WO2015037590A1 - エポキシ樹脂混合物、エポキシ樹脂組成物、硬化物および半導体装置 - Google Patents
エポキシ樹脂混合物、エポキシ樹脂組成物、硬化物および半導体装置 Download PDFInfo
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- WO2015037590A1 WO2015037590A1 PCT/JP2014/073827 JP2014073827W WO2015037590A1 WO 2015037590 A1 WO2015037590 A1 WO 2015037590A1 JP 2014073827 W JP2014073827 W JP 2014073827W WO 2015037590 A1 WO2015037590 A1 WO 2015037590A1
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- epoxy resin
- resin mixture
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- AJNFJHSUXOUPTD-LURJTMIESA-N C[C@@H]1C(O)=CC=CC1 Chemical compound C[C@@H]1C(O)=CC=CC1 AJNFJHSUXOUPTD-LURJTMIESA-N 0.000 description 2
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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- 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
Definitions
- the present invention relates to an epoxy resin mixture, an epoxy resin composition, a cured product thereof, and a semiconductor device suitable for electrical and electronic material applications requiring heat resistance.
- Epoxy resin compositions are widely used in the fields of electrical and electronic parts, structural materials, adhesives, paints, etc. due to their workability and excellent electrical properties, heat resistance, adhesion, moisture resistance (water resistance), etc. It has been.
- Epoxy resins generally have low flame retardancy when the Tg is increased. This is due to an increase in crosslink density.
- high Tg is required for semiconductor peripheral materials that require flame retardancy, it has been an urgent task to develop resins having these contradictory characteristics.
- Japanese Unexamined Patent Publication No. 2013-43958 and International Publication No. 2007/007827 introduce biphenylene aralkyl type resins using dihydroxybenzenes as a technique for solving this problem.
- the above epoxy resin has both high heat resistance and flame retardancy, but on the other hand, mechanical properties are lowered.
- the viscosity of the epoxy resin itself is too high, it was difficult to actually use it as a sealing material.
- the present invention is excellent in the mechanical strength, flame retardancy, and elastic modulus at high temperature of the cured product, which is a property contrary to the heat resistance while having excellent heat resistance of the cured product.
- An object of the present invention is to provide an epoxy resin mixture capable of simultaneously satisfying properties such as low resistance, and to provide an epoxy resin composition, a cured product, and a semiconductor device using the epoxy resin mixture.
- the present invention (1) An epoxy resin mixture obtained by simultaneously reacting a phenol resin (A) represented by the following formula (1) and a biphenol with an epihalohydrin (B);
- a curable resin composition comprising the epoxy resin mixture according to any one of (1) to (4) and a curing agent as essential components; (6) An epoxy resin composition comprising the epoxy resin mixture according to any one of (1) to (4) and a curing catalyst as essential components; (7) A cured product obtained by curing the curable resin composition according to (5) or (6), (8) A semiconductor device obtained by encapsulating a semiconductor chip with the curable resin composition described in (5) or (6) above; About.
- the cured product of the epoxy resin mixture of the present invention has excellent heat resistance, water absorption properties and mechanical properties, insulating materials for electrical and electronic parts, laminated boards (printed wiring boards, build-up boards, etc.), CFRP, etc. It is useful for various composite materials, adhesives, paints and the like.
- the epoxy resin mixture of the present invention is a mixture of an epoxidized product of a phenol resin (A) represented by the following formula (1) and a glycidylated product of a biphenol (B).
- the epoxidized product of biphenol is preferably 5 to 25 area% and more preferably 5 to 19 area% in the area percentage of GPC measurement in the epoxy resin mixture of the present invention.
- the epoxy resin mixture of the present invention preferably has a melt viscosity of 0.05 to 0.30 Pa ⁇ s (ICI melt viscosity 150 ° C. cone plate method).
- the phenol resin used in the present invention is a phenol resin represented by the following formula (1).
- the softening point of the phenol resin represented by the above formula (1) is preferably 55 to 100 ° C., more preferably 55 to 80 ° C., and preferably 60 to 80 ° C.
- the number of repetitions n is preferably 1.05 to 3.0, and more preferably 1.05 to 2.0.
- the ratio of the RP structure and (iii) (phenol)-(biphenylene)-(phenol) structure PP structure is preferably 4> (RP structure) / (RR structure)> 0.5. It is because high heat resistance can be ensured by being in this range. Further, it is preferable that 4> (RP structure) / (PP structure)> 0.5. It is because high flame retardance can be ensured by being in this range.
- the biphenol used in the present invention has the following structure.
- R 1 s a plurality of R 1 s exist independently and each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and k represents an integer of 1 to 4)
- the biphenol having the above structure includes, for example, 2,2 ′ form, 2,4 ′ form, 4,4 ′ form, etc., among which 4,4 ′ form biphenol is preferable.
- a purity of 95% or more can be suitably used.
- a desired epoxy resin mixture is obtained by simultaneously epoxidizing a mixture of a phenol resin and a biphenol represented by the formula (1) with epihalohydrin.
- the ratio of the phenol resin (A) represented by the formula (1) to the biphenol (B) is 1 mol equivalent of the hydroxyl equivalent of the phenol resin (A), and the hydroxyl group of the biphenol (B) is 0.08 to
- the amount is preferably 0.43 times mol, more preferably 0.08 to 0.33 times mol. If it is 0.08 times mol or more, viscosity reduction and mechanical properties are further improved, and if it is 0.43 times mol or less, crystal precipitation is reduced during production, yield is further improved, and heat resistance is improved. The characteristics are also improved.
- the epoxy resin mixture of the present invention can be obtained by reacting a mixture of the phenol resin (A) represented by the formula (1) and the biphenol (B) with epihalohydrin.
- the mixture of the phenol resin (A) and the biphenol (B) is referred to as the phenol resin mixture of the present invention.
- the epoxy equivalent of the epoxy resin mixture of the present invention is 1.02 to 1.13 times the theoretical epoxy equivalent of the phenol resin mixture as a raw material. More preferably, it is 1.03 to 1.10 times. If the ratio is less than 1.02, the epoxy synthesis and purification may be very expensive. If the ratio is more than 1.11, the problem may be caused by the amount of chlorine as described above.
- the total chlorine remaining in the epoxy resin mixture obtained by the reaction is preferably 5000 ppm or less, more preferably 3000 ppm or less, and particularly preferably 1000 ppm or less.
- the adverse effect of the chlorine amount is the same as described above.
- about chlorine ion and sodium ion, 5 ppm or less is preferable respectively, More preferably, it is 3 ppm or less.
- Chlorine ions are described above. Needless to say, cations such as sodium ions are also very important factors particularly in power device applications, and contribute to a defective mode when a high voltage is applied.
- the theoretical epoxy equivalent refers to an epoxy equivalent calculated when the phenolic hydroxyl group of the phenol resin mixture of the present invention is glycidylated without excess or deficiency.
- the epoxy equivalent is within the above range, an epoxy resin excellent in heat resistance and electrical reliability of the cured product can be obtained.
- the epoxy resin mixture of the present invention has a resinous form having a softening point.
- the softening point is preferably from 70 to 110 ° C., more preferably from 80 to 100 ° C. If the softening point is too low, blocking during storage becomes a problem, and there are many problems such as handling at low temperatures. On the other hand, when the softening point is too high, problems such as poor handling may occur during kneading with another resin (for example, a curing agent).
- the melt viscosity is preferably 0.05 to 0.30 Pa ⁇ s (ICI melt viscosity 150 ° C. cone plate method), and more preferably 0.07 to 0.20 Pa ⁇ s. When mixing and using inorganic materials (filler etc.), problems, such as poor fluidity, arise.
- the epihalohydrin used in the method for synthesizing the epoxy resin mixture of the present invention is preferably epichlorohydrin which is easily available industrially.
- the amount of epihalohydrin used is usually 3.0 to 15 mol, preferably 3.0 to 10 mol, more preferably 3.5 to 8.5 mol, particularly preferably 1 mol per mol of the hydroxyl group in the phenol resin mixture of the present invention. Is 4.5 to 8.5 moles. If the amount is less than 3.0 mol, the epoxy equivalent of the resulting epoxy resin mixture may be increased, and the handling workability of the resulting epoxy resin mixture may be deteriorated. If it exceeds 15 moles, the amount of solvent becomes large.
- an alkali metal hydroxide can be used.
- the alkali metal hydroxide that can be used in the above reaction include sodium hydroxide, potassium hydroxide and the like, and a solid substance may be used, or an aqueous solution thereof may be used. From the viewpoint of solubility and handling, it is preferable to use a solid material molded into a flake shape.
- the amount of the alkali metal hydroxide used is usually 0.90 to 1.5 mol, preferably 0.95 to 1.25 mol, more preferably, relative to 1 mol of the hydroxyl group of the raw material phenol resin mixture of the present invention. 0.99 to 1.15 mol.
- quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride may be added as a catalyst.
- the amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of hydroxyl group in the raw material phenol mixture.
- a nonpolar proton solvent such as dimethyl sulfoxide, dioxane, dimethylimidazolidinone
- an alcohol having 1 to 5 carbon atoms examples include alcohols such as methanol, ethanol and isopropyl alcohol.
- the amount of the nonpolar protic solvent or alcohol having 1 to 5 carbon atoms is usually 2 to 50% by weight, preferably 4 to 25% by weight, based on the amount of epihalohydrin used.
- epoxidation may be performed while controlling the moisture in the system by a technique such as azeotropic dehydration.
- the electrical reliability of the cured product of the obtained epoxy resin mixture may be deteriorated, and it is preferable to synthesize by controlling the moisture to 5% or less. Further, when an epoxy resin is obtained using a nonpolar proton solvent, a cured product of an epoxy resin mixture having excellent electrical reliability can be obtained, and therefore a nonpolar proton solvent can be suitably used.
- the reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. In particular, in the present invention, 60 ° C. or higher is preferable for higher-purity epoxidation, and reaction under conditions close to reflux conditions is particularly preferable.
- the reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours, particularly preferably 1 to 3 hours. If the reaction time is short, the reaction does not proceed, and if the reaction time is long, a by-product is formed, which is not preferable. After the reaction product of these epoxidation reactions is washed with water or without washing with water, the epihalohydrin, the solvent and the like are removed under heating and reduced pressure.
- the recovered epoxidized product is a ketone compound having 4 to 7 carbon atoms (for example, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.). It can be dissolved as a solvent and reacted by adding an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide to ensure ring closure.
- an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide
- the amount of the alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, relative to 1 mol of the hydroxyl group of the phenol resin mixture used for the epoxidation.
- the reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.
- the produced salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain the epoxy resin mixture of the present invention.
- the epoxy resin mixture of the present invention exhibits a semi-crystalline resin form.
- a normal epoxy resin mixture is not oriented and becomes a transparent amorphous resin.
- the resin mixture has crystallinity and becomes cloudy and not transparent.
- the semi-crystalline state indicates this state, and the hardness of the resin obtained by making the semi-crystalline state becomes hard, and when kneading and pulverizing, the resin becomes easy to pulverize and has high productivity.
- the semi-crystalline form indicates not only the resin in the white turbid state as described above, but also after being allowed to stand for 10 minutes or more after the reaction in the range of 100 ° C. ⁇ 30 ° C. even in the case of an amorphous transparent resin, Including those that become cloudy by gradually cooling.
- Such a resin also contributes to productivity by promoting crystallization by kneading or the like at the time of preparing the resin composition.
- the epoxidized product of the phenol resin represented by the above formula (1) and bisglycidyloxybiphenyl (however, when the aromatic ring has a substituent, the number of substituents is 4 or less, the number of carbon atoms.
- the reaction under the preferable conditions as described above there is a structure in which the phenol resin structure represented by the above formula (1) and the biphenol structure are connected by epihalohydrin. Exists. Therefore, by simultaneously epoxidizing the phenol resin mixture of the present invention, the structure is formed and the viscosity tends to be relatively low, which is preferable in improving the fluidity which is the object of the present invention. Also, mechanical properties such as toughness are improved.
- the epoxy resin mixture obtained by such a method has low crystallinity and can be easily purified to obtain an epoxy resin mixture with a small amount of residual chlorine. Becomes easy.
- the epoxy resin having a structure in which the phenol resin structure represented by the above formula (1) and the biphenol structure are connected by epihalohydrin is preferably 0.01 to 10 area% in area% of GPC measurement. 0.1 to 10 area% is particularly preferable.
- the epoxy resin composition of the present invention contains the epoxy resin mixture of the present invention, a curing catalyst and / or a curing agent. Moreover, it is preferable to contain another epoxy resin as an arbitrary component.
- the epoxy resin composition of the present invention may contain other types of epoxy resins in addition to the epoxy resin mixture of the present invention.
- the proportion of the epoxy resin mixture of the present invention in the total epoxy resin is preferably 20% by weight or more, more preferably 30% by weight or more, and particularly preferably 40% by weight or more.
- bisphenol A bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetofu Non, o-hydroxy
- phosphonium salts, ammonium salts, and metal compounds are particularly preferable in terms of coloring at the time of curing and changes thereof.
- the salt with halogen may leave halogen in the cured product.
- the curing accelerator is used in an amount of 0.01 to 5.0 parts by weight based on the epoxy resin 100 as necessary.
- the epoxy resin composition of the present invention preferably contains a curing agent.
- a curing agent examples thereof include amine compounds, acid anhydride compounds, amide compounds, phenol resins, carboxylic acid compounds, and the like.
- Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, and nitrogen-containing compounds such as polyamide resins synthesized from linolenic acid and ethylenediamine (amine, Amide compounds); phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methyl hexahydro Phthalic anhydr
- the amount of the curing agent used in the epoxy resin composition of the present invention (hereinafter also referred to as curable resin composition) is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin. When less than 0.7 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.
- a cyanate ester compound as the other component.
- the cyanate ester compound can be made into a heat-resistant cured product having a higher crosslinking density by a reaction with an epoxy resin in addition to a curing reaction alone.
- the cyanate ester resin include 2,2-bis (4-cyanatephenyl) propane, bis (3,5-dimethyl-4-cyanatephenyl) methane, 2,2-bis (4-cyanatephenyl) ethane, These derivatives, aromatic cyanate ester compounds, etc. are mentioned. Further, for example, as described in the above-mentioned curing material, synthesis can be performed by reaction of various phenol resins with hydrocyanic acid or salts thereof.
- those having a structure not having a methylene structure at the benzyl position in the molecule such as 2,2-bis (4-cyanatephenyl) propane and derivatives thereof (partially polymerized products) are particularly preferable. You may use independently and may use 2 or more types together.
- the epoxy resin composition of the present invention may contain a phosphorus-containing compound as a flame retardant imparting component.
- the phosphorus-containing compound may be a reactive type or an additive type.
- Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphoric esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-
- Phosphate esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred.
- the epoxy resin composition of the present invention can be blended with a binder resin as necessary.
- the binder resin include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins. However, it is not limited to these.
- the blending amount of the binder resin is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 100 parts by weight in total of the epoxy resin and the curing agent. 0.05 to 20 parts by weight is used as necessary.
- An inorganic filler can be added to the epoxy resin composition of the present invention as necessary.
- inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like.
- the present invention is not limited to these.
- These fillers may be used alone or in combination of two or more.
- the content of these inorganic fillers is generally 0 to 95% by weight in the epoxy resin composition of the present invention, although it depends on the use, and is particularly preferable when used for sealing materials.
- the epoxy resin composition of the present invention includes an antioxidant, a light stabilizer, a silane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate and calcium stearate, various compounding agents such as pigments, Various thermosetting resins can be added.
- the coupling material is preferably added with an epoxy group-containing coupling material or a thiol-containing coupling material.
- the epoxy resin composition of the present invention can be obtained by uniformly mixing each component.
- the epoxy resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method.
- an epoxy resin component, a curing agent component, and a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, a compounding agent, and the like if necessary, uniformly using an extruder, kneader, roll, planetary mixer, etc. Mix thoroughly until the epoxy resin composition is obtained. If the resulting epoxy resin composition is liquid, the substrate is impregnated with a potting or casting, or poured into a mold and cast. Or cured by heating.
- the obtained epoxy resin composition is solid, it is molded using a cast after casting or a transfer molding machine, and further cured by heating.
- the curing temperature and time are 80 to 200 ° C. and 2 to 10 hours.
- a curing method it is possible to cure at a high temperature at a stretch, but it is preferable to increase the temperature stepwise to advance the curing reaction.
- initial curing is performed at 80 to 150 ° C.
- post-curing is performed at 100 to 200 ° C.
- the temperature is preferably increased in 2 to 8 stages, more preferably 2 to 4 stages.
- the epoxy resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. to obtain a curable resin composition varnish, which contains glass fiber, -A prepreg obtained by impregnating a base material such as bon fiber, polyester fiber, polyamide fiber, alumina fiber or paper and drying by heating is subjected to hot press molding to obtain a cured product of the epoxy resin composition of the present invention.
- the solvent is used in an amount of 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the epoxy resin composition of the present invention and the solvent.
- compositions include adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (including printed circuit boards, wire coatings, sealing materials, Sealants, cyanate resin compositions for substrates) and resist curing agents include additives to other resins such as acrylic ester resins.
- insulating material for electronic materials a sealing material including a printed circuit board, an electric wire coating
- adhesives examples include civil engineering, architectural, automotive, general office, and medical adhesives, as well as electronic material adhesives.
- adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).
- sealing agent and substrate potting sealing for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, etc., dipping, transfer mold sealing, ICs, LSIs for COB, COF, TAB, etc.
- substrate use as which a functionality, such as a network board
- the epoxy resin composition of the present invention is particularly preferably used for a semiconductor device.
- the semiconductor device is a group of IC packages mentioned above.
- the semiconductor device of the present invention can be obtained by sealing a silicon chip installed on a package substrate or a support such as a die with the epoxy resin composition of the present invention.
- the molding temperature and molding method are as described above.
- Epoxy equivalent Conforms to JIS K 7236 (ISO 3001) ICI melt viscosity: compliant with JIS K 7117-2 (ISO 3219) Softening point: compliant with JIS K 7234 Total chlorine: compliant with JIS K 7243-3 (ISO 21672-3) Chlorine ion: JIS K 7243-1 (ISO 21672) -1) compliant GPC: Column (Shodex KF-603, KF-602.5, KF-602, KF-601x2) The coupled eluent is tetrahydrofuran. The flow rate is 0.5 ml / min. Column temperature is 40 ° C Detection: RI (differential refraction detector)
- Example 2 and Comparative Example 1 Using the epoxy resin mixture (EP1) obtained above or a comparative epoxy resin (EP2: the phenol resin was changed to 172 parts in Example 1 and biphenol was not added), the epoxy resin and the curing agent (P-1: phenol aralkyl resin (KAYAHARD GPH-65, manufactured by Nippon Kayaku Co., Ltd.), P-2: phenol aralkyl resin (Millex XLC-3L, manufactured by Mitsui Chemicals, Inc.) at equal equivalents and cured Catalyst (curing accelerator: triphenylphosphine (TPP manufactured by Hokuko Chemical Co., Ltd.)) and, if necessary, filler (fused silica, manufactured by Kashimori, MSR-2122, the filler amount% in the table is a proportion of the total epoxy resin composition) Was mixed and kneaded uniformly using a mixing roll to obtain a curable resin composition.
- P-1 phenol aralkyl resin
- P-2 phenol
- the curable resin composition was pulverized with a mixer and further tableted with a tablet machine. This tableted curable resin composition was transfer molded (175 ° C. ⁇ 60 seconds), and after demolding, cured under the conditions of 160 ° C. ⁇ 2 hours + 180 ° C. ⁇ 6 hours to obtain a test piece for evaluation.
- the physical properties of the cured product were measured as follows. Depending on the evaluation items of the physical properties of the cured product, the type of curing agent used is as shown in Table 1 below.
- the amount of curing accelerator used is 1 for the weight of the epoxy resin in the sample used for evaluation of heat resistance and shrinkage. % And 2% with respect to the weight of the epoxy resin in the sample used for evaluation of flame retardancy.
- the test results are also shown in Table 1 below.
- ⁇ TMA measurement conditions Thermo-mechanical measuring device manufactured by TA-instruments, Q400EM Measurement temperature range: 40 ° C-280 ° C Temperature increase rate: 2 ° C./min ⁇ flame retardant test> -Determination of flame retardancy: performed in accordance with UL94. However, the test was conducted with a sample size of 12.5 mm wide ⁇ 150 mm long and a thickness of 0.8 mm. -Afterflame time: Total afterflame time after 10 times of contact with a set of 5 samples ⁇ Curing shrinkage> Compliant with JISK-6911 (mold shrinkage)
- the epoxy resin composition of the present invention can achieve both high heat resistance and flame retardancy.
- the epoxy equivalent of the obtained epoxy resin mixture (EP3) was 192 g / eq.
- the melt viscosity (ICI melt viscosity cone # 1) at a softening point of 82 ° C. and 150 ° C. was 0.07 Pa ⁇ s.
- Example 5 The epoxy resin mixture (EP3, EP4) or the comparative epoxy resin (EP2) obtained above was used as a curing agent (P-3: phenol novolak (H-1 manufactured by Meiwa Kasei Kogyo Co., Ltd.)), curing catalyst ( Curing accelerator: Triphenylphosphine (TPP manufactured by Hokuko Chemical Co., Ltd.) was blended in the proportions (equivalents) shown in Table 2, and uniformly mixed and kneaded using a mixing roll to obtain a curable resin composition.
- the curable resin composition was pulverized with a mixer and further tableted with a tablet machine. This tableted curable resin composition was transfer molded (175 ° C.
- test results are also shown in Table 2.
- TMA measurement conditions Thermo-mechanical measuring device manufactured by TA-instruments, Q400EM Measurement temperature range: 40 ° C-280 ° C Temperature increase rate: 2 ° C / min ⁇ Peel strength> 180 ° C peel test JIS K-6854-2 compliant Rolled copper foil used
- the cured product of the epoxy resin composition of the present invention has improved toughness while maintaining high heat resistance. That is, the epoxy resin composition of the present invention can achieve both high heat resistance and toughness of the cured product.
- Example 8 The epoxy resin mixture (EP5) or comparative epoxy resin (EP2) obtained above was prepared in accordance with a curing agent (P-4: phenol resin used in Example 1 International Publication No. 2007/007827).
- TPP triphenylphosphine
- the curable resin composition was pulverized with a mixer and further tableted with a tablet machine. This tableted curable resin composition was transfer molded (175 ° C. ⁇ 60 seconds), and after demolding, cured under the conditions of 160 ° C. ⁇ 2 hours + 180 ° C. ⁇ 6 hours to obtain a test piece for evaluation. Using the test specimen for evaluation, the physical properties of the cured product were measured as follows. The test results are also shown in Table 2.
- TMA measurement conditions Thermo-mechanical measuring device manufactured by TA-instruments, Q400EM Measurement temperature range: 40 ° C-280 ° C Temperature increase rate: 2 ° C / min
- ⁇ Measurement conditions for thermal decomposition characteristics Part of the obtained test piece was pulverized by a cycle mill, powdered, passed through a 100 ⁇ m mesh and aligned to a particle size of 75 ⁇ m mesh-on, and a 5-10 mg sample was taken. It was confirmed. The weight loss temperature of 5% was used as an index. Measured with TG-DTA (Td5) Measurement sample: Powdery (100 ⁇ m mesh passed, 75 ⁇ m mesh on) 5-10mg Measurement conditions: Temperature rising rate 10 ° C./min Air flow 200 ml / min 5% weight loss temperature was measured.
- the epoxy resin of the present invention can maintain high properties in other properties while maintaining high heat resistance, despite a significant reduction in viscosity by half or less. That is, the epoxy resin of the present invention is a resin that can improve various properties such as heat resistance that are difficult to achieve.
- the cured product since the cured product has excellent heat resistance, water absorption characteristics and flame retardancy, insulating materials for electrical and electronic parts, laminated boards (printed wiring boards, build-up boards, etc.) and CFRP are used. It is useful for various composite materials, adhesives, paints, etc.
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Abstract
Description
また、日本国特開2013-43958号公報、国際公開第2007/007827号には本課題を解決する手法としてジヒドロキシベンゼン類を利用したビフェニレンアラルキルタイプの樹脂が紹介されている。
しかし、上記のエポキシ樹脂は高い耐熱性と難燃性を両立するが、その反面、機械特性が低下する。またエポキシ樹脂自体の粘度が高すぎるため、封止材として実際に使用するのが難しいものであった。
即ち、本発明は、優れた硬化物の耐熱性を有しながら、該耐熱性と相反する特性である、硬化物の機械強度、難燃性、高温での弾性率に優れ、硬化前は粘度が低い等の特性を同時に満たすことができるエポキシ樹脂混合物を提供することを目的とし、さらに該エポキシ樹脂混合物を用いた、エポキシ樹脂組成物、硬化物および半導体装置を提供することを目的とする。
(1)
下記式(1)で表されるフェノール樹脂(A)とビフェノールを同時にエピハロヒドリン(B)と反応することによって得られるエポキシ樹脂混合物、
(2)フェノール樹脂(A)とビフェノール(B)の比が、(A)の水酸基当量1モル当量に対し、(B)の水酸基が0.08~0.33倍モルである前項(1)に記載のエポキシ樹脂混合物、
(3)
軟化点が80~100℃である前項(1)または(2)に記載のエポキシ樹脂混合物、
(4)
150℃におけるICI溶融粘度(コーンプレート法)が0.05~0.30Pa・sである前項(1)~(3)のいずれか一項に記載のエポキシ樹脂混合物、
(5)
前項(1)~(4)のいずれか一項に記載のエポキシ樹脂混合物と硬化剤を必須成分とする硬化性樹脂組成物、
(6)
前項(1)~(4)のいずれか一項に記載のエポキシ樹脂混合物と硬化触媒を必須成分とするエポキシ樹脂組成物、
(7)
前項(5)又は(6)に記載の硬化性樹脂組成物を硬化した硬化物、
(8)
半導体チップを前項(5)又は(6)に記載の硬化性樹脂組成物を用いて封止して得られる半導体装置、
に関する。
一方、ビフェノールのエポキシ化物は、本発明のエポキシ樹脂混合物中、GPC測定の面積%において、5~25面積%であることが好ましく、5~19面積%であることがより好ましい。
また、本発明のエポキシ樹脂混合物は、溶融粘度が0.05~0.30Pa・s(ICI 溶融粘度 150℃ コーンプレート法)であることが好ましい。
また、繰り返し数であるnとしては1.05~3.0が好ましく、1.05~2.0がより好ましい。
ここで、フェノール樹脂中のn=1の化合物が、(i)(レゾルシン)-(ビフェニルレン)-(レゾルシン)構造であるRR構造、(ii)(レゾルシン)-(ビフェニレン)-(フェノール)構造であるRP構造、(iii)(フェノール)-(ビフェニレン)-(フェノール)構造であるPP構造の比率において、4>(RP構造)/(RR構造)>0.5であることが好ましい。この範囲内にあることで、高い耐熱性を確保できるためである。また、4>(RP構造)/(PP構造)>0.5であることが好ましい。この範囲内にあることで、高い難燃性を確保できるためである。
また、純度は95%以上のものが好適に使用できる。
ここで、前記式(1)で表されるフェノール樹脂(A)とビフェノール(B)の比率はフェノール樹脂(A)の水酸基当量1モル当量に対し、ビフェノール(B)の水酸基は0.08~0.43倍モルであることが好ましく、より好ましくは0.08~0.33倍モルである。
0.08倍モル以上であれば、低粘度化、機械特性がより改善され、0.43倍モル以下であれば、製造時に結晶の析出がより少なくなり、収率がより向上し、また耐熱性もより向上する。
本発明のエポキシ樹脂混合物は前記式(1)で表されるフェノール樹脂(A)とビフェノール(B)の混合物をエピハロヒドリンと反応することで得られる。ここで以降、フェノール樹脂(A)とビフェノール(B)の混合物を本発明のフェノール樹脂混合物と表記する。
本発明のエポキシ樹脂混合物のエポキシ当量は原料となるフェノール樹脂混合物の理論エポキシ当量に対し1.02倍~1.13倍である。より好ましくは1.03~1.10倍である。1.02倍を下回る場合、エポキシの合成、精製に多大な費用がかかることがあり、また1.11倍を超えた場合、上述同様塩素量による課題が生じることがある。
また、反応により得られたエポキシ樹脂混合物に残存している全塩素としては5000ppm以下、より好ましくは3000ppm以下、特に1000ppm以下であることが好ましい。塩素量による悪影響については前述と同様である。なお、塩素イオン、ナトリウムイオンについては各々5ppm以下が好ましく、より好ましくは3ppm以下である。塩素イオンは先に記載し、いうまでも無いが、ナトリウムイオン等のカチオンも、特にパワーデバイス用途においては非常に重要なファクターとなり、高電圧がかかった際の不良モードの一因となる。
ここで、理論エポキシ当量とは、本発明のフェノール樹脂混合物のフェノール性水酸基が過不足なくグリシジル化した時に算出されるエポキシ当量を示す。エポキシ当量が上記範囲内にあることで、硬化物の耐熱性、電気信頼性に優れたエポキシ樹脂を得ることができる。
3.0モルを下回ると得られるエポキシ樹脂混合物のエポキシ当量が大きくなることがあり、また、得られるエポキシ樹脂混合物の取扱い作業性が悪くなる可能性がある。15モルを超えると溶剤量が多量となる。
アルカリ金属水酸化物の使用量は原料の本発明のフェノール樹脂混合物の水酸基1モルに対して通常0.90~1.5モルであり、好ましくは0.95~1.25モル、より好ましくは0.99~1.15モルである。
系中の水分が多い場合には、得られたエポキシ樹脂混合物の硬化物において電気信頼性が悪くなることがあり、水分は5%以下にコントロールして合成することが好ましい。また、非極性プロトン溶媒を使用してエポキシ樹脂を得た際には、電気信頼性に優れるエポキシ樹脂混合物の硬化物が得られるため、非極性プロトン溶媒は好適に使用できる。
これらのエポキシ化反応の反応物を水洗後、または水洗無しに加熱減圧下でエピハロヒドリンや溶媒等を除去する。また更に加水分解性ハロゲンの少ないエポキシ樹脂混合物とするために、回収したエポキシ化物を炭素数4~7のケトン化合物(たとえば、メチルイソブチルケトン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン等が挙げられる。)を溶剤として溶解し、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物の水溶液を加えて反応を行い、閉環を確実なものにすることも出来る。この場合アルカリ金属水酸化物の使用量はエポキシ化に使用したフェノール樹脂混合物の水酸基1モルに対して通常0.01~0.3モル、好ましくは0.05~0.2モルである。反応温度は通常50~120℃、反応時間は通常0.5~2時間である。
通常のエポキシ樹脂混合物は配向せず透明なアモルファス状態の樹脂となる。本発明においては、その樹脂混合物が結晶性を有し、白濁した透明でない状態となる。半晶状とはこの状態を示し、半晶状となることでできた樹脂の硬さが硬くなり、混練、粉砕の際に、粉砕しやすく、生産性の良い樹脂となる。ここで半晶状とは、上述のような白濁した状態の樹脂を示すだけでなく、アモルファス状態の透明な樹脂であっても100℃±30℃の範囲で反応後に10分以上放置した後、徐々に冷却することで、白濁するものも含む。このような樹脂も樹脂組成物作成の際の混練等により、同様に結晶化が促進され、生産性に寄与する。
また、ビフェノールのみをエポキシ化した場合と比較して、このような製法で得られたエポキシ樹脂混合物は結晶性が低いため、精製が容易に行えることから残存塩素量が少ないエポキシ樹脂混合物を得ることが容易となる。
本発明においては、上記式(1)で表されるフェノール樹脂構造とビフェノール構造がエピハロヒドリンによってつながった構造を有するエポキシ樹脂が、GPC測定の面積%において0.01~10面積%であることが好ましく、0.1~10面積%であることが特に好ましい。
硬化促進剤は、エポキシ樹脂100に対して0.01~5.0重量部が必要に応じ用いられる。
本発明においては特に電子材料用途に使用するため、前述のフェノール樹脂が好ましい。
半導体装置とは前述に挙げるICパッケージ群となる。
本発明の半導体装置は、パッケージ基板や、ダイなどの支持体に設置したシリコンチップを本発明のエポキシ樹脂組成物で封止することで得られる。成型温度、成型方法については前述のとおりである。
以下に実施例で用いた各種分析方法について記載する。
エポキシ当量: JIS K 7236 (ISO 3001) に準拠
ICI溶融粘度: JIS K 7117-2 (ISO 3219) に準拠
軟化点: JIS K 7234 に準拠
全塩素: JIS K 7243-3 (ISO 21672-3) に準拠
塩素イオン: JIS K 7243-1 (ISO 21672-1) に準拠
GPC:
カラム(Shodex KF-603、KF-602.5、KF-602、KF-601x2)
連結溶離液はテトラヒドロフラン
流速は0.5ml/min.
カラム温度は40℃
検出:RI(示差屈折検出器)
撹拌機、還流冷却管、撹拌装置を備えたフラスコに、窒素パージを施しながら国際公開第2007/007827号に準拠して製造したフェノール樹脂((a)/(b)=1.3、n=1.5、(RP構造)/(RR構造)=2.15、(RP構造)/(PP構造)=2.1(GPC測定)、水酸基当量134g/eq.、軟化点93℃)132部、4,4’-ビフェノール29.3部(フェノール樹脂(A)の水酸基当量1モル当量に対し、ビフェノール(B)の水酸基は0.32倍モル)、エピクロロヒドリン541部(4.5モル当量 対 フェノール樹脂)、ジメチルスルホキシド124部を加え、撹拌下で溶解し、40~45℃にまで昇温した。次いでフレーク状の水酸化ナトリウム54.6部を90分かけて分割添加した後、更に40℃で1時間、60℃で1時間、70℃で1時間反応を行った。反応終了後,ロータリーエバポレーターを用いて減圧下、過剰のエピクロルヒドリン等の溶剤類を留去した。残留物にメチルイソブチルケトン500部を加え溶解し、水300部で水洗した後、70℃にまで昇温した。撹拌下で30重量%の水酸化ナトリウム水溶液17部を加え、1時間反応を行った後、油層の洗浄水が中性になるまで水洗を行い、得られた溶液から、ロータリーエバポレーターを用いて減圧下にメチルイソブチルケトン等を留去することで本発明のエポキシ樹脂混合物(EP1)201部を得た。得られたエポキシ樹脂混合物(EP1)のエポキシ当量は192g/eq.軟化点95℃、150℃における溶融粘度(ICI溶融粘度 コーン#1)は0.11Pa・sであった。また、得られたエポキシ樹脂混合物(EP1)をゲルパーミエーションクロマトグラフィーで測定した結果、ビフェノールのエポキシ樹脂が15.3面積%含有されていることが確認され、前記式(1)においてn=0のエポキシ化物を28.8面積%、n=1のエポキシ化物を17.6面積%含有していることが確認された。
前記で得られたエポキシ樹脂混合物(EP1)ないし比較用のエポキシ樹脂(EP2:実施例1においてフェノール樹脂を172部に変更し、ビフェノールを添加しなかったもの)を使用し、エポキシ樹脂と硬化剤(P-1:フェノールアラルキル樹脂(日本化薬(株)製 KAYAHARD GPH-65)、P-2:フェノールアラルキル樹脂(三井化学(株)製 ミレックスXLC-3L))を等当量で配合し、硬化触媒(硬化促進剤:トリフェニルホスフィン(北興化学(株)製 TPP))と必要に応じてフィラー(溶融シリカ 瀧森製 MSR-2122 表中のフィラー量%はエポキシ樹脂組成物全体に占める割合)を配合し、ミキシングロールを用いて均一に混合・混練し、硬化性樹脂組成物を得た。この硬化性樹脂組成物をミキサーにて粉砕し、更にタブレットマシーンにてタブレット化した。このタブレット化された硬化性樹脂組成物をトランスファー成型(175℃×60秒)し、更に脱型後160℃×2時間+180℃×6時間の条件で硬化、評価用試験片を得た。
この評価用試験片を用いて、硬化物の物性を以下の要領で測定した。なお、硬化物の物性の評価項目によって、使用する硬化剤種は下記表1の通りとし、硬化促進剤の使用量は、耐熱性及び収縮率の評価に使用する試料ではエポキシ樹脂重量に対し1%とし、難燃性の評価に使用する試料ではエポキシ樹脂重量に対し2%とした。試験結果も下記表1に示す。
熱機械測定装置 TA-instruments製、Q400EM
測定温度範囲:40℃~280℃
昇温速度:2℃/分
<難燃性試験>
・難燃性の判定:UL94に準拠して行った。ただし、サンプルサイズは幅12.5mm×長さ150mmとし、厚さは0.8mmで試験を行った。
・残炎時間:5個1組のサンプルに10回接炎したあとの残炎時間の合計
<硬化収縮>
JISK-6911(成型収縮率)に準拠
撹拌機、還流冷却管、撹拌装置を備えたフラスコに、窒素パージを施しながら国際公開第2007/007827号に準拠して製造したフェノール樹脂((a)/(b)=1.3、n=1.5、(RP構造)/(RR構造)=2.15、(RP構造)/(PP構造)=2.1(GPC測定)、水酸基当量134g/eq.、軟化点93℃)97.8部、4,4’-ビフェノール25.1部(フェノール樹脂(A)の水酸基当量1モル当量に対し、ビフェノール(B)の水酸基は0.37倍モル)、エピクロロヒドリン555部(6モル当量 対 フェノール樹脂)、メタノール55.5部を加え、撹拌下で溶解し、70℃にまで昇温した。次いでフレーク状の水酸化ナトリウム42部を90分かけて分割添加した後、70℃で1時間反応を行った。反応終了後,水洗を行った後、得られた有機層をロータリーエバポレーターを用いて減圧下、過剰のエピクロルヒドリン等の溶剤類を留去した。残留物にメチルイソブチルケトン500部を加え溶解し、70℃にまで昇温した。撹拌下で30重量%の水酸化ナトリウム水溶液10部を加え、1時間反応を行った後、油層の洗浄水が中性になるまで水洗を行い、得られた溶液から、ロータリーエバポレーターを用いて減圧下にメチルイソブチルケトン等を留去することで本発明のエポキシ樹脂混合物(EP3)161部を得た。得られたエポキシ樹脂混合物(EP3)のエポキシ当量は192g/eq.軟化点82℃、150℃における溶融粘度(ICI溶融粘度 コーン#1)は0.07Pa・sであった。また、得られたエポキシ樹脂混合物(EP3)をゲルパーミエーションクロマトグラフィーで測定した結果、ビフェノールのエポキシ樹脂が12.0面積%含有されていることが確認され、前記式(1)においてn=0のエポキシ化物を24.4面積%、n=1のエポキシ化物を16.5面積%含有していることが確認された。
撹拌機、還流冷却管、撹拌装置を備えたフラスコに、窒素パージを施しながら国際公開第2007/007827号に準拠して製造したフェノール樹脂((a)/(b)=1.3、n=1.5、(RP構造)/(RR構造)=2.15、(RP構造)/(PP構造)=2.1(GPC測定)、水酸基当量134g/eq.、軟化点93℃)101.8部、4,4’-ビフェノール22.3部(フェノール樹脂(A)の水酸基当量1モル当量に対し、ビフェノール(B)の水酸基は0.316倍モル)、エピクロロヒドリン555部(6ル当量 対 フェノール樹脂)、ジメチルスルホキシド125部を加え、撹拌下で溶解し、40~45℃にまで昇温した。次いでフレーク状の水酸化ナトリウム42部を90分かけて分割添加した後、更に40℃で1時間、60℃で1時間、70℃で1時間反応を行った。反応終了後,ロータリーエバポレーターを用いて減圧下、過剰のエピクロルヒドリン等の溶剤類を留去した。残留物にメチルイソブチルケトン500部を加え溶解し、水300部で水洗した後、70℃にまで昇温した。撹拌下で30重量%の水酸化ナトリウム水溶液10部を加え、1時間反応を行った後、油層の洗浄水が中性になるまで水洗を行い、得られた溶液から、ロータリーエバポレーターを用いて減圧下にメチルイソブチルケトン等を留去することで本発明のエポキシ樹脂混合物(EP4)159部を得た。得られたエポキシ樹脂混合物(EP4)のエポキシ当量は189g/eq.軟化点98℃、150℃における溶融粘度(ICI溶融粘度 コーン#1)は0.08Pa・sであった。また、得られたエポキシ樹脂混合物(EP4)をゲルパーミエーションクロマトグラフィーで測定した結果、ビフェノールのエポキシ樹脂が14.9面積%含有されていることが確認され、前記式(1)においてn=0のエポキシ化物を29.3面積%、n=1のエポキシ化物を18.6面積%含有していることが確認された。
前記で得られたエポキシ樹脂混合物(EP3,EP4)ないし比較用のエポキシ樹脂(EP2)を、硬化剤(P-3:フェノールノボラック(明和化成工業(株)製 H-1))、硬化触媒(硬化促進剤:トリフェニルホスフィン(北興化学(株)製 TPP))を表2の割合(当量)で配合し、ミキシングロールを用いて均一に混合・混練し、硬化性樹脂組成物を得た。この硬化性樹脂組成物をミキサーにて粉砕し、更にタブレットマシーンにてタブレット化した。このタブレット化された硬化性樹脂組成物をトランスファー成型(175℃×60秒)し、更に脱型後160℃×2時間+180℃×6時間の条件で硬化、評価用試験片を得た。この評価用試験片を用いて、硬化物の物性を以下の要領で測定した。試験結果も表2に示す。
熱機械測定装置 TA-instruments製、Q400EM
測定温度範囲:40℃~280℃
昇温速度:2℃/分
<ピール強度>
・180℃剥離試験 JIS K-6854-2に準拠 圧延銅箔使用
撹拌機、還流冷却管、撹拌装置を備えたフラスコに、窒素パージを施しながら国際公開第2007/007827号に準拠して製造したフェノール樹脂((a)/(b)=1.3、n=1.5、(RP構造)/(RR構造)=2.15、(RP構造)/(PP構造)=2.1(GPC測定)、水酸基当量134g/eq.、軟化点93℃)109.9部、4,4’-ビフェノール16.8部(フェノール樹脂(A)の水酸基当量1モル当量に対し、ビフェノール(B)の水酸基は0.22倍モル)、エピクロロヒドリン463部(5ル当量 対 フェノール樹脂)、ジメチルスルホキシド100部を加え、撹拌下で溶解し、40~45℃にまで昇温した。次いでフレーク状の水酸化ナトリウム42部を90分かけて分割添加した後、更に40℃で1時間、60℃で1時間、70℃で1時間反応を行った。反応終了後、ロータリーエバポレーターを用いて減圧下、過剰のエピクロルヒドリン等の溶剤類を留去した。残留物にメチルイソブチルケトン500部を加え溶解し、水300部で水洗した後、70℃にまで昇温した。撹拌下で30重量%の水酸化ナトリウム水溶液10部を加え、1時間反応を行った後、油層の洗浄水が中性になるまで水洗を行い、得られた溶液から、ロータリーエバポレーターを用いて減圧下にメチルイソブチルケトン等を留去することで本発明のエポキシ樹脂混合物(EP5)169部を得た。得られたエポキシ樹脂混合物(EP5)のエポキシ当量は189g/eq.軟化点83℃、150℃における溶融粘度(ICI溶融粘度 コーン#1)は0.07Pa・sであった。また、得られたエポキシ樹脂混合物(EP5)をゲルパーミエーションクロマトグラフィーで測定した結果、ビフェノールのエポキシ樹脂が11.0面積%含有されていることが確認され、前記式(1)においてn=0のエポキシ化物を29.1面積%、n=1のエポキシ化物を17.7面積%含有していることが確認された。
前記で得られたエポキシ樹脂混合物(EP5)ないし比較用のエポキシ樹脂(EP2)を、硬化剤(P-4:実施例1で使用したフェノール樹脂 国際公開第2007/007827号に準拠して製造したフェノール樹脂((a)/(b)=1.3、n=1.5、(RP構造)/(RR構造)=2.15、(RP構造)/(PP構造)=2.1(GPC測定)、水酸基当量134g/eq.、軟化点93℃))、硬化触媒(硬化促進剤:トリフェニルホスフィン(北興化学(株)製 TPP))を表3の割合(当量)で配合し、ミキシングロールを用いて均一に混合・混練し、硬化性樹脂組成物を得た。この硬化性樹脂組成物をミキサーにて粉砕し、更にタブレットマシーンにてタブレット化した。このタブレット化された硬化性樹脂組成物をトランスファー成型(175℃×60秒)し、更に脱型後160℃×2時間+180℃×6時間の条件で硬化、評価用試験片を得た。
この評価用試験片を用いて、硬化物の物性を以下の要領で測定した。試験結果も表2に示す。
熱機械測定装置 TA-instruments製、Q400EM
測定温度範囲:40℃~280℃
昇温速度:2℃/分
85℃85%の高温高湿槽にて24時間放置後の重量増加%で評価
得られた試験片の一部をサイクルミルにより粉砕し、粉状とし、篩にかけ100μmメッシュ通過、75μmメッシュオンの粒径にそろえ、5-10mgのサンプルをとり、TG-DTAで熱重量減少温度を確認した。5%の重量減少温度を指標とした。
TG-DTAにて測定(Td5)
測定サンプル :粉状 (100μmメッシュ通過、 75μmメッシュオン) 5-10mg
測定条件 : 昇温速度 10℃/ min Air flow 200ml/min5%重量減少温度を測定した。
なお、本出願は、2013年9月12日付で出願された日本国特許出願(特願2013-189035)に基づいており、その全体が引用により援用される。また、ここに引用されるすべての参照は全体として取り込まれる。
Claims (8)
- フェノール樹脂(A)とビフェノール(B)の比が、(A)の水酸基当量1モル当量に対し、(B)の水酸基が0.08~0.33倍モルである請求項1に記載のエポキシ樹脂混合物。
- 軟化点が80~100℃である請求項1または2に記載のエポキシ樹脂混合物。
- 150℃におけるICI溶融粘度(コーンプレート法)が0.05~0.30Pa・sである請求項1~3のいずれか一項に記載のエポキシ樹脂混合物。
- 請求項1~4のいずれか一項に記載のエポキシ樹脂混合物と硬化剤を含有する硬化性樹脂組成物。
- 請求項1~4のいずれか一項に記載のエポキシ樹脂混合物と硬化触媒を含有するエポキシ樹脂組成物。
- 請求項5又は6に記載の硬化性樹脂組成物を硬化した硬化物。
- 半導体チップを請求項5又は6に記載の硬化性樹脂組成物を用いて封止して得られる半導体装置。
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CN107083016A (zh) * | 2017-05-26 | 2017-08-22 | 山东宇世巨化工有限公司 | 一种4,4’‑联苯二酚改性酚醛树脂材料 |
JP2019011481A (ja) * | 2018-10-30 | 2019-01-24 | 味の素株式会社 | 樹脂組成物 |
JP2019011396A (ja) * | 2017-06-29 | 2019-01-24 | Dic株式会社 | エポキシ樹脂の製造方法、エポキシ樹脂、エポキシ樹脂組成物及びその硬化物 |
CN115536813A (zh) * | 2022-09-20 | 2022-12-30 | 江苏扬农锦湖化工有限公司 | 一种高环氧值苯酚-亚联苯型环氧树脂的制备方法 |
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TWI618744B (zh) | 2018-03-21 |
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