen per 1 epoxide equivalent. If the hardener is a polycarboxylic acid or an anhydride thereof, then usually 0.4 to 1.1 equivalents of 2 ~
carboxyl or anhydride groups will be used per 1 epoxide equivalent. If the hardener is a polyo1, then it will be expedient to use 0.75 to 1.25 equivalents of phenolic hydroxyl groups per 1 epoxide equivalent.
The accelerators may generally be used in amounts of 0.1 to 5 % by weight, based on the epoxy novolak resin a).
If desired, reactive diluents may be added to the curable compositions to reduce the viscosity. Exemplary of reactive diluents are styrene oxide, butyl glycidyl ether, 2,2,4-trimethylpentyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ethers or glycidyl esters of synthetic, highly branched, mainly tertiary aliphatic monocarboxylic acids. The novel compositions may also contain as additional customary modifiersplasticisers, extenders, fillers and reinforcing agents, including bitumenous coal tar, bitumen, textile fibres, glass fibres, asbestos fibres, boron fibres, carbon fibres, mineral silicates, mica, quartz flour, hydrated alumina, bentonites, kaolin, silica aerogel or me~al powders such as aluminium powder or iron powder, and also pigments and dyes such as carbon black, oxide pigments and titanium dioxide, additional flame retardants, thixotropic agents, flow control agents such as silicones, waxes and stearates, some of which are also used as mould release agents, adhesion promoters, antioxidants and light stabilisers, and also foaming agents, fungicides or antistatic agents.
Additional flame retardants which may conveniently be used together with the compounds of formula I are phosphorus-containing salts such as ammonium polyphosphates, and also alumina, bismuth oxide, molybdenum oxide or mixtures of these compounds with zinc and/or magnesium oxide or salts, but preferably non-halogenated triphenylphosphates.
Non-halogenated triphenylphosphates may carry sterically hindered phenyl radicals, typically with at least one tert-butyl group, but also at least one methyl group, in ortho-position to the phenolic hydroxyl group.
The novel compositions are used for fabricating cured products such as laminates, but preferably for encapsulating electronic components, typically of electronic c*cuits. They may be used in a formulation adapted to suit each speci~lc end use, in the filled or unfilled state, typically as moulding compounds, dipping resins, casting resins, impregnating resins, laminating resins and matrix resins.
The cure of the novel compositions may be carried out in a manner known per se in one or two steps. The cure is normally carried out by heating to temperatures in the range from 80 to 200C, preferably from 100 to 180C.
The cured products fabricated with the polyepoxides obtainable in the practice of this invention are distinguished by good mechanical, therrnal and chemical properties.
In the preparation of laminating resins, typically of fibrous composite systems, the fibres conventionally used for reinforcing moulding compounds may suitably be used as reinforcing fibres. These fibTes may be organic or inorganic fibres, natural or synthetic fibres such as aramide fibres, and be in the forrn of fibre bundles or continuous fibres. The fibres typically used as reinforcing fibres are glass, asbestos, boron, carbon and metal fibres, preferably carbon and metal fibres. Such fibres and fabrics made theTefrom are commercially available.
The following Examples illustrate the invention in more detail.
Examples 1-3: Test specimens are prepared from the following epoxy cresol novolak having an epoxy value of 200 eq/kg (EOCN 1020, Nippon Kayaku Co.) with the addition of flame retardant A or B or a combination of flame retardant B in admixture with a non-halogenated organic phosphate, and with the addition of the further modi~lers listed in the following Table.
The test specimens contain a silicon chip having an aluminium strip structure (5 ~,lm wide, 1 llm thick) on a thermally oxidised SiO2 substrate. This chip is bonded with an epoxy adhesive to a leadframe made of metal alloy (Alloy 42), and the adhesive is then thermally cured. The contact points of the aluminium strips are then bonded to the leadframe with gold wire, and the structured material so obtained as a whole is subsequently encapsulated with an epoxy novolak system (q.v. the Table). Moulding temperature: 175C for 2 minutes; moulding pressure: 700 NT/cm2. Postcure temperature: 1 80C for ~ hours.
After removal from the mould, the test specimens are tested for the~r conductivity (in ohn~) after storage at 200C. A conductivity greater than 10 ohm is counted as failure.
Test bars are prepared from the same epoxy cresol novolak composition (moulding temperature: 175C for 2 minutes; moulding pressure: 700 NT/cm2; postcure temperature:
180C for 4 hours) and tested for their flammability in accordance with Standard UL 94, -`` 2 ~ J
3rd edition (revised) of September 25, 1987 (vertical flammability test) of Underwriter Laboratories Ltd.
Table (the amounts are given in parts by weight):
Examples:
Components of the epoxy novolak system 1 2 3 -a) epoxidised novolak 393.6 393.6 393.6 b) novolak (hardener) 206.4 206.4 206.4 A) comp. of formula I 101.4 B) comp. of formula I 48.6 32.4 c) non-halogenated phosphate derivative 48.6 48.6 d) silane derivative 6 6 6 e) wax 6 6 6 f) carbonblack 6 6 6 g) phosphine derivative 4.B 4.8 4.8 h) RD-8 (filler) 2400 2400 2400 Bromine content~ based on the total amount of novolak resin (a+b):
Examples 1 and 3 : 2 % by weight in each;
Example 2 : 3 % by weight.
Kev to Table 1:
a) epoxy cresol novolak resin having an epoxy value of 200 eq~g; [EOCN 1020;
supplier: Nippon Kayaku Co];
b) phenol novolak resin TD 2093 [supplier Dainippon Lnk Co];
c) non-halogenated organic phosphate FY 511 [Ciba-Geigy AG; structure according to formula I, wherein Xl and X2 are hydrogen, Y is oxygen and Rl and R2 are methyl,and R3 and R4 together form a group of formula III, wherein Rl is tert-butyl and R2 is methyl];
d) 3-glycidyloxypropyl trimethoxysilane [KBM 403; supplier Shin-Etsu Chem.];
e) camauba resin;
f) carbon black;
g) triphenylphosphine;
h) silicate powder (silica~ having an avera~e particle diameter of 13 ~lm [RD-8; supplier Tatsumori Co];
A) =P ~ ~ Br) C(CH3)3 3 B) O=P~o~Br) ~13C 3 Test results:
inflammability according to Example 1 2 3 (UL 94/2 mm) V-O V-O V-O
conductivity failure rate a~ter storage at 200C for 141 hours 0/15 0/15 0/15 338 hours 0/15 0/15 0/15 It is evident from this Table that the inventive compositions, when tested in accordance with Examples 1, 2 and 3, exhibit excellent inflammability (V-O) and that still no failure in conductivity occurs after 141 and 338 hours at 200C when using a strongly reduced bromine concentration in the resin formulations (2 % and 3 %, respectively). In contrast, comparable tests made without the use of a compound of formula I, but using a corresponding amount of a brominated epoxy novolak resin in admixture with a percentage of Sb203, display a markedly poorer conductivity.
Epoxv novolaks stabilised with or~anic phosphorus compounds The present invention relates to novel compositions comprising an epoxidised novolak and at least one speci~lc organic phosphorus compound as flame retardant, and to the use of said compositions in encapsulating systems and laminating resins.
The flame resistance of polymers can be enhanced in different ways, for example by reducing the organic polymer component by adding fillers of low flammability such as quartz flour, glass or wollastonite, and also by the addition of flame retardants such as boron compounds, metal hydroxides, brominated compounds, halogenated phosphoric acid esters or specific organic phosphorus compounds as disclosed in European patent application 0 456 605.
The flame retardants currently added to the epoxy novolaks which are used in encapsulating systems and in laminating resins and which have to be made flame resistant are usually combinations of brominated organic compounds in admixture with antimony trioxide, the brominated organic compound normally being a brominated and glycidylised novolak.
For some time there have been ongoing efforts to develop replacement products for antimony trioxide for ecological and industrial health reasons, all the more so as antimony trioxide is preferably used in the ~me (dust) form in which it has the best flame retardant effect. If the antimony trioxide component is eliminated, then it is observed that the thermostability of encapsulating compositions is markedly impaired.
Surprisingly, it has now been found that specific combinations of epoxidised novolaks and specific sterically hindered organic (thio)phosphates, without the use of antimony trioxide and with a low halogen concentration in the encapsulating and laminating systems, ensure excellent flame resistance without the other performance properties such as thermal resistance, mechanical strength, dielectric constant or water absorption, being materially influenced.
2~8~f3 Specifically, the invention relates to compositions comprising a) an epoxidised novolak, and b) 0.1 to 100 parts by weight, based on 100 parts by weight of component a), of at least one compound of formula I
X1~0- 1 -Y (I), wherein ~1 is chloro or bromo, X2 is chloro, bromo or hydrogen, and Y is OorS, and Rl and R2 are each independently of the other Cl-C4alkyl, and R3 and R4 are a group of formula II
R,l _o~X1 (II), R2 x2 wherein Rl, R2, Xl and X2 are as defined above, which group calTies identical or different substituents, or R3 and R4, when taken together, forrn a group of formula m R2~R1 ~o~
CH2 (III), C~' 208~0~
wherein Rl and R2 are as defined above.
Xl and X2 are chloro and, preferably, bromo. X2 is preferably hydrogen. Y is preferably oxygen.
Rl and R2 as aLkyl substituents may each independently of the other typically be methyl, ethyl, propyl, isopropyl, butyl or tert-butyl. Rl in ~ormulae I and Il is preferably methyl or tert-butyl and, in formula III, is preferably tert-butyl. The preferred meaning of 1~2 is methyl.
In preferred compounds of formula I, Xl is bromo, X2 is hydrogen and Y is oxygen.
In particularly preferred compounds of formula I, Xl is bromo, X2 is hydrogen, Y is oxygen, Rl is methyl or tert-butyl, R2 is methyl, and R3 and R4 are each an identically substituted group of -formula I~, and Xl, X2, Rl and R2 are as defined above.
Further preferred compounds of forrnula I are those wherein R3 and R4, when taken together, form a group of formula III, and Xl is bromo, X2 is hydrogen, Y is oxygen, Rl and R2 in formula I are rnethyl, and Rl in formula UI is tert-butyl, and R2 in formula III is methyl.
The compounds of forrnula I and the preparation thereof are known and disclosed in European patent application 0 456 605 referred to above.
Suitable epoxidised novolaks are typically epoxy phenol novolak and epoxy cresolnovolak resins which may be obtained by condensing phenolic compounds with aldehydes. Owing to their high functionality - usually 2 to 6 epoxy groups per molecule -they are capable, in conjunction with the customary crosslinking agents, preferably at elevated temperature, of constructing a very compact macromolecular ne~work.
Exemplary of phenolic compounds are phenol, alkylphenols containing up to 9 carbon atoms in the alkyl moiety, typically cresols, xylenols, ethyl-, propyl- and butylphenols, and also phenylphenols, resorcinol, pyrocatechol, hydroquinone, bisphenol A and pyro-gallol.
Exemplary of aldehydes are formaldehyde, acetaldehyde, benzaldehyde and 2 ~ g ~
teraphthalaldehyde .
It is preferred to use phenol-foremaldehyde resins and, more particularly, cresol-formaldehyde resins, for the preparation of which o-, m- or p-cresol or mixtures of these isomers have been used in any or in given rados. The preparation of such resins is known.
It is preferred to use 0.5 to 30 parts by weight and, more particularly, 2 to 20 parts by weight, of a sompound of formula I, based on 100 parts by weight of component a). The optimum amount will depend on the nature of component a) and on the type of compound of formula I, and can be easily computed by simple experimentation.
As the compounds of ~ormula I are ordinarily effective in minor amounts and, in addition, are of low halogen content, they give rise to virtually no undesirable effects in the novolak compared with other known flame retardants.
The compounds of formula I may be used in different physical forms, depending on the type of epoxidised novolak used and on the desired properties. Thus they may be milled to a finely particulate form to enable better dispersion throughout the novolak. Mixtures of different compounds of formula I may also be used.
The novel compositions are suitable for fabricating cured products, typically for encapsulations, for exarnple of electronic components, as of integrated circuits, or for making laminates, in which case a hardener is used for component a).
Mixtures of different novel compositions andlor hardeners may be used. Suitable hardeners are any epoxy resin hardeners, typically cyanamide, dicyandiamide, polycarboxylic acids, polycarboxylic anhydrides, polyamines, polyaminoamides, adducts of amines and polyepoxides, and polyols.
Suitable polycarboxylic acids and their anhydrides are typically phthalic anhydride or tetrahydro- and hexahydrophthalic anhydride, and the acids from which these anhydrides are derived.
Exemplary of polyamines which may suitably be used as hardeners are aliphatic, cycloaliphatic, aromatic and heterocyclic polyamines, such as hexamethylenediarnine, 2 ~ 3 diethylenetriamine, m-xylylenediamine, bis(4-aminocyclohexyl)methane, m- and p-phen-ylenediamine, bis(4-aminophenyl)methane, bis(4-aminophenyl)sulfone and aniline-formaldehyde resins. Suitable polyaminoamides are typically those which are prepared from aliphatic polyamines and dimerised or trimerised unsaturated fatty acids.
Particularly suitable polyol hardeners are mononuclear or polynuclear aromatic polyols, including novolaks, typically resorcinol~ hydroquinone, 2,6-dihydroxytoluene, pyrogallol, 1,1,3-tris(hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxy-phenyl)propane, bis(4-hydroxyphenyl)sulfone and 4,4'-dihydroxybiphenyl, as well as novolaks from formaldehyde or acetaldehyde and phenol, chlorophenol or aLtcylphenols containing up to ~ carbon atoms in the alkyl moiety, preferably phenol and cresol novolaks.
PrefeIred hardeners are polycarboxylic anhydrides, such as tetrahydro- and hexahydrophthalic anhydride, as well as aromatic polyainines, preferably bis(4-aminophenyl)methane, bis(4-aminophenyl)sulfone and m- or p-phenylenediamine, and also, most preferably, polyol hardeners based on novolaks, more particularlycresol-novolaks or phenol-novolaks.
The novel compositions may also contain further conventional modifiers, typically an accelerator and/or other modifiers.
Per se known compounds can also be used as accelerators. Typical examples are:
complexes of amines, preferably tertiary amines such as monoethylamine with boron trifluoride or boron trichloride, tertiary amines such as benzyldimethylamine, urea derivatives such as N-4-chlorophenyl-N',N'-dimethylurea (monuron), unsubstituted or substituted imidazoles such às imidazole or 2-phenylimidazole, and sulfonium salts and tertiary phosphines.
The hardeners are used in the usual effective amounts, i.e. in the amounts suff1cient to cure the novel compositions. The ratio of component a) to the hardener will depend on the type of compounds used, on the requisite curing rate, and on the desired properties of ;he final product, and can be easily determined by those skilled in the art of curing epoxy resins. lf the hardener is an amine, then it will be expedient to use 0.75 to 1.25 equivalents of active hydrogen bound to amino nitrogen per 1 epoxide equivalent. If the hardener is a polycarboxylic acid or an anhydride thereof, then usually 0.4 to 1.1 equivalents of 2 ~
carboxyl or anhydride groups will be used per 1 epoxide equivalent. If the hardener is a polyo1, then it will be expedient to use 0.75 to 1.25 equivalents of phenolic hydroxyl groups per 1 epoxide equivalent.
The accelerators may generally be used in amounts of 0.1 to 5 % by weight, based on the epoxy novolak resin a).
If desired, reactive diluents may be added to the curable compositions to reduce the viscosity. Exemplary of reactive diluents are styrene oxide, butyl glycidyl ether, 2,2,4-trimethylpentyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ethers or glycidyl esters of synthetic, highly branched, mainly tertiary aliphatic monocarboxylic acids. The novel compositions may also contain as additional customary modifiersplasticisers, extenders, fillers and reinforcing agents, including bitumenous coal tar, bitumen, textile fibres, glass fibres, asbestos fibres, boron fibres, carbon fibres, mineral silicates, mica, quartz flour, hydrated alumina, bentonites, kaolin, silica aerogel or me~al powders such as aluminium powder or iron powder, and also pigments and dyes such as carbon black, oxide pigments and titanium dioxide, additional flame retardants, thixotropic agents, flow control agents such as silicones, waxes and stearates, some of which are also used as mould release agents, adhesion promoters, antioxidants and light stabilisers, and also foaming agents, fungicides or antistatic agents.
Additional flame retardants which may conveniently be used together with the compounds of formula I are phosphorus-containing salts such as ammonium polyphosphates, and also alumina, bismuth oxide, molybdenum oxide or mixtures of these compounds with zinc and/or magnesium oxide or salts, but preferably non-halogenated triphenylphosphates.
Non-halogenated triphenylphosphates may carry sterically hindered phenyl radicals, typically with at least one tert-butyl group, but also at least one methyl group, in ortho-position to the phenolic hydroxyl group.
The novel compositions are used for fabricating cured products such as laminates, but preferably for encapsulating electronic components, typically of electronic c*cuits. They may be used in a formulation adapted to suit each speci~lc end use, in the filled or unfilled state, typically as moulding compounds, dipping resins, casting resins, impregnating resins, laminating resins and matrix resins.
The cure of the novel compositions may be carried out in a manner known per se in one or two steps. The cure is normally carried out by heating to temperatures in the range from 80 to 200C, preferably from 100 to 180C.
The cured products fabricated with the polyepoxides obtainable in the practice of this invention are distinguished by good mechanical, therrnal and chemical properties.
In the preparation of laminating resins, typically of fibrous composite systems, the fibres conventionally used for reinforcing moulding compounds may suitably be used as reinforcing fibres. These fibTes may be organic or inorganic fibres, natural or synthetic fibres such as aramide fibres, and be in the forrn of fibre bundles or continuous fibres. The fibres typically used as reinforcing fibres are glass, asbestos, boron, carbon and metal fibres, preferably carbon and metal fibres. Such fibres and fabrics made theTefrom are commercially available.
The following Examples illustrate the invention in more detail.
Examples 1-3: Test specimens are prepared from the following epoxy cresol novolak having an epoxy value of 200 eq/kg (EOCN 1020, Nippon Kayaku Co.) with the addition of flame retardant A or B or a combination of flame retardant B in admixture with a non-halogenated organic phosphate, and with the addition of the further modi~lers listed in the following Table.
The test specimens contain a silicon chip having an aluminium strip structure (5 ~,lm wide, 1 llm thick) on a thermally oxidised SiO2 substrate. This chip is bonded with an epoxy adhesive to a leadframe made of metal alloy (Alloy 42), and the adhesive is then thermally cured. The contact points of the aluminium strips are then bonded to the leadframe with gold wire, and the structured material so obtained as a whole is subsequently encapsulated with an epoxy novolak system (q.v. the Table). Moulding temperature: 175C for 2 minutes; moulding pressure: 700 NT/cm2. Postcure temperature: 1 80C for ~ hours.
After removal from the mould, the test specimens are tested for the~r conductivity (in ohn~) after storage at 200C. A conductivity greater than 10 ohm is counted as failure.
Test bars are prepared from the same epoxy cresol novolak composition (moulding temperature: 175C for 2 minutes; moulding pressure: 700 NT/cm2; postcure temperature:
180C for 4 hours) and tested for their flammability in accordance with Standard UL 94, -`` 2 ~ J
3rd edition (revised) of September 25, 1987 (vertical flammability test) of Underwriter Laboratories Ltd.
Table (the amounts are given in parts by weight):
Examples:
Components of the epoxy novolak system 1 2 3 -a) epoxidised novolak 393.6 393.6 393.6 b) novolak (hardener) 206.4 206.4 206.4 A) comp. of formula I 101.4 B) comp. of formula I 48.6 32.4 c) non-halogenated phosphate derivative 48.6 48.6 d) silane derivative 6 6 6 e) wax 6 6 6 f) carbonblack 6 6 6 g) phosphine derivative 4.B 4.8 4.8 h) RD-8 (filler) 2400 2400 2400 Bromine content~ based on the total amount of novolak resin (a+b):
Examples 1 and 3 : 2 % by weight in each;
Example 2 : 3 % by weight.
Kev to Table 1:
a) epoxy cresol novolak resin having an epoxy value of 200 eq~g; [EOCN 1020;
supplier: Nippon Kayaku Co];
b) phenol novolak resin TD 2093 [supplier Dainippon Lnk Co];
c) non-halogenated organic phosphate FY 511 [Ciba-Geigy AG; structure according to formula I, wherein Xl and X2 are hydrogen, Y is oxygen and Rl and R2 are methyl,and R3 and R4 together form a group of formula III, wherein Rl is tert-butyl and R2 is methyl];
d) 3-glycidyloxypropyl trimethoxysilane [KBM 403; supplier Shin-Etsu Chem.];
e) camauba resin;
f) carbon black;
g) triphenylphosphine;
h) silicate powder (silica~ having an avera~e particle diameter of 13 ~lm [RD-8; supplier Tatsumori Co];
A) =P ~ ~ Br) C(CH3)3 3 B) O=P~o~Br) ~13C 3 Test results:
inflammability according to Example 1 2 3 (UL 94/2 mm) V-O V-O V-O
conductivity failure rate a~ter storage at 200C for 141 hours 0/15 0/15 0/15 338 hours 0/15 0/15 0/15 It is evident from this Table that the inventive compositions, when tested in accordance with Examples 1, 2 and 3, exhibit excellent inflammability (V-O) and that still no failure in conductivity occurs after 141 and 338 hours at 200C when using a strongly reduced bromine concentration in the resin formulations (2 % and 3 %, respectively). In contrast, comparable tests made without the use of a compound of formula I, but using a corresponding amount of a brominated epoxy novolak resin in admixture with a percentage of Sb203, display a markedly poorer conductivity.
Claims (11)
1. A composition comprising a) an epoxidised novolak, and b) 0.1 to 100 parts by weight, based on 100 parts by weight of component a), of at least one compound of formula I
(I) wherein X1 is chloro or bromo, X2 is chloro, bromo or hydrogen, and Y is O or S, and R1 and R2 are each independently of the other C1-C4alkyl, and R3 and R4 are a group of formula II
(II), wherein R1, R2, X1 and X2 are as defined above, which group carries identical or different substituents, or R3 and R4, when taken together, form a group of formula III
(III), wherein R1 and R2 are as defined above.
(I) wherein X1 is chloro or bromo, X2 is chloro, bromo or hydrogen, and Y is O or S, and R1 and R2 are each independently of the other C1-C4alkyl, and R3 and R4 are a group of formula II
(II), wherein R1, R2, X1 and X2 are as defined above, which group carries identical or different substituents, or R3 and R4, when taken together, form a group of formula III
(III), wherein R1 and R2 are as defined above.
2. A composition according to claim 1, wherein X1 is bromo, X2 is hydrogen, and Y is oxygen.
3. A composition according to claim 1, wherein R1 and R2 are each independently of the other methyl, ethyl, propyl, isopropyl, butyl or tert-butyl.
4. A composition according to claim 1, wherein R1 in formulae I and II is methyl or tert-butyl.
5. A composition according to claim 1 which comprises a compound of formula I, wherein X1 is bromo, X2 is hydrogen, Y is oxygen, R1 is methyl or tert-butyl, R2 is methyl, and R3 and R4 are each an identically substituted group of formula II, and X1, X2, R1 and R2 are as defined in claim 5.
6. A composition according to claim 1 which comprises a compound of formula I, wherein R3 and R4, when taken together, form a group of formula III, and X1 is bromo, X2 is hydrogen, Y is oxygen, R1 and R2 in formula I are methyl, and R1 in formula III is tert-butyl, and R2 in formula III is methyl.
7. A composition according to claim 1, which contains 0.5 to 30 % by weight of acompound of formula I.
8. A composition according to claim 1, wherein component a) is an epoxy phenol novolak or an epoxy cresol novolak resin.
9. A composition according to claim 1, wherein the novolak resin is a cresol-formaldehyde resin.
10. Use of a composition according to claim 1 for making laminates or encapsulating systems.
11. Use according to claim 11 for encapsulating electronic components.
FD 4.3/RU/ms*
FD 4.3/RU/ms*
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH307991 | 1991-10-22 | ||
| CH3079/91-2 | 1991-10-22 | ||
| CH3134/91-6 | 1991-10-25 | ||
| CH313491 | 1991-10-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2081000A1 true CA2081000A1 (en) | 1993-04-23 |
Family
ID=25692118
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002081000A Abandoned CA2081000A1 (en) | 1991-10-22 | 1992-10-20 | Epoxy novolaks stabilised with organic phosphorus compounds |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0539327B1 (en) |
| JP (1) | JP3165827B2 (en) |
| AT (1) | ATE124434T1 (en) |
| BR (1) | BR9204086A (en) |
| CA (1) | CA2081000A1 (en) |
| DE (1) | DE59202709D1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2123712A1 (en) | 2008-05-19 | 2009-11-25 | Evonik Degussa GmbH | Epoxy resin composition and electronic part |
| CN102107127B (en) * | 2011-01-11 | 2015-04-22 | 西安蓝晓科技新材料股份有限公司 | Technology for granulating powder |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2653119A1 (en) * | 1976-11-23 | 1978-05-24 | Bayer Ag | PROCESS FOR THE PRODUCTION OF BROMARYLPHOSPHATES |
| KR0156247B1 (en) * | 1989-08-09 | 1998-12-01 | 베르너 발데크 | Phosphorous compounds |
| EP0456605A1 (en) * | 1990-05-09 | 1991-11-13 | Ciba-Geigy Ag | Phosphorous compounds |
-
1992
- 1992-10-13 EP EP92810784A patent/EP0539327B1/en not_active Expired - Lifetime
- 1992-10-13 AT AT92810784T patent/ATE124434T1/en not_active IP Right Cessation
- 1992-10-13 DE DE59202709T patent/DE59202709D1/en not_active Expired - Fee Related
- 1992-10-20 JP JP30631292A patent/JP3165827B2/en not_active Expired - Fee Related
- 1992-10-20 CA CA002081000A patent/CA2081000A1/en not_active Abandoned
- 1992-10-21 BR BR929204086A patent/BR9204086A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| ATE124434T1 (en) | 1995-07-15 |
| JP3165827B2 (en) | 2001-05-14 |
| JPH05230340A (en) | 1993-09-07 |
| DE59202709D1 (en) | 1995-08-03 |
| EP0539327B1 (en) | 1995-06-28 |
| BR9204086A (en) | 1993-05-04 |
| EP0539327A1 (en) | 1993-04-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |