WO2015037584A1 - Epoxy resin mixture, epoxy resin composition, cured product and semiconductor device - Google Patents
Epoxy resin mixture, epoxy resin composition, cured product and semiconductor device Download PDFInfo
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- WO2015037584A1 WO2015037584A1 PCT/JP2014/073807 JP2014073807W WO2015037584A1 WO 2015037584 A1 WO2015037584 A1 WO 2015037584A1 JP 2014073807 W JP2014073807 W JP 2014073807W WO 2015037584 A1 WO2015037584 A1 WO 2015037584A1
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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
- C08G59/22—Di-epoxy compounds
- C08G59/26—Di-epoxy compounds heterocyclic
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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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- 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.
- the heat resistance of the cured product is the heat resistance of the cured product.
- the heat resistance of cured epoxy resins has been regarded as important, but as described above, generally, as the heat resistance is increased, it becomes brittle and mechanical strength is deteriorated. Problems such as increase in viscosity, increase in elastic modulus at high temperature (of the cured product) occur at the same time, and it is difficult to satisfy all the characteristics. Therefore, it has been desired to develop an epoxy resin that can achieve both the heat resistance of the cured product and the characteristics contrary to the heat resistance.
- 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.
- G represents a glycidyl group
- R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
- the epoxy resin mixture according to item (1) which has a softening point of 80 to 100 ° C. (3) 3.
- An epoxy resin composition comprising the epoxy resin mixture according to any one of (1) to (3) and a curing agent.
- An epoxy resin composition comprising the epoxy resin mixture according to any one of (1) to (3) and a curing catalyst.
- the present invention relates to a semiconductor device obtained by sealing a semiconductor chip using the epoxy resin composition described in the above item (4) or (5).
- the epoxy resin mixture of the present invention has a low viscosity, and the cured product has excellent heat resistance, water absorption characteristics and flame retardancy. Therefore, insulating materials for electrical and electronic parts and laminated boards (printed wiring boards, build-up boards, etc.) ) And CFRP and other composite materials, adhesives, paints and the like.
- FIG. 38 shows a 96 Pin QFP lead frame used in Example 22. It is a figure which shows the test piece for test evaluation of the solder crack resistance produced and used in Example 22.
- FIG. 38 shows a 96 Pin QFP lead frame used in Example 22. It is a figure which shows the test piece for test evaluation of the solder crack resistance produced and used in Example 22.
- the epoxy resin mixture of the present invention relates to an epoxy resin mixture containing a compound having a phenolphthalein skeleton derivative structure.
- the basic skeleton of the compound represented by the formula (1) of the present invention is disclosed in British Patent No. 1158606 (Patent Document 1).
- epoxy equivalents per kg is 3.4 (294 g / eq.
- hue is Gardner 8 (40% in methyl glycol)
- softening point is 66 ° C. (kolfer heater)
- An epoxy resin having a phenolphthalein skeleton derivative structure having a chlorine content of 2.2% is disclosed.
- cured physical properties with DDS diaminodiphenyl sulfone
- the epoxy resin described in Patent Document 1 has a very large amount of chlorine, is unsuitable for use in electronic materials, and is very colored, so it is difficult to use in applications that require color. It is suggested that there is.
- the epoxy equivalent was 294 g / eq. Is larger than the theoretical value (252.7 g / eq.), And the large amount of chlorine suggests that the epoxy contains many epihalohydrin structures that remain without ring closure. Nevertheless, if such an epoxy ring has not been completed, crosslinking did not proceed well, and curing with a phenol resin, anionic polymerization with a basic catalyst such as imidazole, and cationic polymerization with an onium salt were performed.
- the present invention is an epoxy resin mixture containing 60 to 75% (gel permeation chromatography area%) of a compound represented by the following formula (1) and 5 to 30% (same as above) of an epoxidized biphenol.
- G represents a glycidyl group
- R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
- the content of the compound represented by the formula (1) exceeds 75%, the crystallinity may be increased or the toughness may be decreased.
- the content of the compound represented by the formula (1) is less than 60%, the epoxy ring is not completely closed, and many compounds having no functional group are contained.
- many of these compounds that could not be ring-closed often contain chlorine, and as an electronic material application, there is concern about the release of chlorine ions under high-temperature and high-humidity conditions and the resulting corrosion of wiring. Absent. Most preferred for R is a hydrogen atom.
- Examples of the alkyl group having 1 to 6 carbon atoms represented by R include alkyl groups having a linear, branched or cyclic structure such as methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Can be mentioned.
- R is preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
- Examples of the alkoxy group having 1 to 6 carbon atoms represented by R include an alkoxy group having a linear, branched or cyclic structure such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group.
- R is preferably a methoxy group, an ethoxy group, or a propoxy group, and particularly preferably a methoxy group.
- the content of the epoxidized biphenol in the epoxy resin mixture of the present invention is particularly preferably 5 to 25%.
- the epoxy equivalent of the epoxy resin mixture of the present invention is usually 1.01 to 1.13 times, preferably 1.02 to 1.10 times the theoretical epoxy equivalent of the phenol skeleton as a raw material.
- the ratio is less than 1.01, the epoxy synthesis and purification may be very expensive.
- the ratio is more than 1.13, the problem may be caused by the amount of chlorine as described above.
- the total chlorine contained in the epoxy resin of the present invention is preferably 5000 ppm or less, more preferably 3000 ppm or less, and particularly preferably 2000 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.
- the theoretical epoxy equivalent indicates an epoxy equivalent calculated when the phenolic hydroxyl group of the phenol compound as a raw material is glycidylated without excess or deficiency.
- the specific epoxy equivalent value is preferably 200.0 g / eq. To 280.0 g / eq., And more preferably 220.0 g / eq. To 250.0 g / eq.
- all R are hydrogen atoms. Particularly preferred.
- 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 130 ° C, more preferably from 80 to 120 ° C.
- the temperature is preferably 80 to 120 ° C, more preferably 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, if the softening point is too high, problems such as poor handling may occur during kneading with other resins.
- the melt viscosity is 0.08 to 0.35 Pa ⁇ s (ICI melt viscosity 150 ° C. cone plate method), more preferably 0.08 to 0.3 Pa ⁇ s, and particularly preferably 0.08 to 0.25 Pa ⁇ s. It is. When mixing and using inorganic materials (filler etc.), problems, such as poor fluidity, arise.
- the compound represented by the formula (1) and the epoxidized product of biphenol may be mixed at a predetermined ratio, but the phenol compound (DPPI) represented by the following formula (4) It may be synthesized by the reaction of a mixture of bisphenol and biphenol with epihalohydrin.
- the phenol compound (DPPI) represented by the formula (4) is synthesized from a phenolphthalein derivative and an aminobenzene derivative (for example, Japanese Patent Application Laid-Open No. 2005-290378).
- phenolphthalein derivatives can be synthesized with phthalic acid and various corresponding phenols. If the phenols used are phenol, phenolphthalein is obtained, and if cresols, cresolphthalein is obtained. .
- examples of the various phenols include phenol, cresol, ethylphenol, propylphenol, xylenol, and methylbutylphenol. In the present invention, the use of phenolphthalein is preferred.
- the structure represented by following formula (2) is mentioned, for example.
- aminobenzene derivatives include those represented by the following formula (3).
- the amount of residual phenolphthalein derivative in the phenol compound (DPPI) is preferably 2% or less, more preferably 1% or less, still more preferably 0.5% or less, and particularly preferably 0.1% or less (high performance liquid chromatography). Measured graphically). When this phenolphthalein derivative remains, coloring tends to increase during the reaction. The same applies to aminobenzene derivatives. Further, the remaining iron content (ICP emission analysis) is one of the factors caused by coloring. The residual iron content is preferably 100 ppm or less, more preferably 50 ppm or less, and particularly preferably 10 ppm or less.
- the phenol compound (DPPI) as the main body is desired to have a purity of 95% or more, more preferably 98% or more.
- the amount of residual phenolphthalein derivative can be adjusted by purification of DPPI (washing, recrystallization, reprecipitation, etc.).
- the DPPI used in the present invention preferably has a softening point of 100 ° C. or higher. When the softening point is 100 ° C. or higher, it contributes to the heat resistance of the resulting epoxy resin mixture.
- the DPPI used in the present invention preferably has a melting point, and the melting point is preferably 200 ° C. or higher.
- the biphenol used in the present invention has a structure represented by the following formula (5).
- R 1 s a plurality of R 1 s exist independently, each representing a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and k represents an integer of 1 to 4)
- Examples of the biphenol having the structure represented by the formula (5) include 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 method for obtaining the epoxy resin mixture of the present invention by reaction of a mixture of a phenol compound (DPPI) and biphenol and epihalohydrin will be described.
- a mixture of a phenol compound (DPPI) and biphenol is referred to as a phenol mixture used in the present invention.
- the phenol mixture used in the present invention may be a mixture of a phenol compound (DPPI) and a biphenol, but the mixing ratio of the phenol compound (DPPI) and the biphenol is a molar ratio, and the phenol compound (DPPI): biphenol is 5: It is preferably 5 to 9: 1, more preferably 6: 4 to 8: 2. Further, in terms of weight ratio, the phenol compound (DPPI): biphenol is preferably 6: 4 to 9: 1, and more preferably 7: 3 to 8.6: 1.4.
- 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 with respect to 1 mol of the hydroxyl group of the phenol mixture used in the present invention.
- the amount is preferably 4.0 to 6.0 mol. If the amount is less than 3.0 mol, the epoxy equivalent may increase, and the workability of the resulting epoxy resin may deteriorate. If it exceeds 15 moles, the amount of solvent becomes large, which is not preferable in terms of waste and productivity.
- 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 from 0.90 to 1.5 mol, preferably from 0.95 to 1.25 mol, more preferably from 1 mol of the hydroxyl group of the phenol mixture used in the present invention as a raw material. Is 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.
- a cured product of the epoxy resin having excellent electrical reliability can be obtained, and therefore a nonpolar proton solvent can be preferably 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 cannot proceed, and if the reaction time is long, a by-product may be formed. 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 mixture used in the present invention used for epoxidation. It is.
- 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 an amorphous resinous shape or a semicrystalline resinous shape.
- a semi-crystalline resin is preferable because it has low viscosity and high mechanical strength and adhesion.
- the compound represented by the formula (1) and bisglycidyloxybiphenyl (however, when the aromatic ring has a substituent, the number of substituents is 4 or less and the number of carbons is 4 or less.
- the reaction under the preferable conditions as described above there is also a structure in which the phenol resin structure represented by the above formula (1) and the biphenol structure are connected by epihalohydrin. Therefore, by epoxidizing the phenol mixture at the same time, the above structure is formed and the viscosity tends to be relatively low, which is preferable in improving the fluidity of the present invention.
- 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 composition of the present invention contains the epoxy resin mixture of the present invention and a curing catalyst (curing accelerator) 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
- curing catalyst examples include amine compounds such as triethylamine, tripropylamine, and tributylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, and imidazole.
- Triazole tetrazole, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2 -Methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2'-methylimidazole (1 ')) Ethyl-s Triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl, 4-methylimidazole (1 ′)) ethyl -S-
- heterocyclic compounds and these heterocyclic compounds and phthalic acid, isophthalic acid, terephthalic acid, Mellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, salts with polyvalent carboxylic acids such as succinic acid, amides such as dicyandiamide, 1,8-diaza-bicyclo (5.4.0) undecene-7, etc.
- Diaza compounds and salts thereof such as tetraphenylborate and phenol novolak, salts with the above polyvalent carboxylic acids or phosphinic acids, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide , Trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide Ammonium salts such as droxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctylmethylammonium acetate, triphenylphosphine, tri (toluyl) pho
- 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 is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of 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 agent, 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 agent it is preferable to add a coupling material having an epoxy group or a coupling agent having a thiol.
- 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.
- the epoxy resin composition of the present invention can be used as a film-type sealing composition.
- the curable resin composition of the present invention is coated on the release film with the varnish, the solvent is removed under heating, and a B-stage adhesive is formed. Get.
- This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like, and a batch film sealing of an optical semiconductor.
- 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-602x2, 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 1 A phenol compound (DPPI1) (compound in which the substituents R are all hydrogen atoms in the above formula (1) SABIC BPPPP purity 99% or more Residual phenolphthalein 200 ppm, iron content ⁇ 5 ppm, melting point 290 ° C.) 137.7 parts, biphenol 27.9 parts, epichlorohydrin 555 parts, dimethyl sulfoxide 139 parts were added, and the water bath was heated to 50 ° C. When the internal temperature exceeded 45 ° C., 44 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by further reaction at 45 ° C. for 2 hours and at 70 ° C. for 1 hour.
- DPPI1 compound in which the substituents R are all hydrogen atoms in the above formula (1)
- an epoxy resin mixture (EP1) was obtained.
- the epoxy equivalent of the obtained epoxy resin mixture was 226 g / eq.
- the softening point was 92 ° C.
- the ICI melt viscosity was 0.15 Pa ⁇ s (150 ° C.)
- the total chlorine amount was 505 ppm
- the hydrolyzable chlorine was 480 ppm
- the chlorine ions were 0.1 ppm
- the sodium ions were 0.1 ppm.
- the compound of the formula (1) was 72 area% (GPC)
- the epoxidized biphenol was 16 area% (GPC).
- bonded were included.
- Example 2 and Comparative Examples 1 and 2 The epoxy resin mixture (EP1) of the present invention obtained in Example 1 and a comparative epoxy resin (EP2; phenol-biphenylene aralkyl type epoxy resin, manufactured by Nippon Kayaku Co., Ltd.
- NC-3000, EP3; trisphenolmethane type epoxy resin Epoxy resin and curing agent (phenol novolak (M-1 made by Meiwa Kasei Kogyo Co., Ltd.) or phenol aralkyl resin (Mitsui Chemicals Co., Ltd., Millex XLC-3L) )
- a curing catalyst curing accelerator, triphenylphosphine (TPP manufactured by Hokuko Chemical Co., Ltd.)
- a filler fused silica, manufactured by Ashimori MSR-2122, if necessary
- This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine.
- the tableted epoxy resin composition of the present invention and the comparative composition were transfer molded (175 ° C. ⁇ 60 seconds), and after demolding, cured under the conditions of 160 ° C. ⁇ 2 hours + 180 ° C. ⁇ 6 hours, a test piece for evaluation Got.
- cured material was measured in the following ways. Also, depending on the evaluation items of the physical properties of the cured product, the type of curing agent to be 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 cured product of Comparative Example 1 is excellent in flame retardancy but has low heat resistance.
- the heat resistance is high but there is no flame retardancy, and the result is that the flame retardant test completely burns, whereas the cured product of the epoxy resin composition of the present invention is high. Both heat resistance and flame retardancy can be achieved. It can also be seen that the shrinkage during curing is good and the dimensional stability is excellent.
- Example 3 and Comparative Example 3 Using the epoxy resin mixture (EP1) of the present invention obtained in Example 1 and the comparative epoxy resin (EP4) obtained in Synthesis Example 1, an epoxy resin and a curing agent (phenol novolak (Maywa Kasei Kogyo Co., Ltd.) ) H-1) or phenol aralkyl resin (Mirex XLC-3L manufactured by Mitsui Chemicals, Inc.)) is blended in equal equivalents, and a curing catalyst (curing accelerator, triphenylphosphine (TPP manufactured by Hokuko Chemical Co., Ltd.)) And a filler (fused silica, made by Kashimori MSR-2122, the filler amount% in the table is the ratio to the total epoxy resin), and mixed and kneaded uniformly using a mixing roll, and the epoxy resin composition for sealing Got.
- a curing agent phenol novolak (Maywa Kasei Kogyo Co., Ltd.) ) H-1) or phenol aralky
- This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine.
- the tableted epoxy resin composition of the present invention and the comparative composition were transfer molded (175 ° C. ⁇ 60 seconds), and after demolding, cured under the conditions of 160 ° C. ⁇ 2 hours + 180 ° C. ⁇ 6 hours, a test piece for evaluation Got.
- cured material was measured in the following ways.
- the type of curing agent to be used is as shown in Table 2 below, and the amount of curing accelerator used is the weight of the epoxy resin in the sample used for the evaluation of heat resistance, mechanical strength and adhesion. 1% relative to the weight of the epoxy resin in the sample used for evaluation of flame retardancy.
- the epoxy resin composition of the present invention has a very low melt viscosity, and the cured product maintains heat resistance derived from the structure of the above formula (1). Furthermore, since the after flame time is shortened in flame retardancy, it is clear that the flame retardancy is improved, and the bending strength and peel strength are better than those of the cured epoxy resin composition.
- Synthesis example 2 In a flask equipped with a stirrer, a reflux condenser, and a stirrer, a phenol compound (DPPI1) (a compound in which the substituents R are all hydrogen atoms in the above formula (1) SABIC PPPBP purity 99% or more residual phenolphthalein 200 ppm, iron ⁇ 5 ppm ) 256 parts, epichlorohydrin 971 parts, benzyltrimethylammonium chloride 3 parts were added, and the temperature of the water bath was raised to 70 ° C. To this, 100 parts of a 49% aqueous sodium hydroxide solution was added dropwise over 90 minutes, followed by further reaction at 70 ° C. for 4 hours.
- DPPI1 a compound in which the substituents R are all hydrogen atoms in the above formula (1)
- an epoxy resin (EP5) having a structure represented by the above formula (1) was obtained by distilling off excess epichlorohydrin and the like from the oil layer under reduced pressure at 140 ° C. using a rotary evaporator. 290 parts were obtained.
- the epoxy resin having the structure represented by the formula (1) obtained has an epoxy equivalent of 297 g / eq.
- the softening point was 95 ° C.
- the ICI melt viscosity was 0.70 Pa ⁇ s (150 ° C.)
- the total chlorine content was 10450 ppm
- the hydrolyzable chlorine was 9700 ppm.
- Example 4 and Comparative Example 4 Using the epoxy resin mixture (EP1) of the present invention obtained in Example 1 and the comparative epoxy resin (EP5) obtained in Synthesis Example 2, an epoxy resin and a curing agent (phenol novolak (Maywa Kasei Kogyo Co., Ltd.) H-1)) is blended in an equivalent amount, and 1% of triphenylphosphine (TPP manufactured by Hokuko Chemical Co., Ltd.) is added as a curing catalyst (curing accelerator) based on the weight of the epoxy resin, and a mixing roll is used. Were mixed and kneaded uniformly to obtain an epoxy resin composition for sealing. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine.
- phenol novolak Maywa Kasei Kogyo Co., Ltd.
- TPP triphenylphosphine
- the tableted epoxy 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.
- cured material was measured in the following ways.
- TMA measurement conditions > ⁇ Thermo-mechanical measuring device, TA-instruments, Q400EM ⁇ Measurement temperature range: 40 °C ⁇ 280 °C ⁇ Temperature increase rate: 2 °C / min
- the viscosity of the epoxy resin composition of the present invention was significantly lower than that of conventionally known epoxy resin compositions, and it was confirmed that the cured product was excellent in heat resistance.
- Example 5 100 parts of biphenol, 971 parts of epichlorohydrin and 97 parts of methanol were added to a flask equipped with a stirrer, a reflux condenser, and a stirrer, and the temperature of the water bath was raised to 70 ° C. After 41 parts of flaky sodium hydroxide was added in portions over 90 minutes, the reaction was further carried out at 70 ° C. for 1 hour. After the reaction, a mixture of the precipitated epoxy resin and sodium chloride was filtered off from the solvents. By washing 5 times with 200 parts of warm water of 70 ° C. and drying, 121 parts of biphenol type epoxy resin (EP7) represented by the above formula (5) was obtained.
- EP7 biphenol type epoxy resin
- the obtained epoxy resin (EP7) and the epoxy resin (EP4) obtained in Synthesis Example 1 were added to 300 parts of tetrahydrofuran at a ratio of 20 parts and 80 parts, respectively, and tetrahydrofuran was added as it was at 180 ° C. under reduced pressure using a rotary evaporator.
- the obtained epoxy resin mixture (EP8) was semi-crystalline and its epoxy equivalent was 247 g / eq.
- the softening point was 95 ° C.
- the ICI melt viscosity was 0.18 Pa ⁇ s (150 ° C.)
- the total chlorine content was 1820 ppm
- the hydrolyzable chlorine was 1670 ppm.
- Examples 6 and 7 Using the epoxy resin mixture (EP1) obtained in Example 1 and the epoxy resin (EP8) obtained in Example 5, an epoxy resin and a curing agent (phenol aralkyl resin (KAYAHARD manufactured by Nippon Kayaku Co., Ltd.) GPH-65)) at equal equivalents, curing catalyst (curing accelerator, triphenylphosphine (TPP manufactured by Hokuko Chemical Co., Ltd. 2% added to the weight of the epoxy resin) and filler (melting) as required Silica MSM-2122, filler amount% in the table is a ratio to the whole epoxy resin composition), and mixed and kneaded uniformly using a mixing roll to obtain an epoxy resin composition for sealing.
- phenol aralkyl resin phenol aralkyl resin (KAYAHARD manufactured by Nippon Kayaku Co., Ltd.) GPH-65
- curing catalyst curing accelerator, triphenylphosphine (TPP manufactured by Hokuko Chemical Co., Ltd. 2% added to the weight of the
- This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine.
- the tableted epoxy 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.
- cured material was measured in the following ways.
- TMA measurement conditions > ⁇ Thermo-mechanical measuring device, 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 contact with 5 samples
- the cured product of the epoxy resin composition of the present invention has improved flame retardancy and good heat resistance.
- the epoxy resin mixture of the present invention is excellent in fluidity, and that the cured product is particularly excellent in flame retardancy and heat resistance, and a semiconductor encapsulant that requires high functionality, It can be seen that it is useful for thin film substrate materials (including interlayer insulating films) that require high filler filling.
- Example 8 A 1-L four-necked flask equipped with a stirrer, a reflux condenser, and a stirrer is charged with a phenol compound (based on the method described in British Patent 1,158,606 example7, purity 99% or more, residual phenolphthalein 14 ppm, iron content ⁇ 5 ppm, melting point 289-290 ° C.) 137.7 parts, 27.9 parts of biphenol, 470 parts of epichlorohydrin and 120 parts of dimethyl sulfoxide were added, and the temperature of the water bath was raised to 50 ° C. When the internal temperature exceeded 45 ° C., 44 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by further reaction at 45 ° C.
- a phenol compound based on the method described in British Patent 1,158,606 example7, purity 99% or more, residual phenolphthalein 14 ppm, iron content ⁇ 5 ppm, melting point 289-290 ° C.
- bonded were included.
- Example 9 A 1-L four-necked flask equipped with a stirrer, a reflux condenser, and a stirrer is charged with a phenol compound (based on the method described in British Patent 1,158,606 example7, purity 99% or more, residual phenolphthalein 14 ppm, iron content ⁇ 5 ppm, melting point 289-290 ° C.) 125.7 parts, biphenol 33.6 parts, epichlorohydrin 463 parts, dimethyl sulfoxide 116 parts were added, and the temperature of the water bath was raised to 50 ° C. When the internal temperature exceeded 45 ° C., 44 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by further reaction at 45 ° C. for 2 hours and at 70 ° C.
- a phenol compound based on the method described in British Patent 1,158,606 example7, purity 99% or more, residual phenolphthalein 14 ppm, iron content ⁇ 5 ppm, melting point 289-290 ° C.
- bonded were included.
- Example 10 A 1-L four-necked flask equipped with a stirrer, a reflux condenser, and a stirrer is charged with a phenol compound (based on the method described in British Patent 1,158,606 example7, purity 99% or more, residual phenolphthalein 14 ppm, iron content ⁇ 5 ppm, melting point 289-290 ° C.) 151.5 parts, biphenol 21.4 parts, epichlorohydrin 463 parts, dimethyl sulfoxide 116 parts were added, and the temperature of the water bath was raised to 50 ° C. When the internal temperature exceeded 45 ° C., 44 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by further reaction at 45 ° C. for 2 hours and at 70 ° C.
- a phenol compound based on the method described in British Patent 1,158,606 example7, purity 99% or more, residual phenolphthalein 14 ppm, iron content ⁇ 5 ppm, melting point 289-290 ° C.
- bonded were included.
- Epoxy resin mixture (EP13, 14, 15) obtained in Examples 8 to 10, comparative epoxy resin EP10 to 12 (EP10: Nippon Kayaku Orthocresol novolak epoxy resin EOCN-1020-70, EP11: Mitsubishi Chemical Use biphenyl type epoxy resin YX-4000H, EP12: Nippon Kayaku biphenyl aralkyl epoxy resin NC-3000), and mix epoxy resin and curing agent (phenol novolac: H-1 made by Meiwa Kasei Kogyo Co.) Then, 1% of triphenylphosphine as a curing accelerator was added to the weight of the epoxy resin, and the mixture was uniformly mixed and kneaded using a mixing roll to obtain an epoxy resin composition for sealing.
- This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine.
- the tableted epoxy 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.
- cured material was measured in the following ways.
- Dynamic viscoelasticity measuring instrument TA-instruments, DMA-2980 Measurement temperature range: -30 to 280 ° C Temperature rate: 2 ° C./min Test piece size: 5 mm ⁇ 50 mm cut out (thickness is about 800 ⁇ m) Tg: The peak point of Tan- ⁇ was defined as Tg.
- the cured product of the epoxy resin composition of the present invention was measured by the same DMA even though it had higher heat resistance than the cured product of the conventionally used epoxy resin composition. It can be seen that the elastic modulus at 250 ° C. is greatly reduced.
- Examples 14 to 16 and Comparative Example 11 In Examples 11 to 13 and Comparative Example 10, the same operation was performed except that the curing agent was changed to biphenyl type phenol aralkyl resin (KAYAHARD GPH-65 manufactured by Nippon Kayaku Co., Ltd.).
- Example 17 and Comparative Example 12 Using the epoxy resin mixture (EP13) obtained in Example 8 and a comparative epoxy resin (EP16; trisphenolmethane type epoxy resin, Nippon Kayaku Co., Ltd. EPPN-501H), each epoxy resin and curing agent (Biphenyl type phenol aralkyl resin: softening point 73 ° C., Japanese Patent Laid-Open No. 2003-113225, synthesized using the method described in Example 1, hydroxyl equivalent 207 g / eq.) Is blended in an equivalent amount, and tri-p is used as a curing accelerator.
- EP16 trisphenolmethane type epoxy resin
- EPPN-501H a comparative epoxy resin
- each epoxy resin and curing agent (Biphenyl type phenol aralkyl resin: softening point 73 ° C., Japanese Patent Laid-Open No. 2003-113225, synthesized using the method described in Example 1, hydroxyl equivalent 207 g / eq.) I
- 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
- ⁇ DMA measurement conditions Dynamic viscoelasticity measuring device: manufactured by TA-instruments, DMA-2980 Measurement temperature range: -30 ° C to 280 ° C Temperature rate: 2 ° C./min Test piece size: 5 mm ⁇ 50 mm cut out (thickness is about 800 ⁇ m).
- Analysis condition Tg Tan ⁇ peak point (tan ⁇ MAX) in DMA measurement was defined as Tg.
- ⁇ 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.
- Table 7 shows that the cured product of the epoxy resin composition of the present invention has not only high heat resistance but also high thermal decomposition characteristics.
- Example 18 A 1-L four-necked flask equipped with a stirrer, a reflux condenser, and a stirrer is charged with a phenol compound (based on the method described in British Patent 1,158,606 example7, purity 99% or more, residual phenolphthalein 14 ppm, iron content ⁇ 5 ppm, melting point 289-290 ° C.) 138 parts, biphenol 28 parts, epichlorohydrin 463 parts, dimethyl sulfoxide 115 parts were added, and the temperature of the water bath was raised to 50 ° C. When the internal temperature exceeded 45 ° C., 44 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by further reaction at 45 ° C. for 2 hours and at 70 ° C.
- a phenol compound based on the method described in British Patent 1,158,606 example7, purity 99% or more, residual phenolphthalein 14 ppm, iron content ⁇ 5 ppm, melting point 289-290 ° C.
- the epoxy equivalent of the obtained epoxy resin is 241 g / eq.
- the softening point was 85.3 ° C.
- the ICI melt viscosity was 0.15 Pa ⁇ s (150 ° C.)
- the total chlorine content was 460 ppm
- the hydrolyzable chlorine was 394 ppm
- the chlorine ions were 0.6 ppm
- the sodium ions were 0.7 ppm.
- the structure of the formula (1) was 69.5 area% (GPC)
- the epoxidized biphenol was 15.0 area% (GPC).
- bonded were included.
- Example 19 A 1-L four-necked flask equipped with a stirrer, a reflux condenser, and a stirrer is charged with a phenol compound (based on the method described in British Patent 1,158,606 example7, purity 99% or more, residual phenolphthalein 14 ppm, iron content ⁇ 5 ppm, melting point 289-290 ° C.) 126 parts, biphenol 34 parts, epichlorohydrin 463 parts, dimethyl sulfoxide 116 parts were added, and the temperature of the water bath was raised to 50 ° C. When the internal temperature exceeded 45 ° C., 43 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 45 ° C.
- a phenol compound based on the method described in British Patent 1,158,606 example7, purity 99% or more, residual phenolphthalein 14 ppm, iron content ⁇ 5 ppm, melting point 289-290 ° C.
- Comparative Example 13 A 1-L four-necked flask equipped with a stirrer, a reflux condenser, and a stirrer is charged with a phenol compound (based on the method described in British Patent 1,158,606 example7, purity 99% or more, residual phenolphthalein 14 ppm, iron content ⁇ 5 ppm, melting point 289-290 ° C.) 102 parts, biphenol 45 parts, epichlorohydrin 462 parts, dimethyl sulfoxide 116 parts were added, and the temperature of the water bath was raised to 50 ° C. When the internal temperature exceeded 45 ° C., 44 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by further reaction at 45 ° C.
- a phenol compound based on the method described in British Patent 1,158,606 example7, purity 99% or more, residual phenolphthalein 14 ppm, iron content ⁇ 5 ppm, melting point 289-290 ° C.
- the other structures mainly include compounds in which the compound of the formula (1), biphenols, and a compound in which the compound of the formula (1) and biphenol are mixed and bonded.
- Examples 20 to 21 and Comparative Example 14 Using the epoxy resin mixture (EP17, EP18, EP19) obtained in Examples 18 and 19 and Comparative Example 13, biphenyl type phenol aralkyl resin (KAYAHARD GPH-65 manufactured by Nippon Kayaku Co., Ltd.) is blended in an equivalent equivalent amount as a curing agent. Then, a curing accelerator (triphenylphosphine manufactured by Hokuko Chemical Co., Ltd.) was added at 1% with respect to the weight of the epoxy resin, and uniformly mixed and kneaded using a mixing roll to obtain an epoxy resin composition. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy resin composition was transfer-molded (175 ° C.
- 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 ⁇ curing shrinkage> Compliant with JISK-6911 (mold shrinkage)
- Example 22 The epoxy resin composition of the present invention having the composition of Example 6 was tested for solder crack resistance.
- 96PinQFP chip size: 7 ⁇ 7 ⁇ thickness 0.1 mm, package size: 14 ⁇ 14 ⁇ thickness 1.35 mm
- lead frame surface is sufficiently wiped with acetone before use, as shown in FIG. (Use a soiled product)
- Use a lead frame for solder crack resistance evaluation set the lead frame in a transfer mold and transfer the tableted epoxy resin composition in the same way as above (175 ° C x 60 seconds)
- three samples were obtained for test evaluation for curing and solder crack resistance under conditions of 160 ° C. ⁇ 2 hours + 180 ° C. ⁇ 6 hours (FIG. 2).
- the obtained three test pieces were allowed to stand for 5 hours in a thermostat set to a relative humidity of 60 ° C./85% RH for moisture absorption, and after this moisture absorption, a solder reflow test at 280 ° C. for 10 seconds was performed. The generation of cracks was visually confirmed for the package cracks caused by the thermal shock at this time, but no cracks were found in any of the samples.
- Examples 23 and 24 The epoxy resin mixture of the present invention (EP18, 19) obtained in Examples 18 and 19 and a curing agent (phenol novolak (H-1 manufactured by Meiwa Kasei Kogyo Co., Ltd.)) were blended in equal equivalents, and a curing catalyst (curing) Add 1% of triphenylphosphine (TPP manufactured by Hokuko Chemical Co., Ltd.) as the accelerator) to the weight of the epoxy resin, and mix and knead uniformly using a mixing roll to obtain an epoxy resin composition for sealing. Obtained.
- This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy 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. Table 9 shows the evaluation results.
- TMA measurement conditions Heat resistance and dimensional stability (linear expansion rate) Thermo-mechanical measuring device manufactured by TA-instruments, Q400EM Measurement temperature range: 40 ° C-280 ° C Temperature increase rate: 2 ° C / min
- ⁇ DMA measurement conditions Dynamic viscoelasticity measuring device: manufactured by TA-instruments, DMA-2980 Measurement temperature range: -30 ° C to 280 ° C Temperature rate: 2 ° C./min Test piece size: 5 mm ⁇ 50 mm cut out (thickness is about 800 ⁇ m).
- Analysis condition Tg Tan ⁇ peak point (tan ⁇ MAX) in DMA measurement was defined as Tg.
- the epoxy resin of the present invention gives a cured product having high heat resistance, high mechanical properties, low linear expansion, and high moisture and water resistance properties and excellent dielectric properties for the level of heat resistance. .
- 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、近年、反りや、はんだリフロー等の半田ショックに対する耐性が非常に強く求められている。特にチップが薄型化していく中、鉛フリー半田の温度(260℃)に耐えられることが求められており、この半田ショックの応力を回避するために高温での弾性率が低く応力を逃すことのできる封止材が求められている。また反りに関してはその抑制のため、高い耐熱性と高温での低弾性率が求められている。この低弾性率と耐熱性は難燃性と同様、相反する特性であり、耐熱性を上げようと架橋密度をあげてしまうと高温での弾性率が高くなり、リフロー時の応力を逃しきれず、チップに負荷がかかる、またパッケージにクラック、反りがでる等の問題が生じる。 However, in recent years, with the development in the electric / electronic field, moisture resistance, adhesion, dielectric properties, low viscosity for high filling of filler (inorganic or organic filler) as well as high purity of resin composition, There is a need for further improvements in various properties such as increased reactivity to shorten the molding cycle. Further, as a structural material, there is a demand for a material that is lightweight and has excellent mechanical properties in applications such as aerospace materials and leisure / sports equipment. Especially in the field of semiconductor encapsulation and substrates (substrate itself or its peripheral materials), as the semiconductor transitions, it becomes increasingly complex with thinning, stacking, systematization, and three-dimensionalization. Required characteristics such as heat resistance and high fluidity are required. In particular, with the expansion of plastic packages to in-vehicle applications, demands for improving heat resistance are becoming more severe. Specifically, heat resistance of 150 ° C. or higher has been required due to an increase in semiconductor driving temperature. In general, the higher the softening point of an epoxy resin, the more the cured product tends to have higher heat resistance. However, on the other hand, since the viscosity tends to increase, it is difficult to use the sealing material. In response to this problem, attempts have been made to provide heat resistance by introducing a naphthalene structure, but there has been a problem that it becomes hard and brittle and the mechanical strength decreases. Moreover, although the polyfunctional epoxy resin is examined, the subject that a flame retardance falls remarkably occurred.
In recent years, resistance to solder shocks such as warping and solder reflow has been extremely demanded. In particular, as the chip becomes thinner, it is required to withstand the temperature of lead-free solder (260 ° C). In order to avoid the stress of this solder shock, the elastic modulus at high temperature is low and the stress is released. There is a need for a sealing material that can be used. Moreover, high heat resistance and low elastic modulus at high temperature are required for suppressing warpage. This low elastic modulus and heat resistance are contradictory properties like flame retardancy, and if the crosslink density is increased in order to increase heat resistance, the elastic modulus at high temperatures will increase, and the stress during reflow cannot be released. This causes problems such as load on the chip and cracks and warpage of the package.
そこで、硬化物の耐熱性及び該耐熱性と相反する特性を両立できるエポキシ樹脂の開発が望まれていた。
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。 One of the properties particularly required for the enhancement of functionality of epoxy resins is the heat resistance of the cured product. Conventionally, the heat resistance of cured epoxy resins has been regarded as important, but as described above, generally, as the heat resistance is increased, it becomes brittle and mechanical strength is deteriorated. Problems such as increase in viscosity, increase in elastic modulus at high temperature (of the cured product) occur at the same time, and it is difficult to satisfy all the characteristics.
Therefore, it has been desired to develop an epoxy resin that can achieve both the heat resistance of the cured product and the characteristics contrary to the heat resistance.
That is, 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.
すなわち本発明は、 As a result of intensive studies in view of the actual situation as described above, the present inventors have completed the present invention.
That is, the present invention
下記式(1)で表される化合物を60~75%(ゲルパーミエーションクロマトグラフィー 面積%)、及び、ビフェノールのエポキシ化物を5~30%(同上)含有するエポキシ樹脂混合物。 (1)
An epoxy resin mixture containing 60 to 75% (gel permeation chromatography area%) of a compound represented by the following formula (1) and 5 to 30% (same as above) of an epoxidized biphenol.
軟化点が80~100℃である前項(1)に記載のエポキシ樹脂混合物。
(3)
150℃におけるICI溶融粘度(コーンプレート法)が0.08~0.35Pa・sである前項(1)又は(2)に記載のエポキシ樹脂混合物。
(4)
前項(1)~(3)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エポキシ樹脂組成物。
(5)
前項(1)~(3)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。
(6)
前項(4)又は(5)に記載のエポキシ樹脂組成物を硬化した硬化物。
(7)
半導体チップを前項(4)又は(5)に記載のエポキシ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。 (2)
The epoxy resin mixture according to item (1), which has a softening point of 80 to 100 ° C.
(3)
3. The epoxy resin mixture according to item (1) or (2), wherein the ICI melt viscosity at 150 ° C. (cone plate method) is 0.08 to 0.35 Pa · s.
(4)
An epoxy resin composition comprising the epoxy resin mixture according to any one of (1) to (3) and a curing agent.
(5)
An epoxy resin composition comprising the epoxy resin mixture according to any one of (1) to (3) and a curing catalyst.
(6)
Hardened | cured material which hardened | cured the epoxy resin composition of the preceding clause (4) or (5).
(7)
The present invention relates to a semiconductor device obtained by sealing a semiconductor chip using the epoxy resin composition described in the above item (4) or (5).
上記データから特許文献1に記載のエポキシ樹脂は塩素量が非常に多く、電子材料用途には不向きであり、また非常に着色があることから色味の必要とされる用途においては使用が困難であることが示唆される。また、エポキシ当量が294g/eq.と理論値(252.7g/eq.)と比較し大きいこと、また塩素量の多さから、エポキシが閉環せずに残留したエピハロヒドリン構造が多く含有されることが示唆され、二官能であるにも関わらず、このようなエポキシ環が完成されていない構造であれば、架橋がうまく進まず、フェノール樹脂による硬化や、イミダゾール等の塩基性触媒によるアニオン重合、オニウム塩等によるカチオン重合を行った際に、その機械特性や吸水性といった特性において課題が生じる場合が多い。特に電子材料用途においてはこれらの硬化だけでなく、アミン系の硬化においても硬化時の塩素の遊離が起因となる配線の腐食等が予想され、電気信頼性を落とす要因となる。
近年特に半導体のチップと基板との接合に銅のワイヤを使用することが多くなってきており、このような電気腐食の課題はいっそう重要となっており、解決すべき課題点となる。
さらに本特許文献1に記載のエポキシ樹脂はその分子内の極性の問題から粘度が高くなる。さらには構造の特性から機械強度や密着性が悪くなるという傾向があり、半導体の封止材等の用途への展開が難しい状態であった。 The epoxy resin mixture of the present invention relates to an epoxy resin mixture containing a compound having a phenolphthalein skeleton derivative structure. The basic skeleton of the compound represented by the formula (1) of the present invention is disclosed in British Patent No. 1158606 (Patent Document 1). According to Patent Document 1, epoxy equivalents per kg is 3.4 (294 g / eq. In terms of current epoxy equivalent), hue is Gardner 8 (40% in methyl glycol), softening point is 66 ° C. (kolfer heater), An epoxy resin having a phenolphthalein skeleton derivative structure having a chlorine content of 2.2% is disclosed. In addition, cured physical properties with DDS (diaminodiphenyl sulfone) are disclosed.
From the above data, the epoxy resin described in Patent Document 1 has a very large amount of chlorine, is unsuitable for use in electronic materials, and is very colored, so it is difficult to use in applications that require color. It is suggested that there is. The epoxy equivalent was 294 g / eq. Is larger than the theoretical value (252.7 g / eq.), And the large amount of chlorine suggests that the epoxy contains many epihalohydrin structures that remain without ring closure. Nevertheless, if such an epoxy ring has not been completed, crosslinking did not proceed well, and curing with a phenol resin, anionic polymerization with a basic catalyst such as imidazole, and cationic polymerization with an onium salt were performed. However, there are many cases where problems arise in the characteristics such as mechanical characteristics and water absorption. Particularly in the case of electronic materials, not only these curings but also amine-based curing is expected to cause corrosion of wiring due to the liberation of chlorine at the time of curing, resulting in a decrease in electrical reliability.
In recent years, in particular, copper wires are increasingly used for bonding a semiconductor chip and a substrate, and such a problem of electrocorrosion is becoming more important and a problem to be solved.
Furthermore, the viscosity of the epoxy resin described in Patent Document 1 increases due to the problem of polarity in the molecule. Furthermore, mechanical strength and adhesion tend to be deteriorated due to the characteristics of the structure, and it has been difficult to develop into applications such as semiconductor sealing materials.
Rで最も好ましいのは水素原子である。Rが示す、上記炭素数1~6のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基等の直鎖、分岐鎖または環状構造を有するアルキル基が挙げられる。ここで、Rはメチル基、エチル基が好ましく、メチル基が特に好ましい。
Rが示す、炭素数1~6のアルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等の直鎖、分岐鎖または環状構造を有するアルコキシ基が挙げられる。ここで、Rはメトキシ基、エトキシ基、プロポキシ基が好ましく、メトキシ基が特に好ましい。 Here, when the content of the compound represented by the formula (1) exceeds 75%, the crystallinity may be increased or the toughness may be decreased. When the content of the compound represented by the formula (1) is less than 60%, the epoxy ring is not completely closed, and many compounds having no functional group are contained. In addition, many of these compounds that could not be ring-closed often contain chlorine, and as an electronic material application, there is concern about the release of chlorine ions under high-temperature and high-humidity conditions and the resulting corrosion of wiring. Absent.
Most preferred for R is a hydrogen atom. Examples of the alkyl group having 1 to 6 carbon atoms represented by R include alkyl groups having a linear, branched or cyclic structure such as methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Can be mentioned. Here, R is preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
Examples of the alkoxy group having 1 to 6 carbon atoms represented by R include an alkoxy group having a linear, branched or cyclic structure such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Here, R is preferably a methoxy group, an ethoxy group, or a propoxy group, and particularly preferably a methoxy group.
また、本発明のエポキシ樹脂に含有されている全塩素としては5000ppm以下が好ましく、より好ましくは3000ppm以下、特に好ましくは2000ppm以下である。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、原料であるフェノール化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。
また、具体的なエポキシ当量の値としては、Rが全て水素原子の場合、210.0g/eq.~280.0g/eq.が好ましく、220.0g/eq.~250.0g/eq.が特に好ましい。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。 The epoxy equivalent of the epoxy resin mixture of the present invention is usually 1.01 to 1.13 times, preferably 1.02 to 1.10 times the theoretical epoxy equivalent of the phenol skeleton as a raw material. When the ratio is less than 1.01, the epoxy synthesis and purification may be very expensive. When the ratio is more than 1.13, the problem may be caused by the amount of chlorine as described above.
Further, the total chlorine contained in the epoxy resin of the present invention is preferably 5000 ppm or less, more preferably 3000 ppm or less, and particularly preferably 2000 ppm or less. The adverse effect of the chlorine amount is the same as described above. In addition, 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.
Here, the theoretical epoxy equivalent indicates an epoxy equivalent calculated when the phenolic hydroxyl group of the phenol compound as a raw material is glycidylated without excess or deficiency.
The specific epoxy equivalent value is preferably 200.0 g / eq. To 280.0 g / eq., And more preferably 220.0 g / eq. To 250.0 g / eq. When all R are hydrogen atoms. Particularly preferred. When 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.
また、溶融粘度は0.08~0.35Pa・s(ICI 溶融粘度 150℃ コーンプレート法)、より好ましくは0.08~0.3Pa・s、特に好ましくは0.08~0.25Pa・sである。無機材料(フィラー等)を混合して用いる場合、流動性が悪い等の課題が生じる。 The epoxy resin mixture of the present invention has a resinous form having a softening point. Here, the softening point is preferably from 70 to 130 ° C, more preferably from 80 to 120 ° C. When all the substituents R are hydrogen atoms, the temperature is preferably 80 to 120 ° C, more preferably 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, if the softening point is too high, problems such as poor handling may occur during kneading with other resins.
The melt viscosity is 0.08 to 0.35 Pa · s (ICI melt viscosity 150 ° C. cone plate method), more preferably 0.08 to 0.3 Pa · s, and particularly preferably 0.08 to 0.25 Pa · s. It is. When mixing and using inorganic materials (filler etc.), problems, such as poor fluidity, arise.
本発明のエポキシ樹脂混合物は、前記式(1)で表される化合物とビフェノールのエポキシ化物を所定の比率で混合しても構わないが、下記式(4)で表されるフェノール化合物(DPPI)とビフェノールの混合物とエピハロヒドリンとの反応によって合成してもよい。 Hereafter, the manufacturing method of the epoxy resin mixture of this invention is described.
In the epoxy resin mixture of the present invention, the compound represented by the formula (1) and the epoxidized product of biphenol may be mixed at a predetermined ratio, but the phenol compound (DPPI) represented by the following formula (4) It may be synthesized by the reaction of a mixture of bisphenol and biphenol with epihalohydrin.
ここで、前記各種フェノール類としては、例えば、フェノール、クレゾール、エチルフェノール、プロピルフェノール、キシレノール、メチルブチルフェノールなどが挙げられる。本発明においてはフェノールフタレインの使用が好ましい。
また、前記合成により得られるフェノールフタレイン誘導体としては、例えば下記式(2)で表される構造が挙げられる。 It is known that phenolphthalein derivatives can be synthesized with phthalic acid and various corresponding phenols. If the phenols used are phenol, phenolphthalein is obtained, and if cresols, cresolphthalein is obtained. .
Here, examples of the various phenols include phenol, cresol, ethylphenol, propylphenol, xylenol, and methylbutylphenol. In the present invention, the use of phenolphthalein is preferred.
Moreover, as a phenolphthalein derivative obtained by the said synthesis | combination, the structure represented by following formula (2) is mentioned, for example.
残存フェノールフタレイン誘導体の量はDPPIの精製(洗浄、再結晶、再沈殿等)によって調整可能である。
また、本発明において使用されるDPPIは、軟化点が100℃以上であることが好ましい。軟化点が100℃以上であることで、生成するエポキシ樹脂混合物の耐熱性に寄与する。特に本発明において使用されるDPPIは融点を有することが好ましく、その融点が200℃以上であることが好ましい。 The amount of residual phenolphthalein derivative in the phenol compound (DPPI) is preferably 2% or less, more preferably 1% or less, still more preferably 0.5% or less, and particularly preferably 0.1% or less (high performance liquid chromatography). Measured graphically). When this phenolphthalein derivative remains, coloring tends to increase during the reaction. The same applies to aminobenzene derivatives. Further, the remaining iron content (ICP emission analysis) is one of the factors caused by coloring. The residual iron content is preferably 100 ppm or less, more preferably 50 ppm or less, and particularly preferably 10 ppm or less. The phenol compound (DPPI) as the main body is desired to have a purity of 95% or more, more preferably 98% or more.
The amount of residual phenolphthalein derivative can be adjusted by purification of DPPI (washing, recrystallization, reprecipitation, etc.).
In addition, the DPPI used in the present invention preferably has a softening point of 100 ° C. or higher. When the softening point is 100 ° C. or higher, it contributes to the heat resistance of the resulting epoxy resin mixture. In particular, the DPPI used in the present invention preferably has a melting point, and the melting point is preferably 200 ° C. or higher.
前記式(5)で表される構造のビフェノールは、例えば2,2’体、2,4’体、4,4’体等が存在するが、中でも4,4’体のビフェノールが好ましい。
また、純度は95%以上のものが好適に使用できる。 (In the formula (5), a plurality of R 1 s exist independently, each representing a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and k represents an integer of 1 to 4)
Examples of the biphenol having the structure represented by the formula (5) include 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.
3.0モルを下回るとエポキシ当量が大きくなることがあり、また、できたエポキシ樹脂の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ため、廃棄物、生産性の面で好ましくない。 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 with respect to 1 mol of the hydroxyl group of the phenol mixture used in the present invention. The amount is preferably 4.0 to 6.0 mol.
If the amount is less than 3.0 mol, the epoxy equivalent may increase, and the workability of the resulting epoxy resin may deteriorate. If it exceeds 15 moles, the amount of solvent becomes large, which is not preferable in terms of waste and productivity.
アルカリ金属水酸化物の使用量は原料の本発明で用いられるフェノール混合物の水酸基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。 In the above reaction, an alkali metal hydroxide can be used. Examples of 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 from 0.90 to 1.5 mol, preferably from 0.95 to 1.25 mol, more preferably from 1 mol of the hydroxyl group of the phenol mixture used in the present invention as a raw material. Is 0.99 to 1.15 mol.
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。 In this reaction, in addition to the above epihalohydrin, it is preferable to use a nonpolar proton solvent (such as dimethyl sulfoxide, dioxane, dimethylimidazolidinone) or an alcohol having 1 to 5 carbon atoms. Examples of the alcohol having 1 to 5 carbon atoms 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. Moreover, epoxidation may be performed while controlling the moisture in the system by a technique such as azeotropic dehydration.
When there is a lot of moisture in the system, 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 the epoxy resin having excellent electrical reliability can be obtained, and therefore a nonpolar proton solvent can be preferably used.
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本発明で用いられるフェノール混合物の水酸基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。 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 cannot proceed, and if the reaction time is long, a by-product may be formed.
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. Further, in order to obtain an epoxy resin mixture with less hydrolyzable halogen, 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. In this case, 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 mixture used in the present invention used for epoxidation. It is. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.
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。 In the epoxy resin mixture of the present invention, the compound represented by the formula (1) and bisglycidyloxybiphenyl (however, when the aromatic ring has a substituent, the number of substituents is 4 or less and the number of carbons is 4 or less. In the reaction under the preferable conditions as described above, there is also a structure in which the phenol resin structure represented by the above formula (1) and the biphenol structure are connected by epihalohydrin. Therefore, by epoxidizing the phenol mixture at the same time, the above structure is formed and the viscosity tends to be relatively low, which is preferable in improving the fluidity of the present invention.
Compared to the case of epoxidizing only biphenol, 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.
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。 Specific examples of the curing catalyst that can be used in the present invention include amine compounds such as triethylamine, tripropylamine, and tributylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, and imidazole. , Triazole, tetrazole, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2 -Methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2'-methylimidazole (1 ')) Ethyl-s Triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl, 4-methylimidazole (1 ′)) ethyl -S-triazine, 2,4-diamino-6 (2'-methylimidazole (1 ')) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenyl Imidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, etc. Various heterocyclic compounds, and these heterocyclic compounds and phthalic acid, isophthalic acid, terephthalic acid, Mellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, salts with polyvalent carboxylic acids such as succinic acid, amides such as dicyandiamide, 1,8-diaza-bicyclo (5.4.0) undecene-7, etc. Diaza compounds and salts thereof such as tetraphenylborate and phenol novolak, salts with the above polyvalent carboxylic acids or phosphinic acids, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide , Trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide Ammonium salts such as droxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctylmethylammonium acetate, triphenylphosphine, tri (toluyl) phosphine, tetraphenylphosphonium bromide, tetraphenyl Phosphines such as phosphonium tetraphenylborate, phosphonium compounds, phenols such as 2,4,6-trisaminomethylphenol, amine adducts, carboxylic acid metal salts (2-ethylhexanoic acid, stearic acid, behenic acid, mistylic acid, etc.) Zinc salts, tin salts, zirconium salts), phosphate ester metals (zinc salts such as octyl phosphate and stearyl phosphate), alkoxy metal salts (trib Le aluminum, tetrapropyl zirconium, etc.), acetylacetonates (acetylacetone zirconium chelate, a metal compound such as acetylacetone titanium chelate) and the like, can be mentioned. In the present invention, phosphonium salts, ammonium salts, and metal compounds are particularly preferable in terms of coloring at the time of curing and changes thereof. When a quaternary salt is used, 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.
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。 The epoxy resin composition of the present invention preferably contains 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 anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, Cyclohe Acid anhydrides such as sun-1,3,4-tricarboxylic acid-3,4-anhydrides; carboxylic acid resins obtained by addition reaction of various alcohols, carbinol-modified silicones and the aforementioned acid anhydrides; bisphenol A, bisphenol F, bisphenol S, 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, phenols (phenol, alkyl-substituted phenol) , Naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphth ) And formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1 Polycondensation with '-biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4'-bis (chloromethyl) benzene or 1,4'-bis (methoxymethyl) benzene And modified products thereof, phenolic resins such as halogenated bisphenols such as tetrabromobisphenol A, condensates of terpenes and phenols; imidazole, trifluoroborane-amine complexes, guanidine derivative compounds, etc. Limited to is not. These may be used alone or in combination of two or more.
In the present invention, the above-described phenol resin is preferable because it is used particularly for electronic materials.
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。 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.
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-602x2、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)
ガラス転移点(Tg):
TMA 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 EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, parts are parts by weight unless otherwise specified. The present invention is not limited to these examples.
The various analysis methods used in the examples are described below.
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-602x2, 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)
Glass transition point (Tg):
TMA thermomechanical measuring device manufactured by TA-instruments, Q400EM
Measurement temperature range: 40 ° C-280 ° C
Temperature increase rate: 2 ° C / min
撹拌機、還流冷却管、撹拌装置を備えた1Lの4つ口フラスコにフェノール化合物(DPPI1)(前記式(1)において置換基Rがすべて水素原子の化合物 SABIC BPPPP 純度99%以上 残留フェノールフタレイン200ppm、鉄分<5ppm、融点290℃)137.7部、ビフェノール27.9部、エピクロロヒドリン555部、ジメチルスルホキシド139部を加え、水浴を50℃にまで昇温した。内温が45℃を越えたところでフレーク状の水酸化ナトリウム44部を90分かけて分割添加した後、更に45℃で2時間、70℃で1時間後反応を行った。反応終了後水洗を行い、油層からロータリーエバポレータを用いて140℃で減圧下、過剰のエピクロルヒドリン等の溶剤を留去した。残留物にメチルイソブチルケトン505部を加え溶解し、水洗により生成した塩化ナトリウム等を除去後、有機層を70℃にまで昇温し、撹拌下で30重量%の水酸化ナトリウム水溶液20部を加え、1時間反応を行った後、洗浄水が中性になるまで水洗を行い、得られた溶液を、ロータリーエバポレータを用いて180℃で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)を210部得た。得られたエポキシ樹脂混合物のエポキシ当量は226g/eq.、軟化点が92℃、ICI溶融粘度0.15Pa・s(150℃)、全塩素量 505ppm、加水分解性塩素 480ppm、塩素イオン0.1ppm、ナトリウムイオン0.1ppmであった。また前記式(1)の化合物は72面積%(GPC)、ビフェノールのエポキシ化物は16面積%(GPC)であった。さらに、前記式(1)の化合物(a)とビフェノールのエポキシ化物(b)は重量比で(a)/(b)=4.5、モル比率で2.64である。他構造については前記式(1)の化合物同士、ビフェノール同士、前記式(1)とビフェノールが混在して結合した化合物を含むものであった。 Example 1
A phenol compound (DPPI1) (compound in which the substituents R are all hydrogen atoms in the above formula (1) SABIC BPPPP purity 99% or more Residual phenolphthalein 200 ppm, iron content <5 ppm, melting point 290 ° C.) 137.7 parts, biphenol 27.9 parts, epichlorohydrin 555 parts, dimethyl sulfoxide 139 parts were added, and the water bath was heated to 50 ° C. When the internal temperature exceeded 45 ° C., 44 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by further reaction at 45 ° C. for 2 hours and at 70 ° C. for 1 hour. After completion of the reaction, washing was performed, and excess solvent such as epichlorohydrin was distilled off from the oil layer under reduced pressure at 140 ° C. using a rotary evaporator. To the residue is added 505 parts of methyl isobutyl ketone and dissolved, and after removing sodium chloride and the like produced by washing with water, the organic layer is heated to 70 ° C., and 20 parts of 30 wt% aqueous sodium hydroxide solution is added with stirring. After reacting for 1 hour, washing is performed until the washing water becomes neutral, and the resulting solution is subjected to the present invention by distilling off methyl isobutyl ketone and the like under reduced pressure at 180 ° C. using a rotary evaporator. 210 parts of an epoxy resin mixture (EP1) was obtained. The epoxy equivalent of the obtained epoxy resin mixture was 226 g / eq. The softening point was 92 ° C., the ICI melt viscosity was 0.15 Pa · s (150 ° C.), the total chlorine amount was 505 ppm, the hydrolyzable chlorine was 480 ppm, the chlorine ions were 0.1 ppm, and the sodium ions were 0.1 ppm. The compound of the formula (1) was 72 area% (GPC), and the epoxidized biphenol was 16 area% (GPC). Further, the compound (a) of the formula (1) and the epoxidized product (b) of biphenol are (a) / (b) = 4.5 by weight ratio and 2.64 by mole ratio. About other structures, the compound of the said Formula (1), biphenols, and the compound which the said Formula (1) and biphenol mixed and were couple | bonded were included.
撹拌機、還流冷却管、撹拌装置を備えた1Lの4つ口フラスコにフェノール化合物(DPPI1)(前記式(1)において置換基Rがすべて水素原子の化合物 SABIC BPPPP 純度99%以上 残留フェノールフタレイン200ppm、鉄分<5ppm、融点290℃)295部、エピクロロヒドリン971部、ジメチルスルホキシド165部を加え、水浴を45℃にまで昇温した。内温が40℃を越えたところでフレーク状の水酸化ナトリウム66部を90分かけて分割添加した後、更に45℃2時間、70℃で1時間後反応を行った。反応終了後水洗を行い、油層からロータリーエバポレータを用いて140℃で減圧下、過剰のエピクロルヒドリン等の溶剤を留去した。残留物にメチルイソブチルケトン760部を加え溶解し、水洗により生成した塩化ナトリウム等を除去後、有機層を70℃にまで昇温し、撹拌下で30重量%の水酸化ナトリウム水溶液30部を加え、1時間反応を行った後、洗浄水が中性になるまで水洗を行い、得られた溶液を、ロータリーエバポレータを用いて180℃で減圧下にメチルイソブチルケトン等を留去することで前記式(1)で表される構造を有するエポキシ樹脂(EP4)を353部得た。得られたエポキシ樹脂のエポキシ当量は267g/eq.、軟化点が99℃、ICI溶融粘度0.91Pa・s(150℃)、全塩素量 540ppm、加水分解性塩素 430ppm、塩素イオン0.1ppm、ナトリウムイオン0.1ppmであった。また前記式(1)の構造の化合物は88面積%(GPC)、残り12面積%は前記式(1)の構造の化合物同士が結合した化合物を含むものであった。 Synthesis example 1
Phenol compound (DPPI1) (compound in which all substituents R are hydrogen atoms in the above formula (1) SABIC BPPPP purity 99% or more residual phenolphthalein in a 1 L four-necked flask equipped with a stirrer, reflux condenser and stirrer 200 ppm, iron content <5 ppm, melting point 290 ° C.) 295 parts, epichlorohydrin 971 parts, dimethyl sulfoxide 165 parts were added, and the temperature of the water bath was raised to 45 ° C. When the internal temperature exceeded 40 ° C., 66 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by further reaction at 45 ° C. for 2 hours and at 70 ° C. for 1 hour. After completion of the reaction, washing was performed, and excess solvent such as epichlorohydrin was distilled off from the oil layer under reduced pressure at 140 ° C. using a rotary evaporator. 760 parts of methyl isobutyl ketone was added to the residue and dissolved, and after removing sodium chloride and the like produced by washing with water, the organic layer was heated to 70 ° C. and 30 parts by weight of 30 wt% sodium hydroxide aqueous solution was added with stirring. After reacting for 1 hour, washing is carried out until the washing water becomes neutral, and the obtained solution is subjected to the above formula by distilling off methyl isobutyl ketone and the like under reduced pressure at 180 ° C. using a rotary evaporator. 353 parts of epoxy resin (EP4) which has a structure represented by (1) was obtained. The epoxy equivalent of the obtained epoxy resin is 267 g / eq. The softening point was 99 ° C., the ICI melt viscosity was 0.91 Pa · s (150 ° C.), the total chlorine content was 540 ppm, the hydrolyzable chlorine was 430 ppm, the chlorine ions were 0.1 ppm, and the sodium ions were 0.1 ppm. The compound having the structure of the formula (1) contained 88 area% (GPC), and the remaining 12 area% contained a compound in which the compounds having the structure of the formula (1) were bonded to each other.
実施例1で得られた本発明のエポキシ樹脂混合物(EP1)と比較用のエポキシ樹脂(EP2;フェノール-ビフェニレンアラルキル型エポキシ樹脂 日本化薬株式会社製 NC-3000、EP3;トリスフェノールメタン型エポキシ樹脂 日本化薬株式会社製 EPPN-502H)、を使用し、エポキシ樹脂と硬化剤(フェノールノボラック(明和化成工業(株)製 H-1)または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対する割合)を入れ、ミキシングロールを用いて均一に混合・混練し、封止用エポキシ樹脂組成物を得た。このエポキシ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本発明及び比較用のエポキシ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。
なお、硬化物の物性は以下の要領で測定した。また、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。 Example 2 and Comparative Examples 1 and 2
The epoxy resin mixture (EP1) of the present invention obtained in Example 1 and a comparative epoxy resin (EP2; phenol-biphenylene aralkyl type epoxy resin, manufactured by Nippon Kayaku Co., Ltd. NC-3000, EP3; trisphenolmethane type epoxy resin Epoxy resin and curing agent (phenol novolak (M-1 made by Meiwa Kasei Kogyo Co., Ltd.) or phenol aralkyl resin (Mitsui Chemicals Co., Ltd., Millex XLC-3L) )) With equal equivalents, a curing catalyst (curing accelerator, triphenylphosphine (TPP manufactured by Hokuko Chemical Co., Ltd.)) and a filler (fused silica, manufactured by Ashimori MSR-2122, if necessary)% in the table Is a proportion of the total epoxy resin composition) and mixed and kneaded uniformly using a mixing roll. To obtain a epoxy resin composition for sealing. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy resin composition of the present invention and the comparative composition were transfer molded (175 ° C. × 60 seconds), and after demolding, cured under the conditions of 160 ° C. × 2 hours + 180 ° C. × 6 hours, a test piece for evaluation Got.
In addition, the physical property of hardened | cured material was measured in the following ways. Also, depending on the evaluation items of the physical properties of the cured product, the type of curing agent to be 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.
JISK-6911(成型収縮率)に準拠
<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 <Curing shrinkage>
Conforms to JISK-6911 (mold shrinkage) <Flame retardance 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 contact with 5 samples
実施例1で得られた本発明のエポキシ樹脂混合物(EP1)と合成例1で得られた比較用のエポキシ樹脂(EP4)を使用し、エポキシ樹脂と硬化剤(フェノールノボラック(明和化成工業(株)製 H-1)または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%はエポキシ樹脂全体に対する割合)を入れ、ミキシングロールを用いて均一に混合・混練し、封止用エポキシ樹脂組成物を得た。このエポキシ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本発明及び比較用のエポキシ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。
なお、硬化物の物性は以下の要領で測定した。また、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2の通りとし、硬化促進剤の使用量は、耐熱性、機械強度及び密着性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。 Example 3 and Comparative Example 3
Using the epoxy resin mixture (EP1) of the present invention obtained in Example 1 and the comparative epoxy resin (EP4) obtained in Synthesis Example 1, an epoxy resin and a curing agent (phenol novolak (Maywa Kasei Kogyo Co., Ltd.) ) H-1) or phenol aralkyl resin (Mirex XLC-3L manufactured by Mitsui Chemicals, Inc.)) is blended in equal equivalents, and a curing catalyst (curing accelerator, triphenylphosphine (TPP manufactured by Hokuko Chemical Co., Ltd.)) And a filler (fused silica, made by Kashimori MSR-2122, the filler amount% in the table is the ratio to the total epoxy resin), and mixed and kneaded uniformly using a mixing roll, and the epoxy resin composition for sealing Got. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy resin composition of the present invention and the comparative composition were transfer molded (175 ° C. × 60 seconds), and after demolding, cured under the conditions of 160 ° C. × 2 hours + 180 ° C. × 6 hours, a test piece for evaluation Got.
In addition, the physical property of hardened | cured material was measured in the following ways. In addition, depending on the evaluation items of the physical properties of the cured product, the type of curing agent to be used is as shown in Table 2 below, and the amount of curing accelerator used is the weight of the epoxy resin in the sample used for the evaluation of heat resistance, mechanical strength and adhesion. 1% relative to the weight of the epoxy resin in the sample used for evaluation of flame retardancy.
・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
<曲げ試験>
・JIS K 6911に準拠 室温と120℃でテストを行った。
<ピール強度>
・180℃剥離試験 JIS K-6854-2に準拠 圧延銅箔使用
<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 <TMA measurement conditions>
・ Thermo-mechanical measuring device, TA-instruments, Q400EM
・ Measurement temperature range: 40 ℃ ~ 280 ℃
・ Temperature increase rate: 2 ° C./min <bending test>
-According to JIS K 6911 The test was performed at room temperature and 120 ° C.
<Peel strength>
180 ° C peel test JIS K-6854-2 compliant Use of rolled copper foil <Flame retardance 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 contact with 5 samples
撹拌機、還流冷却管、撹拌装置を備えたフラスコにフェノール化合物(DPPI1)(前記式(1)において置換基Rがすべて水素原子の化合物 SABIC PPPBP 純度99%以上 残留フェノールフタレイン200ppm、鉄分<5ppm)256部、エピクロロヒドリン971部、ベンジルトリメチルアンモニウムクロライド3部を加え、水浴を70℃にまで昇温した。ここに49%水酸化ナトリウム水溶液100部を90分かけて滴下した後、更に70℃で4時間後反応を行った。反応終了後水洗を行い、油層からロータリーエバポレータを用いて140℃で減圧下、過剰のエピクロルヒドリン等の溶剤を留去することで前記式(1)で表される構造を有するエポキシ樹脂(EP5)を290部得た。得られた前記式(1)で表される構造を有するエポキシ樹脂のエポキシ当量は297g/eq.、軟化点が95℃、ICI溶融粘度0.70Pa・s(150℃)、全塩素量 10450ppm、加水分解性塩素 9700ppmであった。 Synthesis example 2
In a flask equipped with a stirrer, a reflux condenser, and a stirrer, a phenol compound (DPPI1) (a compound in which the substituents R are all hydrogen atoms in the above formula (1) SABIC PPPBP purity 99% or more residual phenolphthalein 200 ppm, iron <5 ppm ) 256 parts, epichlorohydrin 971 parts, benzyltrimethylammonium chloride 3 parts were added, and the temperature of the water bath was raised to 70 ° C. To this, 100 parts of a 49% aqueous sodium hydroxide solution was added dropwise over 90 minutes, followed by further reaction at 70 ° C. for 4 hours. After completion of the reaction, washing with water was carried out, and an epoxy resin (EP5) having a structure represented by the above formula (1) was obtained by distilling off excess epichlorohydrin and the like from the oil layer under reduced pressure at 140 ° C. using a rotary evaporator. 290 parts were obtained. The epoxy resin having the structure represented by the formula (1) obtained has an epoxy equivalent of 297 g / eq. The softening point was 95 ° C., the ICI melt viscosity was 0.70 Pa · s (150 ° C.), the total chlorine content was 10450 ppm, and the hydrolyzable chlorine was 9700 ppm.
実施例1で得られた本発明のエポキシ樹脂混合物(EP1)と合成例2で得られた比較用のエポキシ樹脂(EP5)用い、エポキシ樹脂と硬化剤(フェノールノボラック(明和化成工業(株)製 H-1))を等当量で配合し、硬化触媒(硬化促進剤)としてトリフェニルフォスフィン(北興化学(株)製 TPP)をエポキシ樹脂の重量に対し、1%添加し、ミキシングロールを用いて均一に混合・混練し、封止用エポキシ樹脂組成物を得た。このエポキシ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エポキシ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。
なお、硬化物の物性は以下の要領で測定した。 Example 4 and Comparative Example 4
Using the epoxy resin mixture (EP1) of the present invention obtained in Example 1 and the comparative epoxy resin (EP5) obtained in Synthesis Example 2, an epoxy resin and a curing agent (phenol novolak (Maywa Kasei Kogyo Co., Ltd.) H-1)) is blended in an equivalent amount, and 1% of triphenylphosphine (TPP manufactured by Hokuko Chemical Co., Ltd.) is added as a curing catalyst (curing accelerator) based on the weight of the epoxy resin, and a mixing roll is used. Were mixed and kneaded uniformly to obtain an epoxy resin composition for sealing. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy 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.
In addition, the physical property of hardened | cured material was measured in the following ways.
・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 <TMA measurement conditions>
・ Thermo-mechanical measuring device, TA-instruments, Q400EM
・ Measurement temperature range: 40 ℃ ~ 280 ℃
・ Temperature increase rate: 2 ℃ / min
撹拌機、還流冷却管、撹拌装置を備えたフラスコにビフェノール100部、エピクロロヒドリン971部、メタノール97部を加え、水浴を70℃にまで昇温した。ここにフレーク状の水酸化ナトリウム41部を90分かけて分割添加した後、更に70℃で1時間後反応を行った。反応後、析出したエポキシ樹脂と塩化ナトリウムとの混合物を溶剤類から濾別した。70℃の温水200部で5回洗浄し、乾燥することで、前記式(5)で表されるビフェノール型のエポキシ樹脂(EP7)を121部得た。
得られたエポキシ樹脂(EP7)と合成例1で得られたエポキシ樹脂(EP4)を、それぞれ20部と80部の割合でテトラヒドロフラン300部に加え、そのままロータリーエバポレータにて180℃で減圧下にテトラヒドロフランを留去することで本発明のエポキシ樹脂混合物(EP8)を得た。得られたエポキシ樹脂混合物(EP8)は半晶状であり、そのエポキシ当量は247g/eq.、軟化点が95℃、ICI溶融粘度0.18Pa・s(150℃)、全塩素量 1820ppm、加水分解性塩素 1670ppmであった。 Example 5
100 parts of biphenol, 971 parts of epichlorohydrin and 97 parts of methanol were added to a flask equipped with a stirrer, a reflux condenser, and a stirrer, and the temperature of the water bath was raised to 70 ° C. After 41 parts of flaky sodium hydroxide was added in portions over 90 minutes, the reaction was further carried out at 70 ° C. for 1 hour. After the reaction, a mixture of the precipitated epoxy resin and sodium chloride was filtered off from the solvents. By washing 5 times with 200 parts of warm water of 70 ° C. and drying, 121 parts of biphenol type epoxy resin (EP7) represented by the above formula (5) was obtained.
The obtained epoxy resin (EP7) and the epoxy resin (EP4) obtained in Synthesis Example 1 were added to 300 parts of tetrahydrofuran at a ratio of 20 parts and 80 parts, respectively, and tetrahydrofuran was added as it was at 180 ° C. under reduced pressure using a rotary evaporator. Was distilled off to obtain an epoxy resin mixture (EP8) of the present invention. The obtained epoxy resin mixture (EP8) was semi-crystalline and its epoxy equivalent was 247 g / eq. The softening point was 95 ° C., the ICI melt viscosity was 0.18 Pa · s (150 ° C.), the total chlorine content was 1820 ppm, and the hydrolyzable chlorine was 1670 ppm.
前記実施例1で得られたエポキシ樹脂混合物(EP1)及び、実施例5で得られたエポキシ樹脂(EP8)を使用し、エポキシ樹脂と硬化剤(フェノールアラルキル樹脂(日本化薬(株)製 KAYAHARD GPH-65))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)をエポキシ樹脂の重量に対し2%添加)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対する割合)を入れ、ミキシングロールを用いて均一に混合・混練し、封止用エポキシ樹脂組成物を得た。このエポキシ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エポキシ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。
なお、硬化物の物性は以下の要領で測定した。 Examples 6 and 7
Using the epoxy resin mixture (EP1) obtained in Example 1 and the epoxy resin (EP8) obtained in Example 5, an epoxy resin and a curing agent (phenol aralkyl resin (KAYAHARD manufactured by Nippon Kayaku Co., Ltd.) GPH-65)) at equal equivalents, curing catalyst (curing accelerator, triphenylphosphine (TPP manufactured by Hokuko Chemical Co., Ltd. 2% added to the weight of the epoxy resin) and filler (melting) as required Silica MSM-2122, filler amount% in the table is a ratio to the whole epoxy resin composition), and mixed and kneaded uniformly using a mixing roll to obtain an epoxy resin composition for sealing. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy 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.
In addition, the physical property of hardened | cured material was measured in the following ways.
・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 <TMA measurement conditions>
・ Thermo-mechanical measuring device, TA-instruments, Q400EM
・ Measurement temperature range: 40 ℃ ~ 280 ℃
・ 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 contact with 5 samples
撹拌機、還流冷却管、撹拌装置を備えた1Lの4つ口フラスコにフェノール化合物(イギリス特許1,158,606 example7に記載の手法に準拠して合成 純度99%以上 残留フェノールフタレイン14ppm、鉄分<5ppm、融点289-290℃)137.7部、ビフェノール27.9部、エピクロロヒドリン470部、ジメチルスルホキシド120部を加え、水浴を50℃にまで昇温した。内温が45℃を越えたところでフレーク状の水酸化ナトリウム44部を90分かけて分割添加した後、更に45℃で2時間、70℃で1時間後反応を行った。反応終了後、ロータリーエバポレータを用いて140℃で減圧下、過剰のエピクロルヒドリン等の溶剤を留去した。残留物にメチルイソブチルケトン505部を加え溶解し、水洗により生成した塩化ナトリウム等を除去後、有機層を70℃にまで昇温し、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、洗浄水が中性になるまで水洗を行い、得られた溶液を、ロータリーエバポレータを用いて180℃で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(EP13)を205部得た。得られたエポキシ樹脂混合物のエポキシ当量は236g/eq.、軟化点が92℃、ICI溶融粘度0.15Pa・s(150℃)、全塩素量 309ppm、加水分解性塩素 278ppm、塩素イオン0.1ppm、ナトリウムイオン0.1ppmであった。また前記式(1)の化合物の含有割合は65面積%(GPC)、ビフェノールのエポキシ化物の含有割合は15面積%(GPC)であった。さらに、前記式(1)の化合物(a)とビフェノールのエポキシ化物(b)は重量比で(a)/(b)=4.3、モル比率で2.55である。他構造については前記式(1)の化合物同士、ビフェノール同士、前記式(1)の化合物とビフェノールが混在して結合した化合物を含むものであった。 Example 8
A 1-L four-necked flask equipped with a stirrer, a reflux condenser, and a stirrer is charged with a phenol compound (based on the method described in British Patent 1,158,606 example7, purity 99% or more, residual phenolphthalein 14 ppm, iron content <5 ppm, melting point 289-290 ° C.) 137.7 parts, 27.9 parts of biphenol, 470 parts of epichlorohydrin and 120 parts of dimethyl sulfoxide were added, and the temperature of the water bath was raised to 50 ° C. When the internal temperature exceeded 45 ° C., 44 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by further reaction at 45 ° C. for 2 hours and at 70 ° C. for 1 hour. After completion of the reaction, excess solvent such as epichlorohydrin was distilled off under reduced pressure at 140 ° C. using a rotary evaporator. 505 parts of methyl isobutyl ketone is added to the residue and dissolved, and after removing sodium chloride and the like produced by washing with water, the organic layer is heated to 70 ° C., and 10 parts of 30 wt% aqueous sodium hydroxide solution is added with stirring. After reacting for 1 hour, washing is performed until the washing water becomes neutral, and the resulting solution is subjected to the present invention by distilling off methyl isobutyl ketone and the like under reduced pressure at 180 ° C. using a rotary evaporator. 205 parts of an epoxy resin mixture (EP13) was obtained. The epoxy equivalent of the obtained epoxy resin mixture was 236 g / eq. The softening point was 92 ° C., the ICI melt viscosity was 0.15 Pa · s (150 ° C.), the total chlorine content was 309 ppm, the hydrolyzable chlorine was 278 ppm, the chlorine ions were 0.1 ppm, and the sodium ions were 0.1 ppm. The content ratio of the compound of the formula (1) was 65 area% (GPC), and the content ratio of the epoxidized biphenol was 15 area% (GPC). Furthermore, the compound (a) of the above formula (1) and the epoxidized product (b) of biphenol are (a) / (b) = 4.3 by weight ratio and 2.55 by mole ratio. About other structures, the compound of the said Formula (1), biphenols, and the compound which the compound of the said Formula (1) and biphenol mixed and couple | bonded were included.
撹拌機、還流冷却管、撹拌装置を備えた1Lの4つ口フラスコにフェノール化合物(イギリス特許1,158,606 example7に記載の手法に準拠して合成 純度99%以上 残留フェノールフタレイン14ppm、鉄分<5ppm、融点289-290℃)125.7部、ビフェノール33.6部、エピクロロヒドリン463部、ジメチルスルホキシド116部を加え、水浴を50℃にまで昇温した。内温が45℃を越えたところでフレーク状の水酸化ナトリウム44部を90分かけて分割添加した後、更に45℃で2時間、70℃で1時間後反応を行った。反応終了後、ロータリーエバポレータを用いて140℃で減圧下、過剰のエピクロルヒドリン等の溶剤を留去した。残留物にメチルイソブチルケトン505部を加え溶解し、水洗により生成した塩化ナトリウム等を除去後、有機層を70℃にまで昇温し、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、洗浄水が中性になるまで水洗を行い、得られた溶液を、ロータリーエバポレータを用いて180℃で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(EP14)を195部得た。得られたエポキシ樹脂混合物のエポキシ当量は225g/eq.、軟化点が81℃、ICI溶融粘度0.09Pa・s(150℃)、全塩素量 377ppm、加水分解性塩素 281ppm、塩素イオン0.1ppm、ナトリウムイオン0.1ppmであった。また前記式(1)の化合物の含有割合は63面積%(GPC)、ビフェノールのエポキシ化物の含有割合は19面積%(GPC)であった。さらに、前記式(1)の化合物(a)とビフェノールのエポキシ化物(b)は重量比で(a)/(b)=3.3、モル比率で1.96である。他構造については前記式(1)の化合物同士、ビフェノール同士、前記式(1)の化合物とビフェノールが混在して結合した化合物を含むものであった。 Example 9
A 1-L four-necked flask equipped with a stirrer, a reflux condenser, and a stirrer is charged with a phenol compound (based on the method described in British Patent 1,158,606 example7, purity 99% or more, residual phenolphthalein 14 ppm, iron content <5 ppm, melting point 289-290 ° C.) 125.7 parts, biphenol 33.6 parts, epichlorohydrin 463 parts, dimethyl sulfoxide 116 parts were added, and the temperature of the water bath was raised to 50 ° C. When the internal temperature exceeded 45 ° C., 44 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by further reaction at 45 ° C. for 2 hours and at 70 ° C. for 1 hour. After completion of the reaction, excess solvent such as epichlorohydrin was distilled off under reduced pressure at 140 ° C. using a rotary evaporator. 505 parts of methyl isobutyl ketone is added to the residue and dissolved, and after removing sodium chloride and the like produced by washing with water, the organic layer is heated to 70 ° C., and 10 parts of 30 wt% aqueous sodium hydroxide solution is added with stirring. After reacting for 1 hour, washing is performed until the washing water becomes neutral, and the resulting solution is subjected to the present invention by distilling off methyl isobutyl ketone and the like under reduced pressure at 180 ° C. using a rotary evaporator. 195 parts of an epoxy resin mixture (EP14) was obtained. The epoxy equivalent of the obtained epoxy resin mixture was 225 g / eq. The softening point was 81 ° C., ICI melt viscosity 0.09 Pa · s (150 ° C.), total chlorine amount 377 ppm, hydrolyzable chlorine 281 ppm, chlorine ion 0.1 ppm, sodium ion 0.1 ppm. The content ratio of the compound of the formula (1) was 63 area% (GPC), and the content ratio of the epoxidized biphenol was 19 area% (GPC). Further, the compound (a) of the formula (1) and the epoxidized product (b) of biphenol are (a) / (b) = 3.3 in weight ratio and 1.96 in molar ratio. About other structures, the compound of the said Formula (1), biphenols, and the compound which the compound of the said Formula (1) and biphenol mixed and couple | bonded were included.
撹拌機、還流冷却管、撹拌装置を備えた1Lの4つ口フラスコにフェノール化合物(イギリス特許1,158,606 example7に記載の手法に準拠して合成 純度99%以上 残留フェノールフタレイン14ppm、鉄分<5ppm、融点289-290℃)151.5部、ビフェノール21.4部、エピクロロヒドリン463部、ジメチルスルホキシド116部を加え、水浴を50℃にまで昇温した。内温が45℃を越えたところでフレーク状の水酸化ナトリウム44部を90分かけて分割添加した後、更に45℃で2時間、70℃で1時間後反応を行った。反応終了後、ロータリーエバポレータを用いて140℃で減圧下、過剰のエピクロルヒドリン等の溶剤を留去した。残留物にメチルイソブチルケトン505部を加え溶解し、水洗により生成した塩化ナトリウム等を除去後、有機層を70℃にまで昇温し、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、洗浄水が中性になるまで水洗を行い、得られた溶液を、ロータリーエバポレータを用いて180℃で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(EP15)を210部得た。得られたエポキシ樹脂混合物のエポキシ当量は248g/eq.、軟化点が83℃、ICI溶融粘度0.31Pa・s(150℃)、全塩素量 410ppm、加水分解性塩素 299ppm、塩素イオン0.1ppm、ナトリウムイオン0.1ppmであった。また前記式(1)の化合物の含有割合は72面積%(GPC)、ビフェノールのエポキシ化物の含有割合は12面積%(GPC)であった。さらに、前記式(1)の化合物(a)とビフェノールのエポキシ化物(b)は重量比で(a)/(b)=6.0、モル比率で3.56である。他構造については前記式(1)の化合物同士、ビフェノール同士、前記式(1)の化合物とビフェノールが混在して結合した化合物を含むものであった。 Example 10
A 1-L four-necked flask equipped with a stirrer, a reflux condenser, and a stirrer is charged with a phenol compound (based on the method described in British Patent 1,158,606 example7, purity 99% or more, residual phenolphthalein 14 ppm, iron content <5 ppm, melting point 289-290 ° C.) 151.5 parts, biphenol 21.4 parts, epichlorohydrin 463 parts, dimethyl sulfoxide 116 parts were added, and the temperature of the water bath was raised to 50 ° C. When the internal temperature exceeded 45 ° C., 44 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by further reaction at 45 ° C. for 2 hours and at 70 ° C. for 1 hour. After completion of the reaction, excess solvent such as epichlorohydrin was distilled off under reduced pressure at 140 ° C. using a rotary evaporator. 505 parts of methyl isobutyl ketone is added to the residue and dissolved, and after removing sodium chloride and the like produced by washing with water, the organic layer is heated to 70 ° C., and 10 parts of 30 wt% aqueous sodium hydroxide solution is added with stirring. After reacting for 1 hour, washing is performed until the washing water becomes neutral, and the resulting solution is subjected to the present invention by distilling off methyl isobutyl ketone and the like under reduced pressure at 180 ° C. using a rotary evaporator. 210 parts of an epoxy resin mixture (EP15) was obtained. The epoxy equivalent of the obtained epoxy resin mixture was 248 g / eq. The softening point was 83 ° C., the ICI melt viscosity was 0.31 Pa · s (150 ° C.), the total chlorine content was 410 ppm, the hydrolyzable chlorine was 299 ppm, the chlorine ions were 0.1 ppm, and the sodium ions were 0.1 ppm. The content of the compound of the formula (1) was 72 area% (GPC), and the content of the epoxidized biphenol was 12 area% (GPC). Furthermore, the compound (a) of the formula (1) and the epoxidized product (b) of biphenol are (a) / (b) = 6.0 by weight ratio and 3.56 by mole ratio. About other structures, the compound of the said Formula (1), biphenols, and the compound which the compound of the said Formula (1) and biphenol mixed and couple | bonded were included.
実施例8~10で得られたエポキシ樹脂混合物(EP13、14、15)、比較用のエポキシ樹脂EP10~12(EP10: 日本化薬製 オルソクレゾールノボラックエポキシ樹脂 EOCN-1020-70、EP11: 三菱化学製 ビフェニルタイプエポキシ樹脂 YX-4000H、EP12: 日本化薬製 ビフェニルアラルキルエポキシ樹脂 NC-3000)を使用し、エポキシ樹脂と硬化剤(フェノールノボラック:明和化成工業製 H-1)を等当量で配合し、硬化促進剤としてトリフェニルフォスフィンをエポキシ樹脂の重量に対し、1%添加し、ミキシングロールを用いて均一に混合・混練し、封止用エポキシ樹脂組成物を得た。このエポキシ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エポキシ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。
なお、硬化物の物性は以下の要領で測定した。 Examples 11 to 13 and Comparative Examples 8 to 10
Epoxy resin mixture (EP13, 14, 15) obtained in Examples 8 to 10, comparative epoxy resin EP10 to 12 (EP10: Nippon Kayaku Orthocresol novolak epoxy resin EOCN-1020-70, EP11: Mitsubishi Chemical Use biphenyl type epoxy resin YX-4000H, EP12: Nippon Kayaku biphenyl aralkyl epoxy resin NC-3000), and mix epoxy resin and curing agent (phenol novolac: H-1 made by Meiwa Kasei Kogyo Co.) Then, 1% of triphenylphosphine as a curing accelerator was added to the weight of the epoxy resin, and the mixture was uniformly mixed and kneaded using a mixing roll to obtain an epoxy resin composition for sealing. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy 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.
In addition, the physical property of hardened | cured material was measured in the following ways.
動的粘弾性測定器:TA-instruments、DMA-2980
測定温度範囲:-30~280℃
温速度:2℃/分
試験片サイズ:5mm×50mmに切り出した物を使用した(厚みは約800μm)
Tg:Tan-δのピーク点をTgとした。 <Elastic modulus and heat resistance (DMA)>
Dynamic viscoelasticity measuring instrument: TA-instruments, DMA-2980
Measurement temperature range: -30 to 280 ° C
Temperature rate: 2 ° C./min Test piece size: 5 mm × 50 mm cut out (thickness is about 800 μm)
Tg: The peak point of Tan-δ was defined as Tg.
実施例11~13及び比較例10において、硬化剤をビフェニルタイプフェノールアラルキル樹脂(日本化薬製 KAYAHARD GPH-65)に変更した以外は同様の操作を行った。 Examples 14 to 16 and Comparative Example 11
In Examples 11 to 13 and Comparative Example 10, the same operation was performed except that the curing agent was changed to biphenyl type phenol aralkyl resin (KAYAHARD GPH-65 manufactured by Nippon Kayaku Co., Ltd.).
実施例8で得られたエポキシ樹脂混合物(EP13)と比較用のエポキシ樹脂(EP16;トリスフェノールメタン型エポキシ樹脂 日本化薬株式会社製 EPPN-501H)、を使用し、各々のエポキシ樹脂と硬化剤(ビフェニルタイプフェノールアラルキル樹脂: 軟化点73℃ 日本国特開2003-113225 実施例1に記載の手法を用いて合成 水酸基当量 207g/eq.)を等当量で配合し、硬化促進剤としてトリ-p-トリルフォスフィン(エポキシ樹脂重量に対し、1%)を添加し、ミキシングロールを用いて均一に混合・混練し、封止用エポキシ樹脂組成物を得た。このエポキシ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エポキシ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、下記の測定を行なった。 Example 17 and Comparative Example 12
Using the epoxy resin mixture (EP13) obtained in Example 8 and a comparative epoxy resin (EP16; trisphenolmethane type epoxy resin, Nippon Kayaku Co., Ltd. EPPN-501H), each epoxy resin and curing agent (Biphenyl type phenol aralkyl resin: softening point 73 ° C., Japanese Patent Laid-Open No. 2003-113225, synthesized using the method described in Example 1, hydroxyl equivalent 207 g / eq.) Is blended in an equivalent amount, and tri-p is used as a curing accelerator. -Tolylphosphine (1% based on the weight of the epoxy resin) was added, and the mixture was uniformly mixed and kneaded using a mixing roll to obtain an epoxy resin composition for sealing. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. This tableted epoxy 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. Was done.
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 <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
動的粘弾性測定器:TA-instruments製、DMA-2980
測定温度範囲:-30℃~280℃
温速度:2℃/分
試験片サイズ:5mm×50mmに切り出した物を使用した(厚みは約800μm)。
解析条件Tg:DMA測定に於けるTanδのピーク点(tanδMAX)をTgとした。 <DMA measurement conditions>
Dynamic viscoelasticity measuring device: manufactured by TA-instruments, DMA-2980
Measurement temperature range: -30 ° C to 280 ° C
Temperature rate: 2 ° C./min Test piece size: 5 mm × 50 mm cut out (thickness is about 800 μm).
Analysis condition Tg: Tanδ peak point (tanδMAX) in DMA measurement was defined as Tg.
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。 <Measurement conditions for thermal decomposition characteristics>
Part of the obtained test piece was pulverized by a cycle mill, powdered, passed through a 100 μm mesh and aligned to a particle size of 75 μm 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 (100μm mesh passed, 75μm mesh on) 5-10mg
Measurement conditions: Temperature rising rate 10 ° C./min Air flow 200 ml / min 5% weight loss temperature was measured.
撹拌機、還流冷却管、撹拌装置を備えた1Lの4つ口フラスコにフェノール化合物(イギリス特許1,158,606 example7に記載の手法に準拠して合成 純度99%以上 残留フェノールフタレイン14ppm、鉄分<5ppm、融点289-290℃)138部、ビフェノール28部、エピクロロヒドリン463部、ジメチルスルホキシド115部を加え、水浴を50℃にまで昇温した。内温が45℃を越えたところでフレーク状の水酸化ナトリウム44部を90分かけて分割添加した後、更に45℃で2時間、70℃で1時間後反応を行った。反応終了後、ロータリーエバポレータを用いて140℃で減圧下、過剰のエピクロルヒドリン等の溶剤を留去した。残留物にメチルイソブチルケトン505部を加え溶解し、水洗により生成した塩化ナトリウム等を除去後、有機層を70℃にまで昇温し、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、洗浄水が中性になるまで水洗を行い、得られた溶液を、ロータリーエバポレータを用いて180℃で減圧下にメチルイソブチルケトン等を留去することでエポキシ樹脂(EP17)を189部得た。得られたエポキシ樹脂のエポキシ当量は241g/eq.、軟化点が85.3℃、ICI溶融粘度0.15Pa・s(150℃)、全塩素量 460ppm、加水分解性塩素 394ppm、塩素イオン0.6ppm、ナトリウムイオン0.7ppmであった。また前記式(1)の構造は69.5面積%(GPC)、ビフェノールのエポキシ化物は15.0面積%(GPC)であった。さらに、前記式(1)の化合物(a)とビフェノールのエポキシ化物(b)は重量比で(a)/(b)=4.6、モル比率2.73である。他構造については前記式(1)の化合物同士、ビフェノール同士、前記式(1)の化合物とビフェノールが混在して結合した化合物を含むものであった。 Example 18
A 1-L four-necked flask equipped with a stirrer, a reflux condenser, and a stirrer is charged with a phenol compound (based on the method described in British Patent 1,158,606 example7, purity 99% or more, residual phenolphthalein 14 ppm, iron content <5 ppm, melting point 289-290 ° C.) 138 parts, biphenol 28 parts, epichlorohydrin 463 parts, dimethyl sulfoxide 115 parts were added, and the temperature of the water bath was raised to 50 ° C. When the internal temperature exceeded 45 ° C., 44 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by further reaction at 45 ° C. for 2 hours and at 70 ° C. for 1 hour. After completion of the reaction, excess solvent such as epichlorohydrin was distilled off under reduced pressure at 140 ° C. using a rotary evaporator. 505 parts of methyl isobutyl ketone is added to the residue and dissolved, and after removing sodium chloride and the like produced by washing with water, the organic layer is heated to 70 ° C., and 10 parts of 30 wt% aqueous sodium hydroxide solution is added with stirring. After reacting for 1 hour, washing is carried out until the washing water becomes neutral, and the resulting solution is epoxy resin by distilling off methyl isobutyl ketone and the like under reduced pressure at 180 ° C. using a rotary evaporator. 189 parts of (EP17) were obtained. The epoxy equivalent of the obtained epoxy resin is 241 g / eq. The softening point was 85.3 ° C., the ICI melt viscosity was 0.15 Pa · s (150 ° C.), the total chlorine content was 460 ppm, the hydrolyzable chlorine was 394 ppm, the chlorine ions were 0.6 ppm, and the sodium ions were 0.7 ppm. The structure of the formula (1) was 69.5 area% (GPC), and the epoxidized biphenol was 15.0 area% (GPC). Further, the compound (a) of the formula (1) and the epoxidized product (b) of biphenol are (a) / (b) = 4.6 by weight ratio and 2.73 in molar ratio. About other structures, the compound of the said Formula (1), biphenols, and the compound which the compound of the said Formula (1) and biphenol mixed and couple | bonded were included.
撹拌機、還流冷却管、撹拌装置を備えた1Lの4つ口フラスコにフェノール化合物(イギリス特許1,158,606 example7に記載の手法に準拠して合成 純度99%以上 残留フェノールフタレイン14ppm、鉄分<5ppm、融点289-290℃)126部、ビフェノール34部、エピクロロヒドリン463部、ジメチルスルホキシド116部を加え、水浴を50℃にまで昇温した。内温が45℃を越えたところでフレーク状の水酸化ナトリウム43部を90分かけて分割添加した後、更に45℃で2時間、70℃で1時間後反応を行った。反応終了後、ロータリーエバポレータを用いて140℃で減圧下、過剰のエピクロルヒドリン等の溶剤を留去した。残留物にメチルイソブチルケトン600部を加え溶解し、水洗により生成した塩化ナトリウム等を除去後、有機層を70℃にまで昇温し、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、洗浄水が中性になるまで水洗を行い、得られた溶液を、ロータリーエバポレータを用いて180℃で減圧下にメチルイソブチルケトン等を留去することでエポキシ樹脂(EP18)を190部得た。得られたエポキシ樹脂のエポキシ当量は235g/eq.、軟化点が93.0℃、ICI溶融粘度0.09Pa・s(150℃)、全塩素量 467ppm、加水分解性塩素 388ppm、塩素イオン0.3ppm、ナトリウムイオン0.4ppmであった。また前記式(1)の構造は65.0面積%(GPC)、ビフェノールのエポキシ化物は18.6面積%(GPC)であった。さらに、前記式(1)の化合物(a)とビフェノールのエポキシ化物(b)は重量比で(a)/(b)=3.5、モル比率2.08である。他構造については前記式(1)の化合物同士、ビフェノール同士、前記式(1)の化合物とビフェノールが混在して結合した化合物を含むものであった。 Example 19
A 1-L four-necked flask equipped with a stirrer, a reflux condenser, and a stirrer is charged with a phenol compound (based on the method described in British Patent 1,158,606 example7, purity 99% or more, residual phenolphthalein 14 ppm, iron content <5 ppm, melting point 289-290 ° C.) 126 parts, biphenol 34 parts, epichlorohydrin 463 parts, dimethyl sulfoxide 116 parts were added, and the temperature of the water bath was raised to 50 ° C. When the internal temperature exceeded 45 ° C., 43 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 45 ° C. for 2 hours and at 70 ° C. for 1 hour. After completion of the reaction, excess solvent such as epichlorohydrin was distilled off under reduced pressure at 140 ° C. using a rotary evaporator. After adding 600 parts of methyl isobutyl ketone to the residue and dissolving it, removing sodium chloride and the like produced by washing with water, the organic layer was heated to 70 ° C., and 10 parts of a 30 wt% aqueous sodium hydroxide solution were added with stirring. After reacting for 1 hour, washing is carried out until the washing water becomes neutral, and the resulting solution is epoxy resin by distilling off methyl isobutyl ketone and the like under reduced pressure at 180 ° C. using a rotary evaporator. 190 parts of (EP18) were obtained. The epoxy equivalent of the obtained epoxy resin was 235 g / eq. The softening point was 93.0 ° C., ICI melt viscosity 0.09 Pa · s (150 ° C.), total chlorine amount 467 ppm, hydrolyzable chlorine 388 ppm, chlorine ion 0.3 ppm, sodium ion 0.4 ppm. The structure of the formula (1) was 65.0 area% (GPC), and the epoxidized biphenol was 18.6 area% (GPC). Further, the compound (a) of the formula (1) and the epoxidized product (b) of biphenol are (a) / (b) = 3.5 by weight ratio and 2.08 molar ratio. About other structures, the compound of the said Formula (1), biphenols, and the compound which the compound of the said Formula (1) and biphenol mixed and couple | bonded were included.
撹拌機、還流冷却管、撹拌装置を備えた1Lの4つ口フラスコにフェノール化合物(イギリス特許1,158,606 example7に記載の手法に準拠して合成 純度99%以上 残留フェノールフタレイン14ppm、鉄分<5ppm、融点289-290℃)102部、ビフェノール45部、エピクロロヒドリン462部、ジメチルスルホキシド116部を加え、水浴を50℃にまで昇温した。内温が45℃を越えたところでフレーク状の水酸化ナトリウム44部を90分かけて分割添加した後、更に45℃で2時間、70℃で1時間後反応を行った。反応終了後、ロータリーエバポレータを用いて140℃で減圧下、過剰のエピクロルヒドリン等の溶剤を留去した。残留物にメチルイソブチルケトン505部を加え溶解し、水洗により生成した塩化ナトリウム等を除去後、有機層を70℃にまで昇温し、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、洗浄水が中性になるまで水洗を行い、得られた溶液を、ロータリーエバポレータを用いて180℃で減圧下にメチルイソブチルケトン等を留去することでエポキシ樹脂(EP19)を177部得た。得られたエポキシ樹脂のエポキシ当量は220g/eq.、軟化点が109℃、ICI溶融粘度0.03Pa・s(150℃)、全塩素量 457ppm、加水分解性塩素 401ppm、塩素イオン0.9ppm、ナトリウムイオン0.8ppmであった。また前記式(1)の構造は58.0面積%(GPC)、ビフェノールのエポキシ化物は26.8面積%(GPC)であった。さらに、前記式(1)の化合物(a)とビフェノールのエポキシ化物(b)は重量比で(a)/(b)=2.2、モル比率1.31である。他構造については前記式(1)の化合物同士、ビフェノール同士、前記式(1)の化合物とビフェノールが混在して結合した化合物を主として含むものであった。 Comparative Example 13
A 1-L four-necked flask equipped with a stirrer, a reflux condenser, and a stirrer is charged with a phenol compound (based on the method described in British Patent 1,158,606 example7, purity 99% or more, residual phenolphthalein 14 ppm, iron content <5 ppm, melting point 289-290 ° C.) 102 parts, biphenol 45 parts, epichlorohydrin 462 parts, dimethyl sulfoxide 116 parts were added, and the temperature of the water bath was raised to 50 ° C. When the internal temperature exceeded 45 ° C., 44 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by further reaction at 45 ° C. for 2 hours and at 70 ° C. for 1 hour. After completion of the reaction, excess solvent such as epichlorohydrin was distilled off under reduced pressure at 140 ° C. using a rotary evaporator. 505 parts of methyl isobutyl ketone is added to the residue and dissolved, and after removing sodium chloride and the like produced by washing with water, the organic layer is heated to 70 ° C., and 10 parts of 30 wt% aqueous sodium hydroxide solution is added with stirring. After reacting for 1 hour, washing is carried out until the washing water becomes neutral, and the resulting solution is epoxy resin by distilling off methyl isobutyl ketone and the like under reduced pressure at 180 ° C. using a rotary evaporator. 177 parts of (EP19) were obtained. The epoxy equivalent of the obtained epoxy resin is 220 g / eq. The softening point was 109 ° C., the ICI melt viscosity was 0.03 Pa · s (150 ° C.), the total chlorine amount was 457 ppm, the hydrolyzable chlorine was 401 ppm, the chlorine ion was 0.9 ppm, and the sodium ion was 0.8 ppm. The structure of the formula (1) was 58.0 area% (GPC), and the epoxidized biphenol was 26.8 area% (GPC). Furthermore, the compound (a) of the formula (1) and the epoxidized product (b) of biphenol are (a) / (b) = 2.2 by weight ratio and 1.31 molar ratio. The other structures mainly include compounds in which the compound of the formula (1), biphenols, and a compound in which the compound of the formula (1) and biphenol are mixed and bonded.
実施例18、19及び比較例13で得られたエポキシ樹脂混合物(EP17、EP18、EP19)を使用し、硬化剤としてビフェニルタイプフェノールアラルキル樹脂(日本化薬製 KAYAHARD GPH-65)を等当量で配合し、硬化促進剤(トリフェニルフォスフィン 北興化学製)をエポキシ樹脂の重量に対し1%添加し、ミキシングロールを用いて均一に混合・混練し、エポキシ樹脂組成物を得た。このエポキシ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エポキシ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、収縮率と耐熱性を評価した。収縮率は得られた成型物の金型との差を測定することによって成型収縮の大きさを確認した。耐熱性は以下の要領で測定した。 Examples 20 to 21 and Comparative Example 14
Using the epoxy resin mixture (EP17, EP18, EP19) obtained in Examples 18 and 19 and Comparative Example 13, biphenyl type phenol aralkyl resin (KAYAHARD GPH-65 manufactured by Nippon Kayaku Co., Ltd.) is blended in an equivalent equivalent amount as a curing agent. Then, a curing accelerator (triphenylphosphine manufactured by Hokuko Chemical Co., Ltd.) was added at 1% with respect to the weight of the epoxy resin, and uniformly mixed and kneaded using a mixing roll to obtain an epoxy resin composition. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy 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 this test specimen for evaluation, the shrinkage rate and heat resistance were evaluated. The degree of shrinkage was confirmed by measuring the difference between the mold and the mold of the obtained molding. The heat resistance was measured as follows.
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
<硬化収縮>
JISK-6911(成型収縮率)に準拠 <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 <curing shrinkage>
Compliant with JISK-6911 (mold shrinkage)
前述の実施例6の組成の本発明のエポキシ樹脂組成物において耐半田クラック性の試験を行った。表面が金属の銅製の図1に示す96PinQFP(チップサイズ:7×7×厚み0.1mm、パッケージサイズ:14×14×厚み1.35mm)リードフレーム(使用前にアセトンで十分に表面をふき、汚れを取った物を使用)耐半田クラック性評価用リードフレームとし、リードフレームをトランスファー成型金型にセットし、上記同様にしてタブレット化したエポキシ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、耐半田クラック性の試験評価用試験片を3サンプル得た(図2)。得られた3つの試験片について60℃/85%RHの相対湿度に設定された恒温槽中に5時間放置し吸湿させ、さらにこの吸湿後、280℃×10秒間の半田リフロー試験を行った。この時の熱衝撃によって生じるパッケージクラックについて目視によってクラックの発生を確認したが、いずれのサンプルにもクラックは見当たらなかった。 Example 22
The epoxy resin composition of the present invention having the composition of Example 6 was tested for solder crack resistance. 96PinQFP (chip size: 7 × 7 × thickness 0.1 mm, package size: 14 × 14 × thickness 1.35 mm) lead frame (surface is sufficiently wiped with acetone before use, as shown in FIG. (Use a soiled product) Use a lead frame for solder crack resistance evaluation, set the lead frame in a transfer mold and transfer the tableted epoxy resin composition in the same way as above (175 ° C x 60 seconds) Further, after demolding, three samples were obtained for test evaluation for curing and solder crack resistance under conditions of 160 ° C. × 2 hours + 180 ° C. × 6 hours (FIG. 2). The obtained three test pieces were allowed to stand for 5 hours in a thermostat set to a relative humidity of 60 ° C./85% RH for moisture absorption, and after this moisture absorption, a solder reflow test at 280 ° C. for 10 seconds was performed. The generation of cracks was visually confirmed for the package cracks caused by the thermal shock at this time, but no cracks were found in any of the samples.
実施例18、19で得られた本発明のエポキシ樹脂混合物(EP18、19)と硬化剤(フェノールノボラック(明和化成工業(株)製 H-1))を等当量で配合し、硬化触媒(硬化促進剤)としてトリフェニルフォスフィン(北興化学(株)製 TPP)をエポキシ樹脂の重量に対し、1%添加し、ミキシングロールを用いて均一に混合・混練し、封止用エポキシ樹脂組成物を得た。このエポキシ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エポキシ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。評価結果を表9に示す。 Examples 23 and 24
The epoxy resin mixture of the present invention (EP18, 19) obtained in Examples 18 and 19 and a curing agent (phenol novolak (H-1 manufactured by Meiwa Kasei Kogyo Co., Ltd.)) were blended in equal equivalents, and a curing catalyst (curing) Add 1% of triphenylphosphine (TPP manufactured by Hokuko Chemical Co., Ltd.) as the accelerator) to the weight of the epoxy resin, and mix and knead uniformly using a mixing roll to obtain an epoxy resin composition for sealing. Obtained. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy 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. Table 9 shows the evaluation results.
耐熱性・寸法安定性(線膨張変化率)
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 <TMA measurement conditions>
Heat resistance and dimensional stability (linear expansion rate)
Thermo-mechanical measuring device manufactured by TA-instruments, Q400EM
Measurement temperature range: 40 ° C-280 ° C
Temperature increase rate: 2 ° C / min
動的粘弾性測定器:TA-instruments製、DMA-2980
測定温度範囲:-30℃~280℃
温速度:2℃/分
試験片サイズ:5mm×50mmに切り出した物を使用した(厚みは約800μm)。
解析条件Tg:DMA測定に於けるTanδのピーク点(tanδMAX)をTgとした。
<誘電率、誘電正接>
空洞共振器を使用し、関東電子応用化学製 1GHz用の治具を用いて測定(0.5mmx70mmに切り出したものを使用)
<曲げ試験>
・JIS K 6911に準拠 室温で120℃でテストを行った
<ピール強度>
・180℃剥離試験 JIS K-6854-2に準拠 圧延銅箔使用
<吸水・吸湿率>
・85℃85%の高温高湿槽にて24時間放置後の重量増加%で評価
<KIC:破壊強靭性試験>
・コンパクテンション ASTME-399に準拠 <DMA measurement conditions>
Dynamic viscoelasticity measuring device: manufactured by TA-instruments, DMA-2980
Measurement temperature range: -30 ° C to 280 ° C
Temperature rate: 2 ° C./min Test piece size: 5 mm × 50 mm cut out (thickness is about 800 μm).
Analysis condition Tg: Tanδ peak point (tanδMAX) in DMA measurement was defined as Tg.
<Dielectric constant, dielectric loss tangent>
Measured using a cavity resonator and a 1 GHz jig manufactured by Kanto Denshi Kagaku Kagaku (using one cut into 0.5 mm x 70 mm)
<Bending test>
・ Compliant with JIS K 6911 Tested at 120 ° C. at room temperature <Peel strength>
180 ° C peel test JIS K-6854-2 compliant Use of rolled copper foil <Water absorption / moisture absorption>
・ Evaluation based on weight increase after standing for 24 hours in a high-temperature and high-humidity tank at 85 ° C. and 85% <KIC: fracture toughness test>
・ Compact compliant with ASTME-399
なお、本出願は、2013年9月10日付で出願された日本国特許出願(特願2013-186859)及び2014年7月14日付で出願された日本国特許出願(特願2014-143791)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。 Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on the Japanese patent application filed on September 10, 2013 (Japanese Patent Application No. 2013-186859) and the Japanese patent application filed on July 14, 2014 (Japanese Patent Application No. 2014-143791). Which is incorporated by reference in its entirety. Also, all references cited herein are incorporated as a whole.
In the epoxy resin mixture of the present invention, 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.
Claims (7)
- 下記式(1)で表される化合物を60~75%(ゲルパーミエーションクロマトグラフィー 面積%)、及び、ビフェノールのエポキシ化物を5~30%(同上)含有するエポキシ樹脂混合物。
- 軟化点が80~100℃である請求項1に記載のエポキシ樹脂混合物。 The epoxy resin mixture according to claim 1, having a softening point of 80 to 100 ° C.
- 150℃におけるICI溶融粘度(コーンプレート法)が0.08~0.35Pa・sである請求項1又は請求項2に記載のエポキシ樹脂混合物。 The epoxy resin mixture according to claim 1 or 2, wherein the ICI melt viscosity (cone plate method) at 150 ° C is 0.08 to 0.35 Pa · s.
- 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と硬化剤を含有するエポキシ樹脂組成物。 An epoxy resin composition comprising the epoxy resin mixture according to any one of claims 1 to 3 and a curing agent.
- 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と硬化触媒を含有するエポキシ樹脂組成物。 An epoxy resin composition comprising the epoxy resin mixture according to any one of claims 1 to 3 and a curing catalyst.
- 請求項4又は5に記載のエポキシ樹脂組成物を硬化した硬化物。 Hardened | cured material which hardened | cured the epoxy resin composition of Claim 4 or 5.
- 半導体チップを請求項4又は5に記載のエポキシ樹脂組成物を用いて封止して得られる半導体装置。 A semiconductor device obtained by sealing a semiconductor chip with the epoxy resin composition according to claim 4 or 5.
Priority Applications (3)
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JP2015536583A JP6366590B2 (en) | 2013-09-10 | 2014-09-09 | Epoxy resin mixture, epoxy resin composition, cured product, and semiconductor device |
KR1020167001855A KR20160053907A (en) | 2013-09-10 | 2014-09-09 | Epoxy resin mixture, epoxy resin composition, cured product and semiconductor device |
CN201480049986.XA CN105531297A (en) | 2013-09-10 | 2014-09-09 | Epoxy resin mixture, epoxy resin composition, cured product and semiconductor device |
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JP2014143791 | 2014-07-14 |
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PCT/JP2014/073807 WO2015037584A1 (en) | 2013-09-10 | 2014-09-09 | Epoxy resin mixture, epoxy resin composition, cured product and semiconductor device |
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JP (1) | JP6366590B2 (en) |
KR (1) | KR20160053907A (en) |
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JP2016079366A (en) * | 2014-10-22 | 2016-05-16 | 味の素株式会社 | Resin composition |
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- 2014-09-09 CN CN201480049986.XA patent/CN105531297A/en active Pending
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Also Published As
Publication number | Publication date |
---|---|
KR20160053907A (en) | 2016-05-13 |
JPWO2015037584A1 (en) | 2017-03-02 |
TWI638850B (en) | 2018-10-21 |
CN105531297A (en) | 2016-04-27 |
JP6366590B2 (en) | 2018-08-01 |
TW201522486A (en) | 2015-06-16 |
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