Epoxy resin composition

Abstract: An epoxy resin blend comprising a diglycidylether of substituted or unsubstituted biphenol and a polyepoxy resin derived from an α,α,Ω,Ω-tetrakis(hydroxyphenyl)hydrocarbyl, which exhibits advantageous properties for use in electrical encapsulation compositions.

Description: This invention relates to low-stress epoxy resin compositions useful in encapsulating electrical components. Epoxy resins are used to encapsulate electrical components such as integrated circuits. The optimum properties for encapsulation resins include low melting point in the uncured state (to permit encapsulation of the component at a relatively low temperature), high glass transition temperature in the cured state (to permit encapsulation of a component which can tolerate high operating temperatures), low modulus and low coefficient of thermal expansion of the cured resin (properties related to the ability of the cured resin to resist "stress" or cracking at high operating temperatures), low viscosity (to permit high filler loading of the encapsulation formulation) and low chloride ion content (to minimize aluminum corrosion and resulting failure of the circuit). A problem with epoxy resins for encapsulation, however, is that the conventional method of preparing epoxy resins involves the use of chlorine-containing starting materials. The presence of chloride ions in the resin used to encapsulate an electrical component promotes aluminum corrosion and can cause failure of the integrated circuit in use. The crystalline form of a given epoxy resin contains a relatively low chloride ion content and has relatively low melt viscosity; however, the crystalline form of a resin also has a relatively high melting temperature, making it necessary to use undesirably high temperatures during the encapsulation process. One class of epoxy resins used in electrical encapsulation are epoxidized orthocresol novolac (EOCN) resins. EOCN resins have high glass transition temperatures, but they are difficult to process because of their high viscosities at temperatures normally desired for encapsulation. Another class of epoxy resins suitable for electrical encapsulation are diglycidyl ethers of 3,3',5,5'-tetraalkyl-4,4'-dihydroxybiphenyls. These epoxy resins exhibit the highly desirable property combination of low melt viscosity and low modulus, the latter property being an indication of the ability of the cured composition to resist cracking during high temperature use. However, for some encapsulation applications, the glass transition temperature of these resins is undesirably low. It is therefore an object of the invention to provide an epoxy resin composition which has low melt viscosity, a low melting point, low modulus and high glass transition temperature, which can be used in electrical encapsulation compositions. The invention therefore relates to an epoxy resin composition comprising (a) from 25 to 60 weight percent, based on the weight of components (a) and (b), of a diglycidyl ether of a 4,4'-dihydroxybiphenyl and (b) from 75 to 40 weight percent of a polyglycidyl ether of a phenolic compound having an average epoxide functionality of at least 3.0, which can be represented by the structure in which each R' is independently selected from hydrogen and C 1-4 alkyl and Y is a direct bond or a substituted or unsubstituted divalent hydrocarbyl linking group. It was found that moulding powder compositions comprising the resin blend of the invention have low modulus and good processing viscosity at encapsulation temperatures. Component (a) in the composition according to the invention can be described by chemical structure I: in which each R is selected independently from hydrogen and C 1-4 alkyl, preferably methyl or ethyl. The preferred component (a) is the diglycidyl ether of 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl. The composition according to the invention further comprises a component (b) which can be described by chemical structure II as presented above. Preferred groups R' are methyl and ethyl. Preferred linking groups Y are selected from (CH 2 ) 0-12 and (CH 2 ) m Ar(CH 2 ) m , in which m is 0-4 and Ar is a difunctional arylene moiety, preferably phenylene. Examples of such polyglycidyl ethers (b) are the polyglycidyl ethers of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 1,1,5,5-tetrakis(4-hydroxy-3,5-dimethylphenyl)pentane, 1,1,8,8-tetrakis(3-methyl-4-hydroxyphenyl)octane and α,α,α',α'-tetrakis(4-hydroxyphenyl)-p-xylene. In this context, a "poly" glycidyl ether is one having an average epoxide functionality of at least 3.0, preferably at least 3.5, per molecule. The preferred compound (b) is the tetraglycidyl ether of 1,1,2,2-tetrakis(4-hydroxy-3,5-dimethylphenyl)ethane. Such glycidyl ethers can be prepared by glycidating, by techniques known in the art, the corresponding tetraphenols, which can be prepared by condensing, in the presence of an acidic catalyst, an appropriate dialdehyde, such as glyoxal, isophthalaldehyde and terephthaldehyde, with a stoichiometric excess of a phenol. The components (a) and (b) are present in the mixture in a molar ratio of (a) to (b) of from 25:75 to 60:40 weight percent, based on the weight of the mixture of the resins (a) and (b). For low modulus and optimum processability, the mixture preferably contains from 60 to 40, most preferably of from 55 to 45, weight percent of (b). The preferred blends for electrical encapsulation applications exhibit a glass transition temperature above 180°C, preferably above 200°C, and a melting temperature below 120°C, preferably below 100°C. For maximum performance and low chloride ion content, resins will be selected which are manufactured or purified under conditions which result in crystalline diglycidyl ethers and tetraglycidyl ethers. A "crystalline" epoxy resin is characterized generally by narrow molecular weight distribution and a melting range of typically 20°C (as compared with an amorphous resin, which exhibits only softening with application of heat). The two components of the resin composition of the invention can be combined in any manner which results in an intimate mixture of the epoxy resins. Melt-blending finely-divided particles of the two resins is preferred. The epoxy resin composition of the invention will be used in combination with an effective amount of a curing agent. Suitable curing agents for epoxy resins include amines, phenols, anhydrides and imidazoles. The preferred curing agents for electrical encapsulation formulations are phenolic curing agents, including novolacs such as epoxidized orthocresol novolacs. The curing agent will be present in the composition in an amount effective to cure the epoxy resins, generally an amount within the range of from 1 to 100, preferably of from 30 to 60, weight percent, based on the total weight of (a) and (b). The composition can optionally include a cure accelerator such as a phosphine or an imidazole, generally present in an amount within the range of from 0.1 to 3 weight percent, based on the weight of the epoxy resins. The composition according to the invention is useful in moulding, coating, adhesives and composites applications and has been found to be highly suitable for powder moulding applications such as encapsulation of an electrical component. Moulding compositions for electrical encapsulation will include an inert filler present in an amount of at least 55 weight percent, preferably of from 60 to 90 weight percent, based on the weight of the filled composition. Suitable inert fillers include silica, iron oxide, mica, alumina, talc, antimony trioxide, titanium oxide and the like. The preferred filler for electrical encapsulation formulations is silica. For composites applications, the epoxy resin blend will be used in combination with a fibrous reinforcement such as glass, carbon, quartz, poly(p-phenyleneterephthalamide), polyester, polytetrafluorethylene, poly(p-phenylenebenzobisthiazole), boron, paper, or like materials in chopped, mat or woven form. The moulding formulation will typically contain one or more additives such as, for example, plasticizers, stabilizers, pigments, flow control agents and flame retardants. A brominated epoxy resin or brominated phenolic resin is commonly added to encapsulation formulations to provide flame retardancy. It is also common for the formulation to include an elastomer such as a rubbery butadiene/styrene copolymer, an organopolysiloxane polymer or copolymer, or a carboxy-terminated butadiene acrylonitrile for reduction of the modulus and enhancement of fracture toughness of the cured formulation. The components of the moulding composition are combined so as to provide an intimate mixture of the ingredients of the moulding powder composition and thorough contact between the composition and the filler material. The preferred technique involves mixing the invention resin composition described above with a curing agent, any additives, and the filler, preferably after treatment of the filler with a silane or other coupling agent; grinding the mixture to about 35 mesh particles; dry-blending the particulate mixture; melt-mixing the blend in a roll mill or extruder at an elevated temperature about 15-30°C above the softening point of the blend; and grinding the solidified resin to about 35 mesh. For encapsulation applications, the prepared formulation is cast around the electrical component to be encapsulated by a transfer moulding operation carried out at an elevated temperature sufficient to lower the viscosity of the resin so that it fills the mould and flows around the component, usually at temperatures of from 160-180°C, and an elevated pressure of 68.7 atm. The moulded parts are typically postcured for 1-6 hours at an elevated temperature to develop maximum physical properties. Example 1 Amounts as indicated in table 1, (runs 2, 3 and 4 according to the invention and runs 1, 5 and 6 for comparison) of the diglycidyl ether of 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl (DGE) and the tetraglycidyl ether of 1,1,2,2-tetrakis(4-hydroxy-3,5-dimethylphenyl)ethane (TGE) in powder form were weighed into a one-liter evaporating flask. (Each epoxy resin was crystalline and exhibited a melting range of about 20°C.) The flask was placed on a rotary evaporator equipped with a heated oil bath at 175°C. The flask was lowered into the bath and a full vacuum was applied. After 15 minutes, the flask was removed and inverted in a forced draft oven at 150°C. The molten resin mixture was allowed to drain into a glass container over the next 15 minutes. The container was removed and the resin blend was cooled to room temperature. The resulting solid blend was milled in a hammer mill to 35 mesh. Highest melting temperatures (peak maximum on differential scanning calorimeter) and heats of fusion for the blends of the two resins are shown in Table 1. Table 1 shows that resins blends of the invention have a combination of low melting temperature and low heat of fusion. Run 1 2 3 4 5 6 DGE/TGE (g/g) 0/100 25/75 50/50 60/40 80/20 100/0 Melting Temp. ( °C) 166 150 99 100 103 106 Heat of Fusion (Cal/g) 10.6 2.1 0.8 5.7 10.1 12 Example 2 A moulding composition I according to the invention was prepared by blending, for one hour in a Turbula mixer, the components listed in table 2. The curing agent was Durite SD-1711 (Durite is a trade mark) phenolic novolac from Borden Chemical Co., present in a 85% stoichiometric amount, based on the epoxy resin blend. The brominated epoxy novolac was added for flame retardancy. Triphenylphosphine was used as a cure accelerator. This mixture was blended with fused silica filler coated with a silane coupling agent, and the blend was mixed for one hour in the Turbula mixer. The filled moulding powder formulation was then melt-blended in a twin-screw extruder at 105°C. The extruded compound was allowed to cool and was then milled in a blender to 16 mesh. 2.54 x 7.62 x 0.32 cm test pieces were moulded in an RTM press by heating for four minutes at 175°C and postcuring for 4 hours at 175°C. For comparison, moulding powder compositions II and III were prepared from each of a commercial epoxidized ortho cresol novolac (EOCN-1027 epoxy resin from Nippon Kayaku having a WPE of 193 and from a diglycidyl ether of 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl (DGE) having a WPE of 185 by mixing the components as listed in table 2, as described above. Test pieces we prepared in a similar manner as described for composition I. Composition I II III Epoxy blend run 3, ex 1 102 - - EOCN - 75 - DGE - - 75 Brominated expoxy novalac 10.2 7.5 7.5 Phenolic curing agent 67.1 47.9 50.5 Antimony oxide 10.2 7.5 7.5 Carnuba wax 2.03 1.50 1.50 Triphenyl-phosphine 3.05 0.75 2.25 Fused silica 453 323 337 Properties of the test specimens of compositions I, II and III are shown in Table 3. Also shown in Table 3 are melt viscosities of the resin blend and the comparison resins. Composition I II III Tg, °C, Tan Delta 212 216 174 Tg, °C, TMA 173 173 149 CTE, ppm/°C 50-100 °C Range 23.8 24 24.8 220-240 °C Range 74.7 80 86.1 Flex Properties Strength, atm.10 3 1.24 1.37 1.28 Modulus, atm.10 3 140 161 140 % Elongation 1.0 0.9 1.0 CTE.Modulus, atm.10 6 /°C 1.15 3.86 1.25 Viscosity (mPa/s, 150 °C) 47 844 <0.1 (neat resin)(mPa/s, 180 °C) 18 224 <0.1 As can be seen from Table 2, the composition comprising the epoxy blend according to the invention has a high Tg comparable to that of the composition comprising the EOCN resin and significantly higher than that of the composition comprising the DGE alone. At the same time, the coefficient of thermal expansion (CTE.modulus) of moulding powder composition I is significantly lower than that of composition II and is comparable to that of composition III. Furthermore, the melt viscosity of the composition I is significantly lower than that of composition II.

Claims: Claims for the following Contracting States : BE, DE, FR, GB, IT, NL A composition comprising: (a) from 25 to 60 weight percent, based on the weight of components (a) and (b), of a diglycidyl ether of a 4,4'-dihydroxybiphenyl and (b) from 75 to 40 weight percent of a polyglycidyl ether of a phenolic compound having an average epoxide functionality of at least 3.0, which can be represented by the structure in which each R' is independently selected from hydrogen and C 1-4 alkyl and Y is a direct bond or a substituted or unsubstituted divalent hydrocarbyl linking group. A composition as claimed in claim 1 in which Y is selected from the groups (CH 2 ) 0-12 and (CH 2 ) m Ar(CH 2 ) m , in which m is 0-4 and Ar is phenylene. A composition as claimed in claim 1 or 2, in which component (a) is a diglycidyl ether of a 3,3',5,5'-tetraalkyl-4,4'-dihydroxybiphenyl. A composition as claimed in claim 3 in which component (a) is a diglycidyl ether of 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl. A composition as claimed in any one of claims 1 to 4 in which component (b) is a crystalline polyglycidyl ether of an α,α,Ω,Ω-tetrakis(4-hydroxy-3,5-dialkylphenyl)alkane having an average epoxide functionality of at least 3.0. A composition as claimed in claim 5, in which component (b) is a polyglycidyl ether of 1,1,2,2-tetrakis(4-hydroxy-3,5-dimethylphenyl) ethane. A composition as claimed in any one of the claims 1 to 6 which further comprises an effective amount of a curing agent for components (a) and (b). A composition as claimed in claim 7 in which the curing agent is a phenolic compound. An article of manufacture comprising the cured composition of claim 7 or 8. Claims for the following Contracting State : ES A process for the preparation of a composition by making an intimate mixture of two components, characterized in that one component is (a) from 25 to 60 weight percent, based on the weight of components (a) and (b), of a diglycidyl ether of a 4,4'-dihydroxybiphenyl, and the other component is (b) from 75 to 40 weight percent of a polyglycidyl ether of a phenolic compound having an average epoxide functionality of at least 3.0, which can be represented by the structure in which each R' is independently selected from hydrogen and C 1-4 alkyl and Y is a direct bond or a substituted or unsubstituted divalent hydrocarbyl linking group. A process as claimed in claim 1 in which Y is selected from the groups (CH 2 ) 0-12 and (CH 2 ) m Ar(CH 2 ) m , in which m is 0-4 and Ar is phenylene. A process as claimed in claim 1 or 2, in which component (a) is a diglycidyl ether of a 3,3',5,5'-tetraalkyl-4,4'-dihydroxybiphenyl. A process as claimed in claim 3 in which component (a) is a diglycidyl ether of 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl. A process as claimed in any one of claims 1 to 4 in which component (b) is a crystalline polyglycidyl ether of an α,α,Ω,Ω-tetrakis(4-hydroxy-3,5-dialkylphenyl)alkane having an average epoxide functionality of at least 3.0. A process as claimed in claim 5, in which component (b) is a polyglycidyl ether of 1,1,2,2-tetrakis(4-hydroxy-3,5-dimethylphenyl) ethane. A process as claimed in any one of the claims 1 to 6 which further comprises an effective amount of a curing agent for components (a) and (b). A process as claimed in claim 7 in which the curing agent is a phenolic compound.

Inventors: DANGAYACH KAILASH CHANDRA BANW, DANGAYACH, KAILASH CHANDRA BANWARILAL
Applicants: SHELL INT RESEARCH, SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1991
Main classification: C08G59
IPC codes: H01L23, C08G59