Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
  • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
  • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
  • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
  • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
  • C08L61/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

• the present invention relates to an epoxy resin composition
• an epoxy resin composition comprising a blend of an epoxy resin and a specific alkenyl phenolic resin.
• the invention relates to an epoxy resin composition that can be used in resins for semiconductor insulation, laminated boards, coatings, castings, adhesives, electrically insulating materials and the like because of its excellent workability and of excellent heat resistance and water resistance of a cured product thereof.
• Epoxy resins are excellent in heat resistance, adhesiveness, water resistance, mechanical strength, electrical properties and the like, and therefore are used in various fields. Particularly, in electric and electronic fields, epoxy resins are widely used in insulating casting, laminating materials, encapsulating materials and the like.
• liquid encapsulants comprising an epoxy resin composition using the conventional amine type or acid anhydride type curing agent are poor in moisture resistance as compared with transfer molding materials using phenol novolak resin or the like, and therefore are poor in total reliability as encapsulants . For this reason, reliability improvement of liquid encapsulants has been demanded.
• alkenyl phenol compound as a curing agent
• a liquid diallyl-substituted bifunctional compound obtained from bisphenol A is known.
• a polyalkenyl-substituted polyphenol compound used as a curing agent of maleimide is proposed (see JP-A-2-91113) .
• the former compound is used as a curing agent of epoxy resin, cross-linking reaction does not proceed because of being bifunctional, and heat resistance of a cured product obtained becomes very low. For this reason, there is the problem in using it as a curing agent of epoxy resin.
• the latter is solid at room temperature, and handling property is poor for use as a curing agent of liquid encapsulant. Thus, the latter is improper.
• the present invention provides an epoxy resin composition that has solved the above-mentioned problems and can give a cured product having excellent balance between moisture resistance and heat resistance and, particularly, provides an epoxy resin composition which is very useful as a liquid resin composition for semiconductor encapsulation.
• an epoxy resin composition using as a curing agent an alkenyl phenolic resin that contains a polyalkenyl- substituted polyphenol compound and a dialkenyl- substituted bifunctional phenol compound is excellent in handling property because of it being liquid, and that a cured product excellent in moisture resistance and heat resistance can be obtained therefrom.
• the present invention relates to an epoxy resin composition
• an epoxy resin composition comprising the following component A and component B.
• Component A an epoxy resin having at least two epoxy groups in one molecule
• Component B An alkenyl phenolic resin containing 50-99% by weight of a polyalkenyl-substituted polyphenol compound represented by the formula (1)
• R]_ and R2 each represent a hydrogen atom, a halogen atom or an alkyl group having 1-4 carbon atoms
• R3 and R4 each represent a hydrogen atom, an alkyl group having 1-4 carbon atoms or an alkoxy group having 1-4 carbon atoms
• Y represents an alkenyl group and n is a number of 0-20
• a preferred epoxy resin composition is that one in which 5-150 parts by weight of the alkenyl phenolic resin of the component B is blended in per 100 parts by weight of the epoxy resin of the component A.
• a more preferred embodiment of said epoxy resin composition is that one in which the component A is a liquid epoxy resin at 25 °C selected from a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a naphthalene type epoxy resin, a glycidyl amine type epoxy resin, an aliphatic epoxy resin and an alicyclic epoxy resin .
• epoxy resin compositions in which the polyalkenyl-substituted polyphenol compound represented by the formula (1) and contained in the component B is a compound where R-j_, R2 , R3 and R4 are all hydrogen atoms and Y is an allyl group in the formula ( 1) .
• dialkenyl-substituted bifunctional phenol compound is a diallyl substituted compound of any one of bisphenol A, bisphenol F and naphthalene diol.
• alkenyl phenolic resin and a curing accelerator are blended in an amount of 5-150 parts by weight and an amount of 0.01-10 parts by weight, respectively, per 100 parts by weight of the epoxy resin.
• epoxy resin compositions wherein the curing accelerator is a compound selected from tertiary amines, imidazoles and organophosphines .
• Component A Epoxy resin
• General epoxy resins are used as an epoxy resin having at least two epoxy groups in one molecule, which is a component A in an epoxy resin composition of the present invention.
• Examples of usable epoxy resin include the following materials. Aromatic diglycidyl ethers:
• Diglycidyl ether of bisphenol A diglycidyl ether of bisphenol F, diglycidyl ether of 3, 3 ' , 5, 5 ' -tetramethyl bisphenol A, diglycidyl ether of 3, 3 ', 5, 5 ' -tetramethyl bisphenol F, diglycidyl ether of bisphenol S, diglycidyl ether of dihydroxyphenyl ether, diglycidyl ether of biphenol, diglycidyl ether of 3, 3 ', 5, 5 ' -tetramethyl biphenol, diglycidyl ether of naphthalene diol, and the like.
• Glycidyl esters obtained from phthalic acid, hexahydrophthalic acid, dimer acid or the like, glycidyl amines obtained from aminophenol, diaminodiphenyl methane or the like, aliphatic epoxies obtained from 1,4- butanediol, 1, 6-hexanediol or the like, alicyclic epoxies obtained from cyclohexane dimethanol, hydrogenated bisphenol A or the like, cycloaliphatic epoxies obtained from cycloolefin such as 3, 4-epoxycyclohexylmethyl-3 ' , 4 ' - epoxycyclohexanecarboxylate, and peracetic acid, and the like .
• liquid epoxy resins at 25 °C selected from a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a naphthalene type epoxy resin, a glycidyl amine type epoxy resin, an aliphatic epoxy resin and an alicyclic epoxy resin are preferable from the point that workability is improved when used as a liquid encapsulant .
• Component B alkenyl phenolic resin
• the alkenyl phenolic resin that is a component B in the epoxy resin composition of the present invention functions as a curing agent of the epoxy resin of the component A, and contains 50-99% by weight of a polyalkenyl-substituted polyphenol compound represented by the formula (1)
• R2 each represent a hydrogen atom, a halogen atom or an alkyl group having 1-4 carbon atoms
• R3 and R4 each represent a hydrogen atom, an alkyl group having 1-4 carbon atoms or an alkoxy group having 1-4 carbon atoms
• Y represents an alkenyl group and n is a number of 0-20
• 1-50% by weight of a dialkenyl- substituted bifunctional phenol compound Polyalkenyl phenol compound:
• the polyalkenyl-substituted polyphenol compound of the formula (1) can be produced as follows.
• the polyphenol compound represented by the formula (2) is reacted with an alkali metal such as sodium hydroxide or potassium hydroxide in water or an alcohol solvent to obtain a phenolate corresponding to the respective phenol compound.
• an alkali metal such as sodium hydroxide or potassium hydroxide in water or an alcohol solvent
• a halogenated alkenyl such as allyl chloride, allyl bromide, methallyl chloride, methallyl bromide, 1-propenyl chloride or 1- propenyl bromide is then added to the reaction mixture, and condensation reaction is conducted at a temperature of 40-120 °C for 1-10 hours to obtain alkenyl ether of the polyphenol compound of the formula (2) .
• dialkenyl-substituted bifunctional phenol compound that can be used as the component B together with the polyalkenyl-substituted polyphenyl compound of the formula (1) can be produced as follows.
• bifunctional phenol as a raw material is reacted with an alkali metal such as sodium hydroxide or potassium hydroxide in water or an alcohol solvent to obtain a phenolate corresponding to the bifunctional phenol compound.
• an alkali metal such as sodium hydroxide or potassium hydroxide in water or an alcohol solvent
• a halogenated alkenyl such as allyl chloride, allyl bromide, methallyl chloride, methallyl bromide, 1-propenyl chloride or 1-propenyl bromide is then added to the reaction mixture, and condensation reaction is conducted at a temperature of 40-120 °C for 1-10 hours to obtain dialkenyl ether of the bifunctional phenol.
• Salts by-produced are thereafter washed with water or the like to be removed, and purification is conducted. Claisen rearrangement reaction is then conducted at a temperature of 130-250 °C for 1-20 hours to obtain a polyalkenyl-substituted polyphenol compound.
• the alkenyl phenolic resin that is component B in the epoxy resin composition of the present invention the polyalkenyl-substituted polyphenol compound represented by the formula (1) and the dialkenyl-substituted bifunctional phenol may be used after being produced separately and mixed in appropriate proportions, as mentioned above.
• a liquid alkenyl phenolic resin is obtained, to use a mixture of the polyalkenyl-substituted polyphenol compound represented by the formula (1) and the dialkenyl-substituted bifunctional phenol, the mixture prepared by using a mixture of the polyphenol compound of the formula (2) and the bifunctional phenol compound as raw materials, by conducting the same alkenyl etherification reaction as mentioned above, and by conducting subsequently Claisen rearrangement reaction.
• the polyalkenyl-substituted polyphenol compound represented by the formula (1) obtained by the above reaction is preferred when R]_, R2 R3 and R4 are all hydrogen atoms and Y is an allyl group, from the points that raw materials in producing the polyalkenyl- substituted polyphenol compound are readily available and that an epoxy cured product having excellent heat resistance is obtained.
• dialkenyl substituted materials of bisphenol A, dialkenyl substituted materials of bisphenol F and dialkenyl substituted materials of naphthalene diol are preferable in the points that raw materials are easily available, low viscosity alkenyl phenol resins are obtained, and a cured product having excellent heat resistance is obtained.
• a polyphenol compound represented by the following formula (3) may be contained in a proportion of 50% by weight or less in bisphenol F.
• n is a number in the range of from 1 to 20, and preferably from 1 to 10, is converted into the corresponding polyalkenyl-substituted material by the above-mentioned reaction.
• the blending proportion of the epoxy resin of component A and the alkenyl phenolic resin of component B is such that the alkenyl phenolic resin of component B falls within a range of 5-150 parts by weight, preferably 20-120 parts by weight, per 100 parts by weight of the epoxy resin of component A. If the blending proportion is outside this range, the balance between heat resistance and moisture resistance of the epoxy resin cured product deteriorates, which is not preferable .
• a curing accelerator can be blended with the epoxy resin composition of the present invention.
• the curing accelerator to be blended include the following materials.
• Tributyl phosphine tricyclohexyl phosphine, triphenyl phosphine, tris (dimethoxyphenyl) phosphine, salts thereof, and the like.
• Those curing accelerators may be used alone, but can also be used as a mixture of two kinds or more.
• the amount of the curing accelerator used is 0.01-10 parts by weight, preferably 0.05-5 parts by weight, per 100 parts by weight of the epoxy resin of component A. If the amount of curing accelerator is less than 0.01 part by weight, cure accelerating effect of the epoxy resin of the present invention is small, and if the amount exceeds 10 parts by weight, water resistance of a cured product becomes poor, which is not preferable. If necessary, the following components can be added to the epoxy resin composition of the present invention.
• Powdery reinforcements or fillers such as metal oxides (e.g., aluminum oxide, magnesium oxide or the like), metal carbonates (e.g., calcium carbonate, magnesium carbonate or the like), silicon compounds (e.g., diatomaceous earth powder, basic magnesium silicate, calcined clay, silica fine powder, fused silica, crystalline silica or the like), metal hydroxides (e.g., aluminum hydroxide) kaolin, mica, ground quartz, graphite, molybdenum disulfide, and the like; fibrous reinforcements or fillers, such as glass fibers, ceramic fibers, carbon fibers, alumina fibers, silicon carbide fibers, boron fibers, polyester fibers, polyamide fibers, and the like. Those are blended in an amount of 10-900 parts by weight per 100 parts by weight of the sum of the epoxy resin and the curing agent.
• metal oxides e.g., aluminum oxide, magnesium oxide or the like
• metal carbonates e.g., calcium carbonate,
• coloring materials such as titanium dioxide, iron black, molybdenum red, Prussian blue, ultramarine blue, cadmium yellow, cadmium red, antimony trioxide, red phosphorus, bromo compounds, triphenylphosphate, and the like .
• various curable monomers, oligomers and synthetic resins can be blended.
• examples thereof include epoxy resin diluents such as monoepoxy compound, maleimides, cyanic acid esters, alkyd resins, melamine resins, fluorine resins, acrylic resins, silicone resins, polyester resins, and others that are used alone or as mixtures of two kinds or more thereof.
• the blending proportion of those resins is an amount that does not impair the inherent properties of the resin composition of the present invention, that is, preferably 50 parts by weight or less per 100 parts by weight of the sum of the epoxy resin and the curing agent.
• Examples of blending means of the epoxy resin, the alkenyl phenolic resin and optional components in the present invention include heat-melt mixing, melt kneading with rolls or kneaders, wet mixing using an appropriate organic solvent and dry mixing.
• This allyl phenolic resm was a mixture of 91% by weight of a polyallyl-substituted polyphenol compound and 9% by weight of a diallyl-substituted bifunctional phenol compound, and had a viscosity of 41 Pa • s at 30 °C and a hydroxyl equivalent of 163 (g/eq.) .
• This polyallyl phenolic resin had a viscosity of 1 Pa-s at 30 °C and a hydroxyl equivalent of 162 (g/eq.) .
• Example 1
• compositions were obtained by conducting the same procedure as in Example 1 except for changing the epoxy resin and the alkenyl phenolic resin as shown in Table 1, and cured products were obtained. Physical properties of those cured products are shown in Table 1.
• the epoxy resin composition of the present invention uses a novel liquid alkenyl phenolic resin as a curing agent, and an epoxy resin cured product obtained by curing the same with the curing agent is a cured product having well-balanced heat resistance and moisture resistance. Therefore, the composition can be applied to various uses, and in particular can advantageously be used for applications in electric and electronic fields of a liquid semiconductor encapsulant or the like.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Epoxy Resins (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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Citations (3)

• 1999
  • 1999-12-13 JP JP35252199A patent/JP2001164091A/ja active Pending
• 2000
  • 2000-12-13 AU AU30120/01A patent/AU3012001A/en not_active Abandoned
  • 2000-12-13 WO PCT/EP2000/012730 patent/WO2001044369A1/en not_active Application Discontinuation

Patent Citations (3)

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