WO2015037584A1 - Mélange de résines époxy, composition de résine époxy, produit durci et dispositif semi-conducteur - Google Patents

Mélange de résines époxy, composition de résine époxy, produit durci et dispositif semi-conducteur Download PDF

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Publication number
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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epoxy resin
resin composition
parts
ppm
biphenol
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PCT/JP2014/073807
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English (en)
Japanese (ja)
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政隆 中西
篤彦 長谷川
昌照 木村
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日本化薬株式会社
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Priority to JP2015536583A priority Critical patent/JP6366590B2/ja
Priority to KR1020167001855A priority patent/KR20160053907A/ko
Priority to CN201480049986.XA priority patent/CN105531297A/zh
Publication of WO2015037584A1 publication Critical patent/WO2015037584A1/fr

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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
    • 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
    • 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

Cette invention concerne un mélange de résines époxy capable simultanément de satisfaire des propriétés telles que permettre d'obtenir un produit durci ayant une excellente résistance à la chaleur tout en ayant également une excellente résistance mécanique, résistance à la flamme et un module élastique de température élevé et un mélange ayant une basse viscosité avant le durcissement, des propriétés qui sont en contradiction avec ladite résistance à la chaleur. Le mélange contient de 30 à 75 % (% aire chromatographique par perméation de gel) d'un composé représenté par la formule (1) et de 5 à 30 % (comme ci-dessus) d'un époxyde de biphénol. (1) (Dans la formule, G représente un groupe glycidyle et R représente un atome d'hydrogène, etc.).
PCT/JP2014/073807 2013-09-10 2014-09-09 Mélange de résines époxy, composition de résine époxy, produit durci et dispositif semi-conducteur WO2015037584A1 (fr)

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KR1020167001855A KR20160053907A (ko) 2013-09-10 2014-09-09 에폭시 수지 혼합물, 에폭시 수지 조성물, 경화물 및 반도체 장치
CN201480049986.XA CN105531297A (zh) 2013-09-10 2014-09-09 环氧树脂混合物、环氧树脂组合物、固化物和半导体装置

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WO2016014536A1 (fr) * 2014-07-22 2016-01-28 Sabic Global Technologies B.V. Monomères à chaleur élevée et leurs procédés d'utilisation
WO2016031643A1 (fr) * 2014-08-26 2016-03-03 日本化薬株式会社 Composé de polyester réactif et composition de résine durcissable par rayons d'énergie active l'utilisant
JP2016079366A (ja) * 2014-10-22 2016-05-16 味の素株式会社 樹脂組成物
JP2017071706A (ja) * 2015-10-08 2017-04-13 日本化薬株式会社 エポキシ樹脂組成物、硬化性樹脂組成物およびその硬化物
JPWO2016147735A1 (ja) * 2015-03-18 2018-01-25 三菱瓦斯化学株式会社 樹脂組成物、プリプレグ、金属箔張積層板、樹脂シート、及びプリント配線板
WO2018057057A1 (fr) * 2016-09-26 2018-03-29 Sabic Global Technologies B.V. Compositions composites homogènes amorphes à base de mélanges d'époxy à haute température, articles et leurs utilisations
WO2018057056A1 (fr) * 2016-09-26 2018-03-29 Sabic Global Technologies B.V. Mélanges d'époxy à haute température amorphes homogènes, articles et leurs utilisations
WO2018058116A1 (fr) * 2016-09-26 2018-03-29 Sabic Global Technologies B.V. Compositions époxy haute température et haute ténacité, articles, et leurs utilisations
WO2018057055A1 (fr) * 2016-09-26 2018-03-29 Sabic Global Technologies B.V. Compositions de composite haute température, articles et leurs utilisations
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WO2020175038A1 (fr) * 2019-02-28 2020-09-03 日本ゼオン株式会社 Composition de résine, film de résine et composant électronique
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JPWO2022118723A1 (fr) * 2020-12-03 2022-06-09
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