WO2011114687A1 - 半導体封止用樹脂組成物およびこれを用いた半導体装置 - Google Patents
半導体封止用樹脂組成物およびこれを用いた半導体装置 Download PDFInfo
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- WO2011114687A1 WO2011114687A1 PCT/JP2011/001460 JP2011001460W WO2011114687A1 WO 2011114687 A1 WO2011114687 A1 WO 2011114687A1 JP 2011001460 W JP2011001460 W JP 2011001460W WO 2011114687 A1 WO2011114687 A1 WO 2011114687A1
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- epoxy resin
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- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3218—Carbocyclic compounds
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- 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
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
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- 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
- C08G59/40—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 curing agents used
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- C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
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Definitions
- the present invention relates to a semiconductor sealing resin composition and a semiconductor device using the same.
- Semiconductor devices are sealed for the purpose of protecting semiconductor elements, ensuring electrical insulation, and facilitating handling.
- the sealing of semiconductor elements is mainly performed by transfer molding of an epoxy resin composition because it is excellent in productivity, cost, reliability, and the like.
- In order to meet market demands for smaller, lighter, and higher performance electronic devices not only high integration of semiconductor elements, miniaturization and high density of semiconductor devices, but also new bonding technologies such as surface mounting It has been developed and put into practical use. Such technical trends have spread to resin compositions for semiconductor encapsulation, and the required performance has become more sophisticated and diversified year by year.
- solder used for surface mounting is being switched to lead-free solder due to environmental issues.
- the melting point of lead-free solder is higher than that of conventional lead / tin solder, and the reflow mounting temperature is increased from 220 ° C. to 240 ° C. to 240 ° C. to 260 ° C.
- solder resistance may be insufficient.
- bromine-containing epoxy resins and antimony oxide are used as flame retardants for the purpose of imparting flame retardancy to conventional sealing resin compositions, but these have been used from the viewpoint of environmental protection and safety improvement in recent years. The momentum to eliminate these compounds is increasing.
- Patent Document 1 As a conventional technique, by using a semiconductor resin substrate containing an epoxy resin having a naphthalene skeleton and a phenol resin curing agent having a naphthalene skeleton, a technique for improving high-temperature storage characteristics and solder resistance (for example, Patent Document 1) 2) and a method for improving high-temperature storage characteristics and flame resistance by blending a phosphoric acid-containing compound (for example, see Patent Documents 3 and 4).
- Patent Documents 3 and 4 a technique for improving high-temperature storage characteristics and solder resistance
- these may not have a sufficient balance of continuous formability, adhesion resistance, flame resistance, and solder resistance.
- a sealing resin composition that satisfies a good balance of continuous moldability, flame resistance, solder resistance, and high-temperature storage characteristics is required.
- JP 2007-031691 A Japanese Patent Laid-Open No. 06-216280 JP 2006-161055 A JP 2006-176792 A
- the present invention is a sealing resin having a higher level of continuous moldability, adhesion resistance, flame resistance, solder resistance and high temperature storage characteristics than the conventional level.
- the present invention provides a composition and a highly reliable semiconductor device using the encapsulating resin composition.
- the epoxy resin (A) has the formula (1): (In the formula (1), R1 is a hydrocarbon group having 1 to 6 carbon atoms, and R2 is a hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, which are the same as each other.
- An epoxy resin (A-1) represented by Resin composition for semiconductor encapsulation, wherein the epoxy resin (A-1) comprises a component where n ⁇ 1 in the formula (1) and a component (a1) where n 0 in the formula (1) Is provided.
- the peak intensity of the component (a1) measured by FD-MS is relative to the entire peak of the epoxy resin (A-1).
- P 2 / P 1 is 0.1 or more and 1.0 or less.
- the peak of the component (a1) relative to the total peak area of the epoxy resin (A-1) obtained by gel permeation chromatography is 70 area% or more and 95 area% or less.
- the ICI viscosity of the epoxy resin (A-1) at 150 ° C. is 0.1 dPa ⁇ sec or more and 3.0 dPa ⁇ sec or less. .
- the epoxy resin (A-1) in the semiconductor sealing resin composition, has a softening point at 150 ° C. of 55 ° C. or higher and 90 ° C. or lower.
- the epoxy equivalent of the epoxy resin (A-1) is 210 g / eq or more and 250 g / eq or less.
- the curing agent (B) is a phenol resin-based curing agent.
- the phenol resin-based curing agent in the resin composition for semiconductor encapsulation, includes a phenol resin (B-1) having two or more phenol skeletons, and a hydroxynaphthalene skeleton or dihydroxynaphthalene. And at least one resin selected from the group consisting of naphthol resins (B-2) having a skeleton.
- the phenol resin curing agent is: Phenol resin (b1) represented by formula (2): (In the formula (2), R3 is a hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, which may be the same or different, and c1 is 0 to 4 C2 is an integer of 0 to 3, which may be the same or different from each other, d is an integer of 1 to 10, e is an integer of 0 to 10, and the number of repetitions The structural unit represented by d and the structural unit represented by the number of repetitions e may be continuously arranged, alternately arranged with each other, or randomly arranged).
- Naphthol resin (b2) represented by formula (3):
- R4 is a hydroxyl group or a hydrogen atom
- R5 is a hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, which may be the same or different from each other
- R6 is a hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, which may be the same or different from each other
- f is an integer of 0 to 3
- G is an integer of 0 to 5
- h is an integer of 1 to 2
- m and n are each independently an integer of 1 to 10, m + n ⁇ 2, and represented by a repetition number m.
- the structural unit represented by the number of repeating units n and the structural unit represented by the repeating number n may be arranged in succession, alternately arranged with each other, or randomly arranged with each other. CH 2 -. which is interposed), and naphthol resin (b represented by formula (4) ):
- R7 is a hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, which may be the same or different
- k1 is 0 to 6
- K2 is an integer of 0 to 4, which may be the same or different from each other
- s is an integer of 0 to 10
- t is an integer of 1 to 2).
- the semiconductor sealing resin composition at least one selected from the group consisting of the phenol resin (b1), the naphthol resin (b2), and the naphthol resin (b3).
- the amount of the resin is 50 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the curing agent (B).
- the amount of the inorganic filler (C) is 70% by mass or more and 93% based on the total mass of the semiconductor sealing resin composition. It is below mass%.
- the amount of the epoxy resin (A-1) is 50 parts by mass or more, 100 parts by mass with respect to 100 parts by mass of the epoxy resin (A). It is below mass parts.
- the semiconductor sealing resin composition further includes a curing accelerator (D).
- the curing accelerator (D) in the resin composition for semiconductor encapsulation, includes a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, a phosphonium compound, It contains at least one curing accelerator selected from the group consisting of adducts with silane compounds.
- the resin composition for encapsulating a semiconductor further includes a compound (E) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring.
- the semiconductor sealing resin composition further includes a coupling agent (F).
- the semiconductor sealing resin composition further includes an inorganic flame retardant (G).
- G inorganic flame retardant
- a semiconductor device including a semiconductor element encapsulated with the above semiconductor encapsulating resin composition.
- the present invention exhibits flame resistance without using halogen compounds and antimony compounds, and has a higher level than before, and has excellent balance of continuous formability, adhesion resistance, solder resistance and high temperature storage characteristics.
- a highly reliable semiconductor device using the resin composition and the sealing resin composition can be obtained.
- the resin composition for semiconductor encapsulation of the present invention comprises an epoxy resin (A), a curing agent (B), and an inorganic filler (C),
- the epoxy resin (A) has the formula (1): (In the formula (1), R1 is a hydrocarbon group having 1 to 6 carbon atoms, and R2 is a hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, which are the same as each other. And may be different, a is an integer of 0 to 4, b is an integer of 0 to 4, and n is an integer of 0 or more.)
- the epoxy resin (A-1) represented by these is included.
- the semiconductor device of this invention is characterized by including the semiconductor element sealed with the hardened
- epoxy resin (A) the phenolphthalein type epoxy resin represented by the formula (1) (hereinafter referred to as “epoxy resin (A-1)”) May be used).
- the epoxy resin (A-1) has a basic skeleton in which a phenol nucleus is directly bonded to a phthalic anhydride skeleton. For this reason, the rotational motion of the phenol nucleus is limited, and the toughness and heat resistance of the resulting resin composition are improved.
- the phthalic anhydride skeleton is bulky and has an aromatic structure, the elastic modulus of the resulting resin composition is reduced in a high temperature range, a quick foam layer is formed in a combustion test, and better flame resistance Is obtained.
- Such characteristics derived from the phthalic anhydride skeleton structure also contribute to the improvement of solder resistance of the obtained resin composition.
- the epoxy resin (A-1) includes a component having a polymerization degree n ⁇ 1 which is a polyfunctional component, and thus the solder resistance is remarkably improved.
- n + 1 highly polar lactone structures are contained in one molecule, so that a chelate interaction with the metal surface is developed, and further, (n + 2) epoxy groups are included, thereby cross-linking density at the metal interface.
- the adhesion to the metal is considered to be improved.
- Another reason is considered to be that the hydroxyl group of the linker is replaced with an epoxy group, resulting in low water absorption as compared with a normal bisphenol type epoxy resin.
- Component (a1) has a structure containing a phthalic anhydride skeleton and a phenol nucleus bound thereto. The phenol nucleus is strongly bonded to the phthalic anhydride skeleton, and the phenol nucleus cannot rotate freely.
- the water absorption of the resin composition can be reduced, and the toughness and heat resistance can be improved.
- the polar structure such as carbonyl structure and ether structure in the molecule improves the adhesion to the metal surface, and together with the low water absorption and low thermal modulus, the solder resistance of the semiconductor encapsulated package is further improved.
- the elastic modulus in the high temperature range is reduced, a quick foam layer can be formed in the combustion test, and better flame resistance can be obtained.
- n in the formula (1) can be obtained by field desorption mass spectrometry (FD-MS). For each peak detected by FD-MS analysis measured in the detected mass (m / z) range of 50 to 2000, the molecular weight and the number of repetitions n can be obtained from the detected mass (m / z). Each n component can be identified by collating with each peak in GPC measurement. Furthermore, the content ratio (mass ratio) of each component can be determined from the intensity ratio of each peak.
- FD-MS field desorption mass spectrometry
- the content ratio of these components in the epoxy resin (A-1) can be calculated from the ratio of the peak intensity of FD-MS.
- the epoxy resin (A-1) may be any polyfunctional component having a structure with a polymerization degree n ⁇ 1, and the glycidyl ether in the n repeating unit structures in the formula (1) is glycidylated. It may contain a component which is a hydroxyl group.
- the ratio P 2 / P 1 of the peak intensity P 2 of the component (a2) to the peak intensity P 1 of the component (a1) measured by FD-MS is preferably 0.1 or more and 1.0 or less. More preferably, it is 0.3 or more and 0.8 or less.
- the content ratio of the component (a1) in the epoxy resin (A-1) is 70 area% or more with respect to the total peak area of the epoxy resin (A-1) in gel permeation chromatography (GPC) measurement. Is more preferable, and 80% by area or more is more preferable.
- the lower limit of the content rate of a component (a1) is in said range, the fluidity
- the upper limit of the content rate of a component (a1) is 95 area% or less by gel permeation chromatography (GPC) measurement, and it is further more preferable that it is 90 area% or less.
- the upper limit of the content ratio of the monomer component is within the above range, the balance between the flow characteristics and curability of the resin composition is good, and the continuous moldability is good.
- the viscosity of the epoxy resin (A-1) is preferably 0.1 dPa ⁇ sec or more and 3.0 dPa ⁇ sec or less, and 0.2 dPa ⁇ sec or more and 2.0 dPa ⁇ sec in ICI viscosity measurement at 150 ° C. More preferably, it is 0.3 dPa * sec or more and 1.5 dPa * sec or less.
- the lower limit value of the ICI viscosity is within the above range, the curability and flame resistance of the resin composition are good.
- the upper limit is within the above range, the fluidity of the resin composition is good.
- the ICI viscosity is M.M. S. tea. It can be measured using an ICI cone plate viscometer manufactured by Engineering Co., Ltd.
- the softening point of the epoxy resin (A-1) at 150 ° C. is preferably 55 ° C. or higher and 90 ° C. or lower, and more preferably 65 ° C. or higher and 80 ° C. or lower.
- the resin composition has good adhesion resistance.
- the upper limit is not more than the above range, the fluidity of the resin composition becomes good.
- the epoxy equivalent of the epoxy resin (A-1) is preferably 210 g / eq or more and 250 g / eq or less, and more preferably 225 g / eq or more and 240 g / eq or less. When the epoxy equivalent is within the above range, the fluidity, curability and flame resistance of the resin composition are good.
- the epoxy resin (A-1) is obtained by a two-stage glycidylation reaction.
- a mixture containing phenolphthaleins and epihalohydrins and, if necessary, an organic solvent is heated and stirred at 60 to 100 ° C. to advance the etherification reaction of the phenolphthaleins and epihalohydrins
- Glycidylation is carried out by adding an alkali metal hydroxide sequentially or continuously under a temperature condition of 50 to 100 ° C., and the reaction is carried out at 50 to 100 ° C. in order to carry out the reaction sufficiently.
- the molecular weight of the intermediate of the target epoxy resin (A-1) can be controlled.
- an epihalohydrin is subjected to a glycidylation reaction 1 to 3 times the weight of phenolphthalein
- an intermediate product of an epoxy resin (A-1) containing n ⁇ 1 component can be synthesized.
- an intermediate is formed by reacting the product obtained in the first step with epihalohydrins in the presence of a quaternary ammonium salt and an alkali metal hydroxide at a temperature of 50 to 100 ° C.
- the alcoholic hydroxyl group of the product can be glycidylated.
- unreacted epihalohydrin is recovered by distillation, and an organic solvent such as toluene and methyl isobutyl ketone (MIBK) is added thereto, followed by a water washing-dehydration-filtration-desolvation step to obtain the desired epoxy resin.
- MIBK methyl isobutyl ketone
- a solvent such as dioxane or dimethyl sulfoxide (DMSO) may be used in the reaction.
- the phenolphthalein used as a raw material for the epoxy resin (A-1) is not particularly limited as long as it has a structure having a phthalic anhydride skeleton and two phenols bonded to a carbonyl group on one side.
- Examples of satisfying this condition include phenolphthalein, cresolphthalein, dimethoxyphenolphthalein, dichlorophenolphthalein, ⁇ -naphtholphthalein and the like. From the viewpoint of easy industrial availability, the use of phenolphthalein is particularly preferable. These phenolphthaleins can be used alone or in admixture of two or more.
- epichlorohydrin, epibromohydrin and the like can be used as the epihalohydrin, and epichlorohydrin which is easily available industrially is preferable.
- the amount of epihalohydrin used is preferably 1.0 mol or more and 8.0 mol or less, more preferably 2.0 mol or more and 5.0 mol or less with respect to 1 mol of the hydroxyl group of the phenolphthalein in the first stage reaction. preferable. When it is below the above range, the reaction becomes incomplete and the yield may be deteriorated. On the other hand, when it exceeds the above range, the cost may increase and the amount of chlorine contained in the product may increase.
- the second stage reaction 0.5 mol or more and 5.0 mol or less are preferable, and 1.0 mol or more and 3.0 mol or less are preferable with respect to 1 mol of the alcoholic hydroxyl group of the product of the first step reaction. More preferred.
- the reaction becomes incomplete and epoxidation of the alcoholic hydroxyl group is difficult.
- the above upper limit is exceeded, the cost may increase and the amount of chlorine contained in the product may increase.
- tetramethylammonium chloride, tetramethylammonium bromide, or the like can be used as the quaternary ammonium salt.
- the amount of the quaternary ammonium salt used is preferably 0.01 mol or more and 0.50 mol or less, preferably 0.03 mol or more and 0.20 mol with respect to 1 mol of the alcoholic hydroxyl group of the product of the first stage reaction. The following is more preferable.
- alkali metal hydroxide sodium hydroxide, potassium hydroxide or the like can be used, but sodium hydroxide is preferable.
- the amount of alkali metal hydroxide used is preferably 1 to 10 equivalents, more preferably 1 to 2 equivalents, relative to 1 equivalent of the hydroxyl group to be glycidylated.
- the alkali metal hydroxide may be solid or an aqueous solution.
- Epoxy resins that can be used in combination include novolac epoxy resins such as phenol novolac epoxy resins, cresol novolac epoxy resins, and triphenolmethane epoxy resins; phenol aralkyl epoxy resins having a phenylene skeleton, and phenol aralkyl epoxy having a biphenylene skeleton.
- Aralkyl-type epoxy resins such as resins; Naphthalene-type epoxy resins such as naphthol aralkyl-type epoxy resins having a phenylene skeleton, naphthol aralkyl-type epoxy resins having a biphenylene skeleton, and dihydroxynaphthalene-type epoxy resins; triglycidyl isocyanurate, monoallyl diglycidyl isocyan Triazine core-containing epoxy resin such as nurate; Bridged cyclic structure such as dicyclopentadiene-modified phenolic epoxy resin It includes hydrogen compound-modified phenol type epoxy resins.
- the epoxy equivalent is 100 g / eq or more and 500 g. / Eq or less is preferable. These may be used alone or in combination of two or more.
- the blending ratio of the epoxy resin (A-1) is 50 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the epoxy resin (A). Is preferably 60 parts by mass or more and 100 parts by mass or less, and particularly preferably 70 parts by mass or more and 100 parts by mass or less.
- the lower limit of the blending ratio is not less than the above range, the continuous moldability, adhesion resistance, flame resistance, solder resistance and high temperature storage characteristics are improved while maintaining good fluidity and curability of the resin composition. be able to.
- the lower limit of the blending ratio of the entire epoxy resin is not particularly limited, but is preferably 2% by mass or more and more preferably 4% by mass or more in the total resin composition. Sufficient fluidity
- liquidity can be acquired as the lower limit of a mixture ratio is more than the said range.
- the upper limit of the blending ratio of the entire epoxy resin is not particularly limited, but is preferably 15% by mass or less, and more preferably 13% by mass or less in the entire resin composition. When the upper limit value of the blending ratio is not more than the above range, good solder resistance can be obtained.
- the curing agent (B) used in the resin composition for semiconductor encapsulation of the present invention may be a phenol resin curing agent.
- the phenol resin-based curing agent of the present invention has a phenol resin (B-1) having a repeating unit structure containing two or more phenol skeletons (hereinafter sometimes referred to as “phenol resin (B-1)”) and hydroxy.
- phenol resin (B-1) a phenol resin having a repeating unit structure containing two or more phenol skeletons
- B-1 phenol resin
- the resin composition Due to the synergistic effect of using the epoxy resin (A-1) in combination with these phenol resin curing agents, the resin composition has an excellent balance of solder resistance, high-temperature storage characteristics, high adhesion and continuous moldability. Can be.
- Phenol resin (B-1) is preferable from the viewpoint of high temperature storage characteristics and continuous moldability of the resin composition, and naphthol resin (B-2) is preferable from the viewpoint of flow characteristics and solder resistance. It is preferable to select the phenol resin curing agent in accordance with the characteristics required for the resin composition for semiconductor encapsulation.
- the hydroxyl group equivalent of the phenol resin-based curing agent is 80 g / eq or more and 400 g / eq or less. It is preferable that it is 90 g / eq or more and 210 g / eq or less.
- the hydroxyl equivalent is within this range, the crosslink density of the cured product of the resin composition is increased, and the cured product can have high heat resistance.
- the phenol resin (B-1) is not particularly limited as long as it has a repeating unit structure containing two benzene rings to which a phenolic hydroxyl group is bonded.
- phenols and acetylaldehydes are essential raw materials.
- a phenol resin (b1) represented by the formula (2) those having an average value of d of 1 or more are particularly preferable because of excellent continuous moldability. Examples of such compounds include MEH-7500 manufactured by Meiwa Kasei Co., Ltd., HE910-20 manufactured by Air Water Co., Ltd., and the like as commercial products.
- R3 is a hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, which may be the same or different, and c1 is 0 to 4 C2 is an integer of 0 to 3, which may be the same or different from each other, d is an integer of 1 to 10, e is an integer of 0 to 10, and the repetition number d And the structural unit represented by the number of repetitions e may be continuously arranged, alternately arranged with each other, or randomly arranged.
- the naphthol resin (B-2) is not particularly limited as long as it has a structure having a hydroxynaphthalene skeleton or a dihydroxynaphthalene skeleton, but has a structure represented by the formula (3) from the viewpoint of heat resistance.
- the naphthol resin (b2) and / or the naphthol resin (b3) represented by the formula (4) is more preferable, and the naphthol resin (b3) represented by the formula (4) is particularly preferable.
- R4 of the naphthol resin (b2) is preferably a hydroxyl group from the viewpoints of curability and continuous moldability, and is preferably a hydrogen atom from the viewpoints of solder resistance and flame resistance.
- R4 is a hydroxyl group or a hydrogen atom
- R5 is a hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, which may be the same or different from each other
- R6 is a hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, which may be the same or different from each other
- f is an integer of 0 to 3
- G is an integer of 0 to 5
- h is an integer of 1 to 2
- m and n are each independently an integer of 1 to 10, m + n ⁇ 2, and represented by a repetition number m.
- the structural unit represented by the number of repeating units n and the structural unit represented by the repeating number n may be arranged in succession, alternately arranged with each other, or randomly arranged with each other. CH 2- intervenes.
- R7 is a hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, which may be the same or different, and k1 is 0 to 6 And k2 is an integer of 0 to 4, which may be the same or different from each other, s is an integer of 0 to 10, and t is an integer of 1 to 2.
- the resin composition for encapsulating a semiconductor of the present invention can be used in combination with another curing agent as long as the effect of using the curing agent (B) is not impaired.
- curing agent which can be used together,
- curing agent etc. can be mentioned.
- polyaddition type curing agent examples include aliphatic polyamines such as diethylenetriamine, triethylenetetramine, and metaxylenediamine, aromatic polyamines such as diaminodiphenylmethane, m-phenylenediamine, and diaminodiphenylsulfone, dicyandiamide, and organic acid dihydrazide.
- aliphatic polyamines such as diethylenetriamine, triethylenetetramine, and metaxylenediamine
- aromatic polyamines such as diaminodiphenylmethane, m-phenylenediamine, and diaminodiphenylsulfone, dicyandiamide, and organic acid dihydrazide.
- Polyamine compounds including: Acids including alicyclic acid anhydrides such as hexahydrophthalic anhydride and methyltetrahydrophthalic anhydride, aromatic acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic acid Anhydrides; Polyphenol compounds such as novolak-type phenol resins and phenol polymers; Polymercaptan compounds such as polysulfides, thioesters and thioethers; Isocyanate compounds such as isocyanate; and organic acids such as carboxylic acid-containing polyester resins.
- Acids including alicyclic acid anhydrides such as hexahydrophthalic anhydride and methyltetrahydrophthalic anhydride, aromatic acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic acid Anhydrides; Polyphenol compounds such as novolak-type phenol resins and
- catalyst-type curing agent examples include tertiary amine compounds such as benzyldimethylamine and 2,4,6-trisdimethylaminomethylphenol; imidazole compounds such as 2-methylimidazole and 2-ethyl-4-methylimidazole; Examples include Lewis acids such as BF 3 complex.
- condensation type curing agent examples include phenol resin-based curing agents such as a phenol aralkyl resin having a phenylene skeleton and a resol type phenol resin; a urea resin such as a methylol group-containing urea resin; and a melamine such as a methylol group-containing melamine resin. Resin etc. are mentioned.
- a phenol resin-based curing agent is preferable from the viewpoint of balance of flame resistance, moisture resistance, electrical characteristics, curability, storage stability, and the like.
- the phenol resin-based curing agent is a monomer, oligomer, or polymer in general having two or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are not particularly limited.
- phenol novolak resin cresol novolak Novolak resins such as resins; modified phenol resins such as terpene-modified phenol resins and dicyclopentadiene-modified phenol resins; phenol aralkyl resins having a phenylene skeleton and / or a biphenylene skeleton; bisphenol compounds such as bisphenol A and bisphenol F
- the hydroxyl equivalent is preferably 90 g / eq or more and 250 g / eq or less from the viewpoint of curability.
- the blending ratio of at least one phenol resin curing agent selected from the group consisting of phenol resin (B-1) and naphthol resin (B-2) is as follows: It is preferably 50 parts by mass or more and 100 parts by mass or less, more preferably 60 parts by mass or more and 100 parts by mass or less, and 70 parts by mass or more and 100 parts by mass with respect to 100 parts by mass of the curing agent (B). It is particularly preferred that the amount is not more than parts.
- the blending ratio is within the above range, a synergistic effect by the combination with the epoxy resin (A-1) can be obtained.
- the lower limit of the total amount of the curing agent (B) in the resin composition for semiconductor encapsulation is preferably 0.8% by mass or more, more preferably, relative to the total amount of the resin composition for semiconductor encapsulation. It is 1.5 mass% or more. When the lower limit is within the above range, the resulting resin composition has good fluidity.
- curing agent (B) in the resin composition for semiconductor sealing is with respect to the whole quantity of the resin composition for semiconductor sealing, Preferably it is 10 mass% or less, More preferably It is 8 mass% or less. When the upper limit is within the above range, the resulting resin composition has good solder resistance.
- the phenol resin-based curing agent and the epoxy resin are the number of epoxy groups (EP) of all epoxy resins and the phenolic hydroxyl group of all phenol resin-based curing agents. It is preferable that the equivalent ratio (EP) / (OH) to the number (OH) is 0.8 to 1.3. When the equivalent ratio is within the above range, sufficient curing characteristics can be obtained when the resulting resin composition is molded.
- an inorganic filler (C) is used in the resin composition for semiconductor encapsulation of the present invention.
- an inorganic filler (C) used for the resin composition for semiconductor sealing of this invention The inorganic filler generally used in the said field
- the particle size of the inorganic filler is desirably 0.01 ⁇ m or more and 150 ⁇ m or less from the viewpoint of filling properties into the mold cavity.
- content of the inorganic filler (C) in the resin composition for semiconductor sealing is not specifically limited, Preferably it is 70 mass% or more with respect to the total mass of the resin composition for semiconductor sealing, More preferably Is 73 mass% or more, more preferably 80 mass% or more.
- the lower limit value of the content is not less than the above range, it is possible to suppress the moisture absorption amount of the cured product of the resulting resin composition for semiconductor encapsulation, and to reduce the decrease in strength, and therefore, curing with good solder crack resistance. You can get things.
- the upper limit value of the content of the inorganic filler in the semiconductor sealing resin composition is preferably 93% by mass or less, more preferably 91% by mass with respect to the total amount of the semiconductor sealing resin composition.
- the resulting resin composition has good fluidity and good moldability.
- inorganic hydroxides such as metal hydroxides such as aluminum hydroxide and magnesium hydroxide, zinc borate, and zinc molybdate, which will be described later, these inorganic flame retardants and the above inorganic fillers are used.
- the total amount is preferably within the above range.
- the semiconductor sealing resin composition of the present invention may further contain a curing accelerator (D).
- the curing accelerator (D) has the effect of promoting the crosslinking reaction between the epoxy resin and the curing agent, and can control the balance between fluidity and curability at the time of curing of the resin composition for semiconductor encapsulation.
- the curing characteristics of the cured product can also be changed.
- curing accelerators (D) include organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and phosphorus atom-containing curing accelerations such as adducts of phosphonium compounds and silane compounds.
- Agents include nitrogen atom-containing curing accelerators such as 1,8-diazabicyclo (5,4,0) undecene-7, benzyldimethylamine, 2-methylimidazole, and among these, phosphorus atom-containing curing accelerators are preferable. Curability can be obtained.
- Compounds are more preferred. Tetra-substituted phosphonium compounds are particularly preferred when emphasizing fluidity, and phosphobetaine compounds, phosphine compounds and quinones when emphasizing the low thermal modulus of a cured resin cured resin composition.
- An adduct with a compound is particularly preferred, and an adduct of a phosphonium compound and a silane compound is particularly preferred when importance is attached to latent curing properties.
- Examples of the organic phosphine that can be used in the semiconductor sealing resin composition of the present invention include a first phosphine such as ethylphosphine and phenylphosphine, a second phosphine such as dimethylphosphine and diphenylphosphine, trimethylphosphine, triethylphosphine, and tributyl. Third phosphine such as phosphine and triphenylphosphine can be mentioned.
- Examples of the tetra-substituted phosphonium compound that can be used in the semiconductor sealing resin composition of the present invention include a compound represented by the formula (5).
- P represents a phosphorus atom
- R8, R9, R10 and R11 represent an aromatic group or an alkyl group
- A represents at least one selected from the group consisting of a hydroxyl group, a carboxyl group, and a thiol group.
- AH represents an aromatic organic acid having in the aromatic ring at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, and a thiol group
- x and y Is an integer from 1 to 3
- z is an integer from 0 to 3
- x y.
- the compound represented by the formula (5) is obtained, for example, as follows, but is not limited thereto. First, a tetra-substituted phosphonium halide, an aromatic organic acid and a base are mixed in an organic solvent and mixed uniformly to generate an aromatic organic acid anion in the solution system. Subsequently, when water is added, the compound represented by Formula (5) can be precipitated.
- R8, R9, R10 and R11 bonded to the phosphorus atom are phenyl groups
- AH is a compound having a hydroxyl group in an aromatic ring, that is, phenols
- A is The anion of the phenol is preferable.
- Examples of the phosphobetaine compound that can be used in the semiconductor sealing resin composition of the present invention include a compound represented by the formula (6).
- X1 represents an alkyl group having 1 to 3 carbon atoms
- Y1 represents a hydroxyl group
- i is an integer of 0 to 5
- j is an integer of 0 to 4.
- the compound represented by the formula (6) is obtained as follows, for example. First, it is obtained through a step of bringing a triaromatic substituted phosphine, which is a third phosphine, into contact with a diazonium salt and replacing the triaromatic substituted phosphine with a diazonium group of the diazonium salt.
- a triaromatic substituted phosphine which is a third phosphine
- Examples of the adduct of a phosphine compound and a quinone compound that can be used in the semiconductor sealing resin composition of the present invention include compounds represented by the formula (7).
- P represents a phosphorus atom
- R12, R13, and R14 represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and may be the same or different from each other.
- R15, R16 and R17 each represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and may be the same or different from each other, and R15 and R16 may be bonded to form a cyclic structure. .
- Examples of the phosphine compound used for the adduct of the phosphine compound and the quinone compound include aromatic compounds such as triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, and tris (benzyl) phosphine.
- aromatic compounds such as triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, and tris (benzyl) phosphine.
- Those having a substituent or a substituent such as an alkyl group and an alkoxyl group are preferred, and examples of the substituent such as an alkyl group and an alkoxyl group include those having 1 to 6 carbon atoms. From the viewpoint of availability, triphenylphosphine is
- examples of the quinone compound used for the adduct of the phosphine compound and the quinone compound include o-benzoquinone, p-benzoquinone and anthraquinones, and among them, p-benzoquinone is preferable from the viewpoint of storage stability.
- the adduct can be obtained by contacting and mixing in a solvent capable of dissolving both organic tertiary phosphine and benzoquinone.
- a solvent capable of dissolving both organic tertiary phosphine and benzoquinone.
- ketones such as acetone and methyl ethyl ketone which have low solubility in the adduct are preferable.
- the present invention is not limited to this.
- R12, R13 and R14 bonded to a phosphorus atom are phenyl groups, and R15, R16 and R17 are hydrogen atoms, that is, 1,4-benzoquinone and triphenylphosphine
- a compound to which is added is preferable in that the elastic modulus during heating of the cured product of the resin composition for semiconductor encapsulation can be kept low.
- Examples of the adduct of a phosphonium compound and a silane compound that can be used in the semiconductor sealing resin composition of the present invention include compounds represented by the formula (8).
- P represents a phosphorus atom
- Si represents a silicon atom
- R18, R19, R20 and R21 each independently represents an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group.
- X2 is an organic group bonded to the groups Y2 and Y3
- X3 is an organic group bonded to the groups Y4 and Y5
- Y2 and Y3 are protons
- the donating group represents a group formed by releasing a proton
- the groups Y2 and Y3 in the same molecule are combined with a silicon atom to form a chelate structure
- Y4 and Y5 are formed by a proton donating group releasing a proton.
- the groups Y4 and Y5 in the same molecule are bonded to a silicon atom to form a chelate structure, and X2 and X3 may be the same or different from each other, and Y2, Y3, Y4, Preliminary Y5 may be the being the same or different, Z1 is an organic group or an aliphatic group, an aromatic ring or a heterocyclic ring.
- R18, R19, R20 and R21 are, for example, phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, naphthyl group, hydroxynaphthyl group, benzyl group, methyl group, ethyl group, n -Butyl group, n-octyl group, cyclohexyl group, etc.
- aromatic groups having no substituent such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, hydroxynaphthyl group or unsubstituted The aromatic group is more preferable.
- X2 is an organic group bonded to Y2 and Y3.
- X3 is an organic group that binds to groups Y4 and Y5.
- Y2 and Y3 are groups formed by proton-donating groups releasing protons, and groups Y2 and Y3 in the same molecule are combined with a silicon atom to form a chelate structure.
- Y4 and Y5 are groups formed by proton-donating groups releasing protons, and groups Y4 and Y5 in the same molecule are combined with a silicon atom to form a chelate structure.
- the groups X2 and X3 may be the same or different from each other, and the groups Y2, Y3, Y4, and Y5 may be the same or different from each other.
- the groups represented by -Y2-X2-Y3- and Y4-X3-Y5- in the formula (8) are composed of groups in which a proton donor releases two protons.
- proton donors examples include catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2′-biphenol, 1,1′-bi-2-naphthol, salicylic acid, -Hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol and glycerin, etc.
- catechol, 1,2-dihydroxynaphthalene, and 2,3-dihydroxynaphthalene are more preferable.
- Z1 in the formula (8) represents an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and Reactive substitution of aliphatic hydrocarbon groups such as octyl group, aromatic hydrocarbon groups such as phenyl group, benzyl group, naphthyl group and biphenyl group, glycidyloxypropyl group, mercaptopropyl group, aminopropyl group and vinyl group Among them, a methyl group, an ethyl group, a phenyl group, a naphthyl group, and a biphenyl group are more preferable from the viewpoint that the thermal stability of the compound of the formula (8) is improved.
- a silane compound such as phenyltrimethoxysilane and a proton donor such as 2,3-dihydroxynaphthalene are added to a flask containing methanol, and then dissolved.
- Sodium methoxide-methanol solution is added dropwise with stirring.
- crystals are precipitated. The precipitated crystals are filtered, washed with water, and vacuum dried to obtain an adduct of a phosphonium compound and a silane compound.
- the compounding ratio of the curing accelerator (D) that can be used in the resin composition for semiconductor encapsulation of the present invention is preferably 0.1% by mass or more and 1% by mass or less in the total resin composition.
- the blending amount of the curing accelerator (D) is within the above range, sufficient curability and fluidity can be obtained.
- the resin composition for encapsulating a semiconductor of the present invention further includes a compound (E) (hereinafter also referred to as “compound (E)”) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring. May be included. Even when a phosphorus atom-containing curing accelerator having no latent property is used as the curing accelerator (D) for promoting the crosslinking reaction between the phenol resin and the epoxy resin by using the compound (E), the resin The reaction during melt kneading of the compound can be suppressed, and a semiconductor sealing resin composition can be obtained stably.
- the compound (E) also has an effect of lowering the melt viscosity of the resin composition for semiconductor encapsulation and improving the fluidity.
- a monocyclic compound represented by the formula (9) or a polycyclic compound represented by the formula (10) can be used, and these compounds have a substituent other than a hydroxyl group. You may do it.
- one of R22 and R26 is a hydroxyl group, the other is a hydrogen atom, a hydroxyl group, or a substituent other than a hydroxyl group, and R23, R24, and R25 are other than a hydrogen atom, a hydroxyl group, or a hydroxyl group.
- R32 and R33 are a hydroxyl group
- the other is a hydrogen atom, a hydroxyl group or a substituent other than a hydroxyl group
- R27, R28, R29, R30 and R31 are a hydrogen atom, a hydroxyl group or a hydroxyl group.
- Examples of the monocyclic compound represented by the formula (9) include catechol, pyrogallol, gallic acid, gallic acid ester, and derivatives thereof.
- Examples of the polycyclic compound represented by the formula (10) include 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and derivatives thereof.
- a compound in which a hydroxyl group is bonded to each of two adjacent carbon atoms constituting an aromatic ring is preferable because of easy control of fluidity and curability.
- the mother nucleus is a compound having a low volatility and a highly stable weighing naphthalene ring.
- the compound (E) can be a compound having a naphthalene ring such as 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene and derivatives thereof.
- These compounds (E) may be used individually by 1 type, or may use 2 or more types together.
- the compounding amount of the compound (E) is preferably 0.01% by mass or more and 1% by mass or less, more preferably 0.03% by mass or more and 0.8% by mass in the entire resin composition for encapsulating a semiconductor. % Or less, particularly preferably 0.05% by mass or more and 0.5% by mass or less.
- the lower limit value of the compounding amount of the compound (E) is within the above range, a sufficient viscosity reduction and fluidity improvement effect of the resin composition for semiconductor encapsulation can be obtained.
- the upper limit value of the compounding amount of the compound (E) is within the above range, there is little possibility of causing cracks at the lowering of the curability and continuous moldability of the semiconductor sealing resin composition and at the solder reflow temperature.
- a coupling agent (F) can be further added to the resin composition for semiconductor encapsulation of the present invention in order to improve the adhesion between the epoxy resin and the inorganic filler.
- examples thereof include, but are not limited to, epoxy silane, amino silane, ureido silane, mercapto silane, etc., and react or act between the epoxy resin and the inorganic filler to improve the interfacial strength between the epoxy resin and the inorganic filler. Anything can be used.
- the coupling agent (F) can also increase the effect of the compound (E) to lower the melt viscosity of the resin composition and improve the fluidity when used in combination with the aforementioned compound (E). is there.
- epoxy silane examples include ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, and ⁇ - (3,4 epoxycyclohexyl) ethyltrimethoxysilane. Etc.
- aminosilane examples include ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropylmethyldimethoxy.
- Silane N-phenyl ⁇ -aminopropyltriethoxysilane, N-phenyl ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltriethoxysilane, N-6- (aminohexyl) 3-amino And propyltrimethoxysilane.
- ureidosilanes include ⁇ -ureidopropyltriethoxysilane and hexamethyldisilazane.
- Examples of mercaptosilane include ⁇ -mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfide, and bis (3-triethoxysilylpropyl) disulfide.
- Examples thereof include a silane coupling agent that exhibits the same function as a mercaptosilane coupling agent by thermal decomposition. These silane coupling agents may be blended in advance with a hydrolysis reaction. These silane coupling agents may be used alone or in combination of two or more.
- the lower limit of the blending ratio of the coupling agent (F) that can be used for the semiconductor sealing resin composition of the present invention is preferably 0.01% by mass or more, more preferably 0.05% in the total resin composition. It is at least 0.1% by mass, particularly preferably at least 0.1% by mass. If the lower limit of the blending ratio of the coupling agent (F) is within the above range, the interface strength between the epoxy resin and the inorganic filler does not decrease, and good solder crack resistance in the semiconductor device can be obtained. it can.
- 1.0 mass% or less is preferable in all the resin compositions, More preferably, it is 0.8 mass% or less, Most preferably, it is 0.6 mass% or less.
- the upper limit of the blending ratio of the coupling agent (F) is within the above range, the interface strength between the epoxy resin and the inorganic filler does not decrease, and good solder crack resistance in the semiconductor device can be obtained. it can. Moreover, if the mixture ratio of a coupling agent (F) is in the said range, the water absorption of the hardened
- an inorganic flame retardant (G) can be further added to improve the flame resistance.
- examples thereof include, but are not limited to, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, zinc borate, and zinc molybdate. These inorganic flame retardants (G) may be used alone or in combination of two or more.
- the blending ratio of the inorganic flame retardant (G) that can be used in the resin composition for semiconductor encapsulation of the present invention is preferably 0.5% by mass or more and 6.0% by mass or less in the total resin composition.
- the effect which improves flame resistance can be acquired, without impairing sclerosis
- an ion trap agent (H) can be further added in order to improve moisture resistance reliability such as HAST (Highly Accelerated Temperature and Humidity Stress Test).
- HAST Highly Accelerated Temperature and Humidity Stress Test
- examples of the ion trapping agent (H) include hydrotalcites and hydrated oxides of elements selected from magnesium, aluminum, bismuth, titanium and zirconium. These may be used alone or in combination of two or more. May be used in combination. Of these, hydrotalcites are preferred.
- the compounding amount of the ion trap agent (H) is not particularly limited, but is preferably 0.05% by mass or more and 3% by mass or less, and 0.1% by mass or more and 1% by mass or less of the entire resin composition for semiconductor encapsulation. Is more preferable.
- the blending amount is within the above range, a sufficient ion scavenging action is exhibited, an effect of improving the moisture resistance reliability is obtained, and an adverse effect on other material properties is small.
- colorants such as carbon black, bengara and titanium oxide; natural waxes such as carnauba wax; synthetic waxes such as polyethylene wax; stearic acid and zinc stearate Release agents such as higher fatty acids and their metal salts or paraffins; low-stress additives such as silicone oils and silicone rubbers; inorganic ion exchangers such as bismuth oxide hydrates; non-inorganic difficulty such as phosphate esters and phosphazenes You may mix
- the resin composition for encapsulating a semiconductor of the present invention is obtained by uniformly mixing an epoxy resin (A), a curing agent (B), an inorganic filler (C), and other components described above at room temperature using, for example, a mixer. To mix.
- melt kneading using a kneader such as a heating roll, a kneader or an extruder, and then cooling and pulverizing as necessary to adjust to a desired degree of dispersion and fluidity.
- a kneader such as a heating roll, a kneader or an extruder, and then cooling and pulverizing as necessary to adjust to a desired degree of dispersion and fluidity.
- the semiconductor device of the present invention will be described.
- a method of manufacturing a semiconductor device using the resin composition for semiconductor encapsulation of the present invention for example, after a lead frame or a circuit board on which a semiconductor element is mounted is placed in a mold cavity, the resin for semiconductor encapsulation is used.
- molding methods such as a transfer mold, a compression mold, and an injection mold, is mentioned.
- Examples of the semiconductor element to be sealed include, but are not limited to, an integrated circuit, a large-scale integrated circuit, a transistor, a thyristor, a diode, and a solid-state imaging element.
- DIP dual in-line package
- PLCC chip carrier with plastic lead
- QFP quad flat package
- LQFP low profile quad flat package
- SOP Small Outline Package
- SOJ Small Outline J Lead Package
- TSOP Thin Small Outline Package
- TQFP Tape Carrier Package
- BGA ball grid array
- CSP chip size package
- a semiconductor device in which a semiconductor element is encapsulated by a molding method such as transfer molding of a resin composition for encapsulating a semiconductor is used as it is or at a temperature of about 80 ° C. to 200 ° C. for about 10 minutes to 10 hours. After completely curing this resin composition, it is mounted on an electronic device or the like.
- FIG. 1 is a view showing a cross-sectional structure of a semiconductor device using a resin composition for encapsulating a semiconductor according to the present invention.
- the semiconductor element 1 is fixed on the die pad 3 via the die bond material cured body 2.
- the electrode pad of the semiconductor element 1 and the lead frame 5 are connected by a gold wire 4.
- the semiconductor element 1 is sealed with a cured body 6 of the resin composition for semiconductor encapsulation of the present invention.
- FIG. 2 is a diagram showing a cross-sectional structure of an example of a single-side sealed semiconductor device using the resin composition for semiconductor sealing according to the present invention.
- the semiconductor element 1 On the surface of the substrate 8, the semiconductor element 1 is fixed via the die-bonding material cured body 2 on the solder resist 7 of the laminated body in which the layer of the solder resist 7 is formed. Note that the solder resist 7 on the electrode pad is removed by a developing method so that the electrode pad is exposed in order to establish conduction between the semiconductor element and the substrate. Therefore, the semiconductor device of FIG. 2 is designed to connect the electrode pad of the semiconductor element 1 and the electrode pad on the substrate 8 by the gold wire 4.
- a semiconductor device in which only one side of the substrate 8 on which the semiconductor element 1 is mounted is sealed is formed by molding a semiconductor sealing resin composition and forming a cured body 6 of the semiconductor sealing resin composition. be able to.
- the electrode pads on the substrate 8 are bonded to the solder balls 9 on the non-sealing surface side on the substrate 8 inside.
- epoxy resin (A) the following epoxy resins 1 to 3 were used. Of these, the epoxy resins 1 and 2 correspond to the epoxy resin (A-1).
- Epoxy resin 1 synthesized by a two-step reaction.
- a separable flask is equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet, phenolphthalein (Tokyo Chemical Industry Co., Ltd.) 100 parts by mass, epichlorohydrin (Tokyo Chemical Industry Co., Ltd.) After weighing 150 parts by mass and heating to 90 ° C. to dissolve, 50 parts by mass of sodium hydroxide (solid fine particles, purity 99% reagent) are gradually added over 4 hours, and the temperature is further raised to 100 ° C. And reacted for 2 hours. The reaction was stopped when the color of the solution became yellow.
- Epoxy resin 2 Same as Epoxy resin 1 except that 100 parts by mass of phenolphthalein (manufactured by Tokyo Chemical Industry Co., Ltd.) and 300 parts by mass of epichlorohydrin (manufactured by Tokyo Chemical Industry Co., Ltd.) were used in the first stage reaction.
- An epoxy resin 2 (epoxy equivalent 225 g / eq, softening point 65 ° C., ICI viscosity 1.50 dPa ⁇ sec at 150 ° C.) was obtained by the operation.
- Epoxy resin 3 When synthesizing the above-mentioned epoxy resin 2, tetrahydrofuran was added to the purified intermediate after the first-stage reaction to prepare a 10% sample solution, followed by column chromatography fractionation.
- the separation column used was a column container having an inner diameter of 80 mm and a length of 300 mm packed with polystyrene gel (manufactured by Yamazen Co., Ltd., particle diameter: 40 ⁇ m, pore size: 60 mm), a separatory funnel, column, refractive index (RI) detector, Separating and collecting valves were connected in series.
- epoxy resin 3 (epoxy equivalent 218 g / eq, softening point 53 ° C., ICI viscosity 0.30 dPa ⁇ sec at 150 ° C.) was obtained.
- the FD-MS measurement of the epoxy resins 1 to 3 was performed under the following conditions. After adding 1 g of the solvent dimethyl sulfoxide to 10 mg of the epoxy resin samples 1 to 3 and sufficiently dissolving them, they were applied to the FD emitter and subjected to measurement.
- the FD-MS system uses the MS-FD15A manufactured by JEOL Ltd. as the ionization unit and the MS-700 model name double-focusing mass spectrometer manufactured by JEOL Ltd. connected to the detector. It was measured in the range (m / z) 50 to 2000.
- the following phenol resins 1 to 6 were used as the phenol resin as the curing agent (B).
- Phenolic resin-based curing agent 1 Phenol novolac type phenolic resin (PR-HF-3, manufactured by Sumitomo Bakelite Co., Ltd., hydroxyl equivalent weight 102 g / eq, softening point 80 ° C., ICI viscosity 1.08 dPa ⁇ sec at 150 ° C.).
- Phenolic resin curing agent 2 Phenol aralkyl type phenolic resin having a phenylene skeleton (Mirex XLC-4L manufactured by Mitsui Chemicals, Inc., hydroxyl equivalent 168 g / eq, softening point 62 ° C., ICI viscosity 0.76 dPa ⁇ sec at 150 ° C.).
- Phenolic resin-based curing agent 3 Phenol aralkyl type phenolic resin having a biphenylene skeleton (GPH-65 manufactured by Nippon Kayaku Co., Ltd., hydroxyl equivalent weight 203 g / eq, softening point 67 ° C., ICI viscosity 0.68 dPa ⁇ sec at 150 ° C.).
- Phenolic resin-based curing agent 4 Triphenolmethane type resin phenol resin (MEH-7500, manufactured by Meiwa Kasei Co., Ltd., hydroxyl group equivalent 97 g / eq, softening point 110 ° C., ICI viscosity 5.8 dPa ⁇ sec at 150 ° C.).
- Phenol resin curing agent 5 A separable flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet, and 116.3 parts by mass of 37% formaldehyde aqueous solution (formalin 37% manufactured by Wako Pure Chemical Industries, Ltd.) Concentration 98 mass% 37.7 parts by mass of sulfuric acid, m-xylene (special grade reagent manufactured by Kanto Chemical Co., Inc., m-xylene, boiling point 139 ° C., molecular weight 106, purity 99.4%) were weighed and then purged with nitrogen Heating was started.
- m-xylene special grade reagent manufactured by Kanto Chemical Co., Inc., m-xylene, boiling point 139 ° C., molecular weight 106, purity 99.4%
- the system was stirred for 6 hours while maintaining a temperature range of 90 to 100 ° C., cooled to room temperature, and then neutralized by gradually adding 150 parts by mass of 20% by mass sodium hydroxide.
- 150 parts by mass of 20% by mass sodium hydroxide 150 parts by mass of 20% by mass sodium hydroxide.
- 839 parts by mass of phenol and 338 parts by mass of ⁇ , ⁇ ′-dichloro-p-xylene were added and heated while performing nitrogen substitution and stirring, while maintaining the system temperature in the range of 110 to 120 ° C.
- the reaction was allowed for 5 hours.
- the hydrochloric acid gas generated in the system by the above reaction was discharged out of the system by a nitrogen stream. After completion of the reaction, unreacted components and water were distilled off under reduced pressure conditions of 150 ° C. and 2 mmHg.
- the average values of p, q, and r are 1.8, 0.3, and 0.6, respectively, and in formula (12), the left end of the molecule is a hydrogen atom, and the right end is Phenol structure or xylene structure.) .
- Phenol resin curing agent 6 A separable flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet, 1,6-naphthalenediol (Tokyo Chemical Industry Co., Ltd., melting point 136 ° C., molecular weight 160.2) , Purity 99.5%) 100 parts by mass, 4,4′-bischloromethylbiphenyl (manufactured by Wako Pure Chemical Industries, Ltd., purity 97.5%, molecular weight 251) 31.5 parts by mass, pure water 0.6 mass After weighing the part, it was heated while being purged with nitrogen, and stirring was started at the start of melting.
- 1,6-naphthalenediol Tokyo Chemical Industry Co., Ltd., melting point 136 ° C., molecular weight 160.2
- Purity 99.5% 100 parts by mass
- 4,4′-bischloromethylbiphenyl manufactured by Wako Pure Chemical Industries, Ltd., purity 97.5%, mo
- the system was allowed to react for 2 hours while maintaining the system temperature in the range of 150 ° C to 160 ° C.
- hydrochloric acid generated in the system by the reaction was discharged out of the system by a nitrogen stream.
- the remaining hydrochloric acid and water were distilled off under reduced pressure conditions of 150 ° C. and 2 mmHg, and the phenol resin curing agent 6 represented by the formula (13) (hydroxyl equivalent 102 g / eq, softening point 75 ° C., 150 ° C.
- the ICI viscosities of epoxy resins 1 to 3 and phenol resin curing agents 1 to 6 are S. tea. Measurement was performed using an ICI corn plate viscometer manufactured by Engineering Co., Ltd.
- inorganic filler (C) fused spherical silica FB560 (average particle size 30 ⁇ m) manufactured by Denki Kagaku Kogyo Co., Ltd. 87.7 mass%, synthetic spherical silica SO-C2 manufactured by Admatex Co., Ltd. (average particle size 0.5 ⁇ m)
- Curing accelerator 1 Curing accelerator represented by formula (14).
- Curing accelerator 2 A curing accelerator represented by the formula (15).
- silane coupling agent (F) the following silane coupling agents 1 to 3 were used.
- Silane coupling agent 1 ⁇ -mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-803)
- Silane coupling agent 2 ⁇ -glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403)
- Silane coupling agent 3 N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-573)
- Aluminum hydroxide (Sumitomo Chemical Co., Ltd., CL-303) was used as the inorganic flame retardant (G).
- As the release agent carnauba wax (Nikko carnauba, melting point 83 ° C.) manufactured by Nikko Fine Co., Ltd. was used.
- Example 1 The following components were mixed at room temperature with a mixer, melt kneaded with a heating roll at 80 ° C. to 100 ° C., then cooled and then pulverized to obtain a resin composition.
- Epoxy resin 1 8.83 parts by mass, Phenol resin-based curing agent 1 3.67 parts by mass, 86.5 parts by weight of inorganic filler 1
- Curing accelerator 1 0.4 parts by mass, Silane coupling agent 1 0.1 parts by mass, Silane coupling agent 2 0.05 parts by mass, Silane coupling agent 3 0.05 parts by mass, Carbon black 0.3 parts by mass, Carnauba wax 0.1 parts by weight,
- the obtained resin composition was evaluated for the following items. The evaluation results are shown in Table 1.
- Evaluation item Spiral flow Using a low-pressure transfer molding machine (KTS-15, manufactured by Kotaki Seiki Co., Ltd.), a spiral flow measurement mold according to EMMI-1-66 was maintained at 175 ° C., injection pressure 6.9 MPa. The resin composition for semiconductor encapsulation obtained above was injected under a pressure time of 120 seconds, and the flow length was measured. The spiral flow is a fluidity parameter, and the larger the value, the better the fluidity. The unit is cm. The resin composition obtained in Example 1 showed 75 cm.
- Continuous moldability 7.5 g of the resin composition obtained above was loaded into a tablet with a size ⁇ 16 mm using a rotary tableting machine, and tableted with a tableting pressure of 600 Pa to obtain a tablet.
- the tablet was loaded into a tablet supply magazine and set inside the molding apparatus.
- a low-pressure transfer automatic molding machine SY-COMP, manufactured by Cynex Co., Ltd.
- a silicon chip or the like is sealed with a resin composition tablet under conditions of a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, and a curing time of 60 seconds.
- the molding for obtaining the semiconductor device was continuously performed up to 300 shots. At this time, the molding state of the semiconductor device (whether or not unfilled) is confirmed every 25 shots, ⁇ for those that have been continuously molded for 500 shots or more, ⁇ for 300 shots or more and less than 500 shots, for less than 300 shots was marked with x.
- the resin composition obtained in Example 1 showed good continuous moldability of 500 shots or more.
- Adhesion test The obtained resin composition was adjusted with a powder molding press (S-20-A, manufactured by Tamagawa Machinery Co., Ltd.) to a mass of 15 g, size ⁇ 18 mm ⁇ height about 30 mm, and tableting pressure Tablets were obtained by tableting at 600 Pa.
- S-20-A powder molding press
- Tablets were obtained by tableting at 600 Pa.
- the tablet supply magazine loaded with the obtained tablet is set in the molding apparatus, but the tablet in the magazine set in the molding apparatus is used until molding is actually used for molding.
- the magazine was in a stand-by state, and a maximum of 13 pieces were stacked vertically at a surface temperature of about 35 ° C.
- the tablet is fed and transported in the molding device by raising the push-up pin from the bottom of the magazine, so that the top tablet is pushed out from the top of the magazine and lifted by the mechanical arm to the transfer molding pot. Be transported. At this time, if the tablet sticks up and down during standby in the magazine, a conveyance failure occurs.
- Flame resistance Semiconductor sealing using a low-pressure transfer molding machine (KTS-30, manufactured by Kotaki Seiki Co., Ltd.) under conditions of a mold temperature of 175 ° C., an injection time of 15 seconds, a curing time of 120 seconds, and an injection pressure of 9.8 MPa.
- the resin composition for injection was injection-molded to produce a 3.2 mm-thick flame resistance test piece, and heat-treated at 175 ° C. for 4 hours. About the obtained test piece, the flame resistance test was done according to the specification of UL94 vertical method.
- the table shows the fire resistance rank after the determination.
- the resin composition for encapsulating a semiconductor obtained in Example 1 exhibited good flame resistance such as Fmax: 4 seconds, ⁇ F: 11 seconds, and fire resistance rank: V-0.
- Solder resistance test 1 For semiconductor encapsulation using a low-pressure transfer molding machine (Daiichi Seiko Co., Ltd., GP-ELF) under conditions of a mold temperature of 180 ° C., an injection pressure of 7.4 MPa, and a curing time of 120 seconds.
- a lead frame or the like on which a semiconductor element (silicon chip) is mounted by injecting a resin composition is sealed and molded, and a lead frame made of 80 pQFP (Quad Flat Package, Cu oxide spot), the size is 14 ⁇ 20 mm ⁇ thickness 2.
- the semiconductor element is 7 ⁇ 7 mm ⁇ thickness 0.35 mm, and the semiconductor element and the inner lead portion of the lead frame are bonded by a gold wire with a diameter of 25 ⁇ m.
- Solder Resistance Test 2 Same as Solder Resistance Test 1 except that six semiconductor devices heat-treated at 175 ° C. for 4 hours in the above-mentioned solder resistance test 1 were treated at 30 ° C. and 60% relative humidity for 96 hours. The test was conducted. The semiconductor device obtained in Example 1 showed a good reliability of 0/6.
- High-temperature storage characteristics For semiconductor encapsulation using a low-pressure transfer molding machine (Daiichi Seiko Co., Ltd., GP-ELF) under conditions of a mold temperature of 180 ° C. and an injection pressure of 6.9 ⁇ 0.17 MPa for 90 seconds.
- the resin composition is injected to seal and mold a lead frame on which a semiconductor element (silicon chip) is mounted.
- a 16-pin DIP Dual Inline Package, 42 alloy lead frame, the size is 7 mm ⁇ 11.5 mm ⁇ thickness
- the thickness of the semiconductor element is 5 ⁇ 9 mm ⁇ thickness 0.35 mm
- the semiconductor element is formed by forming an oxide layer having a thickness of 5 ⁇ m on the surface and further forming an aluminum wiring pattern having a line and space of 10 ⁇ m on the oxide layer. And the aluminum wiring pad portion and the lead frame pad portion on the element are bonded by a gold wire having a diameter of 25 ⁇ m).
- a device was made. The initial resistance value of 10 semiconductor devices heat-treated at 175 ° C. for 4 hours as a post cure was measured, and a high-temperature storage treatment at 185 ° C. for 1000 hours was performed.
- Example 1 When the resistance value of the semiconductor device is measured after the high temperature treatment, a semiconductor device having 130% or more of the initial resistance value is regarded as defective. When the number of defective semiconductor devices is 0, the number of defective semiconductor devices is 1 to 10. X was displayed. The semiconductor device obtained in Example 1 showed a good reliability of 0/10.
- Examples 1 to 12 are resin compositions containing an epoxy resin (A-1) represented by the formula (1), a phenol resin curing agent (B), and an inorganic filler (C).
- Comparative Examples 1 to 4 using a phenolphthalein type epoxy resin 3 different from the epoxy resin (A-1) represented by the formula (1) are also affected by the combined phenol resin curing agent, At least one of continuous formability, adhesion resistance, solder resistance, and high-temperature storage characteristics was inferior.
- Comparative Examples 2 and 3 using the phenol resin curing agents 2 and 3 having a relatively low softening point the tablets are easily fixed in the adhesion test, and these curing agents have low curability, The continuous formability was poor.
- Comparative Example 4 using a triphenolmethane type phenolic resin curing agent 4 having a high softening point and excellent curability and heat resistance, high-temperature storage characteristics are good, but continuous formability, adhesion resistance, and solder resistance. However, the results were as satisfactory as the examples.
- the epoxy resin As the epoxy resin, the following epoxy resins 4 to 8 were used. Of these, the epoxy resin 4 corresponds to the epoxy resin (A-1).
- Epoxy resin 4 A separable flask is equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet, and 100 parts by weight of phenolphthalein (Tokyo Chemical Industry Co., Ltd.) and 350 parts by mass of epichlorohydrin (Tokyo Chemical Industry Co., Ltd.) are weighed. After heating to 90 ° C. and dissolving, 50 parts by mass of sodium hydroxide (solid fine particles, 99% purity reagent) is gradually added over 4 hours, and the temperature is further raised to 100 ° C. for 2 hours. I let you. The reaction was stopped when the color of the solution became yellow.
- phenolphthalein Tokyo Chemical Industry Co., Ltd.
- epichlorohydrin Tokyo Chemical Industry Co., Ltd.
- the epoxy resin 4 containing the compound to be obtained (epoxy equivalent 235 g / eq, softening point 67 ° C., ICI viscosity 1.1 dPa ⁇ sec at 150 ° C.) was obtained.
- Epoxy resin 5 Triphenolmethane type epoxy resin (E-1032H60, manufactured by Mitsubishi Chemical Corporation, hydroxyl equivalent 171 g / eq, softening point 59 ° C., ICI viscosity 1.30 dPa ⁇ sec at 150 ° C.).
- Epoxy resin 6 Orthocresol novolac type epoxy resin (manufactured by DIC Corporation, EPLICLON N660, hydroxyl group equivalent 210 g / eq, softening point 62 ° C., ICI viscosity 2.34 dPa ⁇ sec at 150 ° C.).
- Epoxy resin 7 Phenol aralkyl type epoxy resin having a phenylene skeleton (manufactured by Nippon Kayaku Co., Ltd., NC-2000, hydroxyl group equivalent 238 g / eq, softening point 52 ° C., ICI viscosity 1.2 dPa ⁇ sec at 150 ° C.).
- Epoxy resin 8 A phenol aralkyl type epoxy resin having a biphenylene skeleton (manufactured by Nippon Kayaku Co., Ltd., NC-3000, hydroxyl group equivalent 276 g / eq, softening point 57 ° C., ICI viscosity 1.150 dPa ⁇ sec at 150 ° C.).
- the GPC measurement of the epoxy resin 4 was performed under the following conditions. 6 ml of solvent tetrahydrofuran (THF) was added to 20 mg of a sample of epoxy resin 4 and sufficiently dissolved, and subjected to GPC measurement.
- the GPC system includes WATERS module W2695, Tosoh Corporation's TSK GUARDCOLUMN HHR-L (diameter 6.0 mm, tube length 40 mm, guard column), Tosoh Corporation's TSK-GEL GMHHR-L (diameter 7.8 mm, A tube having a tube length of 30 mm and two polystyrene gel columns) and a differential refractive index (RI) detector W2414 manufactured by WATERS, in series, was used. The flow rate of the pump was 0.5 ml / min, the temperature in the column and the differential refractometer was 40 ° C., and measurement was performed by injecting the measurement solution from a 100 ⁇ l injector.
- Phenol resins 2 to 9 were used as the phenol resin as the curing agent (B).
- the phenol resins 2 to 6 are as described above.
- the phenol resin curing agents 4 and 9 correspond to the phenol resin (B-1)
- the phenol resin curing agents 6, 7, and 8 correspond to the naphthol resin (B-2).
- Phenolic resin-based curing agent 7 copolymerized resin of naphthol novolak resin and cresol novolak resin (Kayahared CBN manufactured by Nippon Kayaku Co., Ltd., hydroxyl equivalent 139 g / eq, softening point 90 ° C., ICI viscosity 1.50 dPa ⁇ sec).
- Phenolic resin-based curing agent 8 naphthol aralkyl type phenol resin having a phenylene skeleton (SN-485 manufactured by Tohto Kasei Co., Ltd., hydroxyl equivalent: 210 g / eq, softening point: 87 ° C., ICI viscosity: 1.78 dPa ⁇ sec at 150 ° C.)
- Phenol resin curing agent 9 copolymer type phenol resin of triphenolmethane type resin and phenol novolac resin (HE910-20 manufactured by Air Water Co., Ltd., hydroxyl equivalent weight 101 g / eq, softening point 88 ° C., ICI viscosity at 150 ° C. 1.5 dPa ⁇ sec).
- Example 13 The following components were mixed at room temperature with a mixer, melt kneaded with a heating roll at 80 ° C. to 100 ° C., then cooled and then pulverized to obtain a resin composition for semiconductor encapsulation.
- Epoxy resin 4 8.97 parts by mass Phenol resin curing agent 4 3.53 parts by mass Inorganic filler 1 86.5 parts by mass Curing accelerator 1 0.4 parts by mass Silane coupling agent 1 0.1 parts by mass Silane coupling Agent 2 0.05 part by weight Silane coupling agent 3 0.05 part by weight Carbon black 0.3 part by weight Carnauba wax 0.1 part by weight Spiral flow, flame resistance, water absorption of the obtained semiconductor sealing resin composition Rate, continuous formability, solder resistance and high-temperature storage characteristics were evaluated.
- the evaluation method of spiral flow, flame resistance, continuous formability, solder resistance and high temperature storage characteristics is as described above. The evaluation results are shown in Table 5.
- Boiling water absorption using a low-pressure transfer molding machine (KTS-30, manufactured by Kotaki Seiki Co., Ltd.), a disk-shaped test piece having a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, a curing time of 120 s, a diameter of 50 mm, and a thickness of 3 mm was molded and heat-treated at 175 ° C. for 4 hours.
- KTS-30 low-pressure transfer molding machine
- a disk-shaped test piece having a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, a curing time of 120 s, a diameter of 50 mm, and a thickness of 3 mm was molded and heat-treated at 175 ° C. for 4 hours.
- the mass change before the moisture absorption treatment of the test piece and after the boiling treatment in pure water for 24 hours was measured, and the water absorption rate of the test piece was shown as a percentage.
- the unit is mass%.
- Examples 14 to 24, Comparative Examples 5 to 10 According to the formulations shown in Table 5, Table 6, and Table 7, a semiconductor sealing resin composition was produced in the same manner as in Example 13, and evaluated in the same manner as in Example 13. The evaluation results are shown in Table 5, Table 6, and Table 7.
- Examples 13 to 24 include an epoxy resin (A-1) represented by the formula (1) and a phenol resin (B-1) having a repeating unit structure including two phenol skeletons, or a hydroxynaphthalene skeleton or a dihydroxynaphthalene skeleton.
- a resin composition comprising a naphthol resin (B-2) having an inorganic filler (C), a combination of an epoxy resin (A-1) and another epoxy resin, a phenol resin (B-1) ) Or naphthol resin (B-2) of a different type, a combination of phenol resin (B-1) and another phenol resin curing agent, a type of curing accelerator (D) changed, Including any inorganic flame retardant (G), fluidity (spiral flow), flame resistance, water absorption, solder resistance, high temperature storage characteristics, continuous formability Excellent results in the balance was obtained.
- G inorganic flame retardant
- fluidity spiral flow
- Comparative Example 9 using a phenol aralkyl type epoxy resin 7 having a phenylene skeleton and a phenol aralkyl type phenol resin 2 having a phenylene skeleton, and a phenol aralkyl type epoxy resin 8 having a biphenylene skeleton and a phenol having a biphenylene skeleton
- the comparative example 10 using the aralkyl type phenol resin 3 was a combination aiming at high flame resistance and high solder resistance, the high temperature storage characteristic was remarkably bad.
- semiconductor sealing exhibits flame resistance without using a halogen compound and an antimony compound, and has a higher level of continuous molding, adhesion resistance, solder resistance, and high temperature storage characteristics than before.
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Abstract
Description
前記エポキシ樹脂(A)が式(1):
(式(1)において、R1は炭素数1~6の炭化水素基であり、R2は炭素数1~6の炭化水素基または炭素数6~14の芳香族炭化水素基であり、互いに同じであっても異なっていてもよく、aは0~4の整数であり、bは0~4の整数であり、nは0以上の整数である。)
で表されるエポキシ樹脂(A-1)を含み、
前記エポキシ樹脂(A-1)が、前記式(1)においてn≧1である成分と、前記式(1)においてn=0である成分(a1)とを含む、半導体封止用樹脂組成物が提供される。
式(2)で表されるフェノール樹脂(b1):
(式(2)において、R3は炭素数1~6の炭化水素基または炭素数6~14の芳香族炭化水素基であり、互いに同じであっても異なっていてもよく、c1は0~4の整数であり、c2は0~3の整数であり、、互いに同じであっても異なっていてもよく、dは1~10の整数であり、eは0~10の整数であり、繰り返し数dで表される構造単位と繰り返し数eで表される構造単位は、それぞれが連続で並んでいても、お互いが交互に並んでいても、ランダムに並んでいてもよい。)、
式(3)で表されるナフトール樹脂(b2):
(式(3)において、R4は水酸基または水素原子であり、R5は炭素数1~6の炭化水素基または炭素数6~14の芳香族炭化水素基であり、互いに同じであっても異なっていてもよく、R6は炭素数1~6の炭化水素基または炭素数6~14の芳香族炭化水素基であり、互いに同じであっても異なっていてもよく、fは0~3の整数であり、gは0~5の整数であり、hは1~2の整数であり、m、nは互いに独立して1~10の整数であり、m+n≧2であり、繰り返し数mで表される構造単位と繰り返し数nで表される構造単位とは、それぞれが連続で並んでいても、お互いが交互に並んでいても、ランダムに並んでいてもよいが、それぞれの間には必ず-CH2-が介在する。)、および
式(4)で表されるナフトール樹脂(b3):
(式(4)において、R7は炭素数1~6の炭化水素基または炭素数6~14の芳香族炭化水素基であり、互いに同じであっても異なっていてもよく、k1は0~6の整数であり、k2は0~4の整数であり、、互いに同じであっても異なっていてもよく、sは0~10の整数であり、tは1~2の整数である。)、
からなる群より選択される少なくとも1種の樹脂を含む。
前記エポキシ樹脂(A)が式(1):
(式(1)において、R1は炭素数1~6の炭化水素基であり、R2は炭素数1~6の炭化水素基または炭素数6~14の芳香族炭化水素基であり、互いに同じであっても異なっていてもよく、aは0~4の整数であり、bは0~4の整数であり、nは0以上の整数である。)
で表されるエポキシ樹脂(A-1)を含む。本発明において、上記エポキシ樹脂(A-1)は、式(1)においてn≧1である成分と、式(1)においてn=0である成分(a1)とを含む。また、本発明の半導体装置は、上記半導体封止用樹脂組成物の硬化物で封止された半導体素子を含むことを特徴とする。以下、本発明について詳細に説明する。
(式(2)において、R3は炭素数1~6の炭化水素基または炭素数6~14の芳香族炭化水素基であり、互いに同じであっても異なっていてもよく、c1は0~4の整数であり、c2は0~3の整数であり、互いに同じであっても異なっていてもよく、dは1~10の整数であり、eは0~10の整数であり、繰り返し数dで表される構造単位と繰り返し数eで表される構造単位は、それぞれが連続で並んでいても、お互いが交互に並んでいても、ランダムに並んでいてもよい。)
(式(3)において、R4は水酸基または水素原子であり、R5は炭素数1~6の炭化水素基または炭素数6~14の芳香族炭化水素基であり、互いに同じであっても異なっていてもよく、R6は炭素数1~6の炭化水素基または炭素数6~14の芳香族炭化水素基であり、互いに同じであっても異なっていてもよく、fは0~3の整数であり、gは0~5の整数であり、hは1~2の整数であり、m、nは互いに独立して1~10の整数であり、m+n≧2であり、繰り返し数mで表される構造単位と繰り返し数nで表される構造単位とは、それぞれが連続で並んでいても、お互いが交互に並んでいても、ランダムに並んでいてもよいが、それぞれの間には必ず-CH2-が介在する。)
(式(4)において、R7は炭素数1~6の炭化水素基または炭素数6~14の芳香族炭化水素基であり、互いに同じであっても異なっていてもよく、k1は0~6の整数であり、k2は0~4の整数であり、互いに同じであっても異なっていてもよく、sは0~10の整数であり、tは1~2の整数ある。)
(式(5)において、Pはリン原子を表し、R8、R9、R10およびR11は芳香族基またはアルキル基を表し、Aはヒドロキシル基、カルボキシル基、チオール基からなる群から選ばれる少なくとも1つの基を芳香環に有する芳香族有機酸のアニオンを表し、AHはヒドロキシル基、カルボキシル基、チオール基からなる群から選ばれる少なくとも1つの基を芳香環に有する芳香族有機酸を表し、xおよびyは1~3の整数であり、zは0~3の整数であり、かつx=yである。)
(式(6)において、X1は炭素数1~3のアルキル基を表し、Y1はヒドロキシル基を表し、iは0~5の整数であり、jは0~4の整数である。)
(式(7)において、Pはリン原子を表し、R12、R13およびR14は炭素数1~12のアルキル基または炭素数6~12のアリール基を表し、互いに同一であっても異なっていてもよく、R15、R16およびR17は水素原子または炭素数1~12の炭化水素基を表し、互いに同一であっても異なっていてもよく、R15とR16が結合して環状構造となっていてもよい。)
(式(8)において、Pはリン原子を表し、Siは珪素原子を表し、R18、R19、R20およびR21は、それぞれ独立して、芳香環または複素環を有する有機基、あるいは脂肪族基を表し、互いに同一であっても異なっていてもよく、X2は、基Y2およびY3と結合する有機基であり、X3は、基Y4およびY5と結合する有機基であり、Y2およびY3は、プロトン供与性基がプロトンを放出してなる基を表し、同一分子内の基Y2およびY3が珪素原子と結合してキレート構造を形成する。Y4およびY5はプロトン供与性基がプロトンを放出してなる基を表し、同一分子内の基Y4およびY5が珪素原子と結合してキレート構造を形成する。X2、およびX3は互いに同一であっても異なっていてもよく、Y2、Y3、Y4、およびY5は互いに同一であっても異なっていてもよく、Z1は芳香環または複素環を有する有機基、あるいは脂肪族基である。)
(式(9)において、R22およびR26のいずれか一方が水酸基であり、他方は水素原子、水酸基、または水酸基以外の置換基であり、R23、R24、およびR25は水素原子、水酸基または水酸基以外の置換基である。)
(式(10)において、R32およびR33のいずれか一方は水酸基であり、他方は水素原子、水酸基または水酸基以外の置換基であり、R27、R28、R29、R30およびR31は水素原子、水酸基または水酸基以外の置換基である。)
これらのうち、エポキシ樹脂1および2がエポキシ樹脂(A-1)に該当する。
シランカップリング剤1:γ-メルカプトプロピルトリメトキシシラン(信越化学工業株式会社製、KBM-803)
シランカップリング剤2:γ-グリシドキシプロピルトリメトキシシラン(信越化学工業株式会社製、KBM-403)
シランカップリング剤3:N-フェニル-3-アミノプロピルトリメトキシシラン(信越化学工業株式会社製、KBM-573)
離型剤は、日興ファイン株式会社製のカルナバワックス(ニッコウカルナバ、融点83℃)を使用した。
以下の成分をミキサーにて常温で混合し、80℃~100℃の加熱ロールで溶融混練を行い、その後冷却し、次いで粉砕して、樹脂組成物を得た。
エポキシ樹脂1 8.83質量部、
フェノール樹脂系硬化剤1 3.67質量部、
無機充填材1 86.5質量部、
硬化促進剤1 0.4質量部、
シランカップリング剤1 0.1質量部、
シランカップリング剤2 0.05質量部、
シランカップリング剤3 0.05質量部、
カーボンブラック 0.3質量部、
カルナバワックス 0.1質量部、
得られた樹脂組成物を、以下の項目について評価した。評価結果を表1に示す。
スパイラルフロー:低圧トランスファー成形機(コータキ精機株式会社製、KTS-15)を用いて、EMMI-1-66に準じたスパイラルフロー測定用金型に、175℃、注入圧力6.9MPa、保圧時間120秒間の条件にて上記で得られた半導体封止用樹脂組成物を注入し、流動長を測定した。スパイラルフローは、流動性のパラメータであり、数値が大きい方が、流動性が良好である。単位はcmである。実施例1で得られた樹脂組成物は、75cmを示した。
これらのうち、エポキシ樹脂4がエポキシ樹脂(A-1)に該当する。
セパラブルフラスコに撹拌装置、温度計、還流冷却器、窒素導入口を装着し、フェノールフタレイン(東京化成工業株式会社製)100質量部、エピクロルヒドリン(東京化成工業株式会社製)350質量部を秤量し、90℃に加熱して溶解させた後、水酸化ナトリウム(固形細粒状、純度99%試薬)50質量部を4時間かけて徐々に添加し、さらに100℃に昇温して2時間反応させた。溶液の色が黄色になった時点で反応を停止した。反応後、蒸留水150質量部を加えて振とうした後に、水層を棄却する操作(水洗)を洗浄水が中性になるまで繰り返し行った後、油層を125℃、2mmHgの減圧条件でエピクロルヒドリンを留去した。得られた固形物にメチルイソブチルケトン250質量部を加えて溶解し、70℃に加熱し、30質量%水酸化ナトリウム水溶液13質量部を1時間かけて添加し、さらに1時間反応した後、静置し、水層を棄却した。油層に蒸留水150質量部を加えて水洗操作を行い、洗浄水が中性になるまで同様の水洗操作を繰り返し行った後、加熱減圧によってメチルイソブチルケトンを留去し、式(11)で表される化合物を含むエポキシ樹脂4(エポキシ当量235g/eq、軟化点67℃、150℃におけるICI粘度1.1dPa・sec)を得た。エポキシ樹脂4のGPCチャートを図6に示す。GPCの結果より、式(11)で表される化合物において、n=0である成分が86面積%含まれるほか、n=1の成分、n=2の成分およびその他の副生成物が合計で14面積%含まれることが確認できた。
これらのうち、フェノール樹脂系硬化剤4、9がフェノール樹脂(B-1)に、フェノール樹脂系硬化剤6、7、8がナフトール樹脂(B-2)に該当する。
以下の成分をミキサーにて常温で混合し、80℃~100℃の加熱ロールで溶融混練を行い、その後冷却し、次いで粉砕して、半導体封止用樹脂組成物を得た。
エポキシ樹脂4 8.97質量部
フェノール樹脂系硬化剤4 3.53質量部
無機充填材1 86.5質量部
硬化促進剤1 0.4質量部
シランカップリング剤1 0.1質量部
シランカップリング剤2 0.05質量部
シランカップリング剤3 0.05質量部
カーボンブラック 0.3質量部
カルナバワックス 0.1質量部
得られた半導体封止用樹脂組成物を、スパイラルフロー、耐燃性、吸水率、連続成形性、耐半田性および高温保管特性について評価した。スパイラルフロー、耐燃性、連続成形性、耐半田性および高温保管特性の評価方法は、上記のとおりである。評価結果を表5に示す。
Claims (19)
- 前記エポキシ樹脂(A-1)が、前記式(1)においてn=1である成分(a2)を含み、
FD-MSで測定される、前記成分(a1)のピーク強度が、前記エポキシ樹脂(A-1)のピーク全体に対して、50%以上、90%以下であり、前記成分(a2)のピーク強度が、前記エポキシ樹脂(A-1)のピーク全体に対して、10%以上、50%以下である、請求項1に記載の半導体封止用樹脂組成物。 - FD-MSで測定される、前記成分(a1)のピーク強度P1に対する前記成分(a2)のピーク強度P2の比P2/P1が、0.1以上、1.0以下である、請求項2に記載の半導体封止用樹脂組成物。
- ゲルパーミエーションクロマトグラフィーで得られる前記エポキシ樹脂(A-1)の全ピーク面積に対して、前記成分(a1)のピーク面積が、70面積%以上、95面積%以下である、請求項1に記載の半導体封止用樹脂組成物。
- 前記エポキシ樹脂(A-1)の150℃におけるICI粘度が0.1dPa・sec以上、3.0dPa・sec以下である、請求項1に記載の半導体封止用樹脂組成物。
- 前記エポキシ樹脂(A-1)の150℃における軟化点が55℃以上、90℃以下である、請求項1に記載の半導体封止用樹脂組成物。
- 前記エポキシ樹脂(A-1)のエポキシ当量が210g/eq以上、250g/eq以下である、請求項1に記載の半導体封止用樹脂組成物。
- 前記硬化剤(B)がフェノール樹脂系硬化剤である、請求項1に記載の半導体封止用樹脂組成物。
- 前記フェノール樹脂系硬化剤が、2個以上のフェノール骨格を有するフェノール樹脂(B-1)、およびヒドロキシナフタレン骨格またはジヒドロキシナフタレン骨格を有するナフトール樹脂(B-2)からなる群より選択される少なくとも1種の樹脂を含む、請求項8に記載の半導体封止用樹脂組成物。
- 前記フェノール樹脂系硬化剤が、
式(2)で表されるフェノール樹脂(b1):
(式(2)において、R3は炭素数1~6の炭化水素基または炭素数6~14の芳香族炭化水素基であり、互いに同じであっても異なっていてもよく、c1は0~4の整数であり、c2は0~3の整数であり、互いに同じであっても異なっていてもよく、dは1~10の整数であり、eは0~10の整数であり、繰り返し数dで表される構造単位と繰り返し数eで表される構造単位は、それぞれが連続で並んでいても、お互いが交互に並んでいても、ランダムに並んでいてもよい。)、
式(3)で表されるナフトール樹脂(b2):
(式(3)において、R4は水酸基または水素原子であり、R5は炭素数1~6の炭化水素基または炭素数6~14の芳香族炭化水素基であり、互いに同じであっても異なっていてもよく、R6は炭素数1~6の炭化水素基または炭素数6~14の芳香族炭化水素基であり、互いに同じであっても異なっていてもよく、fは0~3の整数であり、gは0~5の整数であり、hは1~2の整数であり、m、nは互いに独立して1~10の整数であり、m+n≧2であり、繰り返し数mで表される構造単位と繰り返し数nで表される構造単位とは、それぞれが連続で並んでいても、お互いが交互に並んでいても、ランダムに並んでいてもよいが、それぞれの間には必ず-CH2-が介在する。)、および
式(4)で表されるナフトール樹脂(b3):
(式(4)において、R7は炭素数1~6の炭化水素基または炭素数6~14の芳香族炭化水素基であり、互いに同じであっても異なっていてもよく、k1は0~6の整数であり、k2は0~4の整数であり、互いに同じであっても異なっていてもよく、sは0~10の整数であり、tは1~2の整数ある。)、
からなる群より選択される少なくとも1種の樹脂を含む、請求項9に記載の半導体封止用樹脂組成物。 - 前記フェノール樹脂(b1)、前記ナフトール樹脂(b2)、および前記ナフトール樹脂(b3)からなる群より選択される少なくとも1種の樹脂の量が、前記硬化剤(B)100質量部に対して、50質量部以上、100質量部以下である、請求項10に記載の半導体封止用樹脂組成物。
- 前記無機充填材(C)の量が、前記半導体封止用樹脂組成物の全質量に対して70質量%以上、93質量%以下である、請求項1に記載の半導体封止用樹脂組成物。
- 前記エポキシ樹脂(A-1)の量が、前記エポキシ樹脂(A)100質量部に対して、50質量部以上、100質量部以下である、請求項1に記載の半導体封止用樹脂組成物。
- 硬化促進剤(D)をさらに含む、請求項1に記載の半導体封止用樹脂組成物。
- 前記硬化促進剤(D)が、テトラ置換ホスホニウム化合物、ホスホベタイン化合物、ホスフィン化合物とキノン化合物との付加物、ホスホニウム化合物とシラン化合物との付加物からなる群から選択される少なくとも1種の硬化促進剤を含む、請求項14記載の半導体封止用樹脂組成物。
- 芳香環を構成する2個以上の隣接する炭素原子にそれぞれ水酸基が結合した化合物(E)をさらに含む、請求項1に記載の半導体封止用樹脂組成物。
- カップリング剤(F)をさらに含む、請求項1に記載の半導体封止用樹脂組成物。
- 無機難燃剤(G)をさらに含む、請求項1に記載の半導体封止用樹脂組成物。
- 請求項1に記載の半導体封止用樹脂組成物で封止された半導体素子を含む半導体装置。
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