WO2013136769A1 - 封止用樹脂組成物およびこれを用いる電子装置 - Google Patents
封止用樹脂組成物およびこれを用いる電子装置 Download PDFInfo
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- WO2013136769A1 WO2013136769A1 PCT/JP2013/001590 JP2013001590W WO2013136769A1 WO 2013136769 A1 WO2013136769 A1 WO 2013136769A1 JP 2013001590 W JP2013001590 W JP 2013001590W WO 2013136769 A1 WO2013136769 A1 WO 2013136769A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
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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
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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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
- C08G59/3218—Carbocyclic compounds
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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
- C08G59/40—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
- C08G59/62—Alcohols or phenols
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Definitions
- the present invention relates to a sealing resin composition and an electronic device using the same. More specifically, for example, the present invention relates to a resin composition for sealing an electronic component such as a semiconductor, and an electronic device including the electronic component sealed with such a resin composition.
- SiC / GaN power semiconductor devices semiconductor devices having elements using SiC or GaN mounted with elements using SiC (silicon carbide) or GaN (gallium nitride) (Referred to as Patent Document 1).
- Such devices can not only significantly reduce power loss compared to conventional Si-based devices, but also operate at higher voltages, higher currents, and higher temperatures such as 200 ° C. or higher. Since this is possible, it is expected to expand to applications that have been difficult to apply to conventional Si power semiconductor devices.
- elements capable of operating under severe conditions represented by elements (semiconductor elements) using SiC / GaN, are used for the semiconductor sealing material provided in the semiconductor device in order to protect these elements.
- heat resistance more than conventional is required.
- a resin composition containing a cured product of an epoxy-based resin composition as a main material is used as a semiconductor sealing material from the viewpoint of adhesiveness, electrical stability, and the like. Yes.
- the glass transition temperature (Tg) is used as an index representing the heat resistance of the cured product of such a resin composition. This is because the resin composition (cured product) becomes rubbery in a temperature region of Tg or higher, and the strength and adhesive strength are reduced due to this. Therefore, as a method for increasing the Tg, the epoxy group equivalent of the epoxy resin contained in the resin composition or the hydroxyl group equivalent of the curing agent (phenolic resin curing agent) is lowered to increase the crosslink density, or these functional groups. A technique such as making the structure connecting the (epoxy group and hydroxyl group) rigid is employed.
- a weight reduction rate due to thermal decomposition is used as an index representing the heat resistance of the resin composition.
- the weight reduction of the resin composition occurs due to thermal decomposition of the connection portion between the epoxy resin having a low binding energy and the curing agent. Therefore, it is disadvantageous to reduce the weight reduction rate in a semiconductor sealing material having a high functional group density. Therefore, the purpose of the method for reducing the weight reduction rate and the method for obtaining the high Tg described above are contradictory.
- the resin skeleton formed by the epoxy resin and the curing agent and the functional group density are designed under optimum conditions, and have a high Tg and a low weight loss rate. Realization of a resin composition designed to have the above has been desired.
- the present invention provides a resin composition capable of realizing both improvement in glass transition temperature (Tg) and reduction in weight reduction rate due to thermal decomposition, and has been obtained from the resin composition.
- An electronic device having excellent reliability at high temperature is provided by providing a cured product as a sealing material for sealing an electronic component such as a semiconductor element.
- a resin composition for sealing containing a phenol resin curing agent represented by the formula (1A), an epoxy resin represented by the formula (2A), and a release agent having a 5% weight loss temperature of 240 ° C. or higher.
- a resin composition is provided.
- two Y's each independently represent a hydroxyphenyl group represented by Formula (1B) or Formula (1C), and X represents Formula (1D) or Formula (1E).
- n represents a number of 0 or more, and when n is 2 or more, two or more Xs may be the same or different from each other
- R 1 represents each independently a hydrocarbon group having 1 to 5 carbon atoms, and a represents an integer of 0 to 4).
- R 2 and R 3 each independently represent a hydrocarbon group having 1 to 5 carbon atoms
- b is an integer of 0 to 4
- c is an integer of 0 to 3.
- An integer d represents an integer of 0 to 3
- e represents an integer of 0 to 2.
- two Y's each independently represent a glycidylated phenyl group represented by Formula (2B) or Formula (2C)
- X represents Formula (2D) or Formula (2E).
- n represents a number of 0 or more, and when n is 2 or more, two or more Xs may be the same or different from each other independently of each other.
- R 1 each independently represent a hydrocarbon group having 1 to 5 carbon atoms, and a represents an integer of 0 to 4.
- R 2 and R 3 each independently represent a hydrocarbon group having 1 to 5 carbon atoms, b is an integer of 0 to 4, and c is an integer of 0 to 3.
- An integer, d represents an integer of 0 to 3, and e represents an integer of 0 to 2.
- the content of the phenol resin curing agent in the resin composition is A1 (mass%), and the content of the epoxy resin is A2 (mass). %),
- the value of A1 / (A1 + A2) is 0.2 or more and 0.9 or less.
- the phenol resin curing agent in the encapsulating resin composition, has a hydroxyl group equivalent of 90 g / eq or more and 190 g / eq or less.
- the epoxy resin in the sealing resin composition, has an epoxy equivalent of 160 g / eq or more and 290 g / eq or less.
- the sealing resin composition further includes an inorganic filler.
- the sealing resin composition further includes at least one curing accelerator represented by the formulas (6) to (9).
- P represents a phosphorus atom
- R 4 , R 5 , R 6 and R 7 represent an aromatic group or an alkyl group
- A represents at least one selected from a hydroxyl group, a carboxyl group, and a thiol group.
- AH represents an aromatic organic acid having an aromatic ring to which at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group is bonded.
- R 8 represents an alkyl group having 1 to 3 carbon atoms
- R 9 represents a hydroxyl group
- f is 0 to 5
- g is 0 to 3
- R 10 , R 11 and R 12 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
- R 13 , R 14 and R 15 each represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and may be the same or different from each other, and R 14 and R 15 are bonded to each other.
- a cyclic group may be formed.
- P represents a phosphorus atom
- Si represents a silicon atom
- R 16 , R 17 , R 18 and R 19 are each an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group.
- R 20 is an organic group bonded to the groups Y 2 and Y 3
- R 21 is an organic group bonded to the groups Y 4 and Y 5 .
- Y 2 and Y 3 represent a group formed by releasing a proton from a proton donating group, and groups Y 2 and Y 3 in the same molecule are bonded to a silicon atom to form a chelate structure
- Y 4 and Y 3 5 represents a group formed by releasing a proton from a proton donating group, and groups Y 4 and Y 5 in the same molecule are combined with a silicon atom to form a chelate structure
- R 20 and R 21 are identical to each other.
- Y 2 , Y 3 , Y 4 and Y 5 may be the same or different from each other
- Z 1 is an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group.
- the sealing resin composition further includes a coupling agent.
- the resin composition for sealing containing the epoxy resin represented by Formula (2A) and the mold release agent whose 5% weight reduction temperature is 240 degreeC or more is provided.
- two Y's each independently represent a glycidylated phenyl group represented by Formula (2B) or Formula (2C)
- X represents Formula (2D) or Formula (2E).
- n represents a number of 0 or more, and when n is 2 or more, two or more Xs may be the same or different from each other independently of each other.
- R 1 each independently represent a hydrocarbon group having 1 to 5 carbon atoms, and a represents an integer of 0 to 4.
- R 2 and R 3 each independently represent a hydrocarbon group having 1 to 5 carbon atoms, b is an integer of 0 to 4, and c is an integer of 0 to 3.
- An integer, d represents an integer of 0 to 3, and e represents an integer of 0 to 2.
- the glass transition temperature (Tg) of the sealing resin composition is 200 ° C. or higher, and the weight of the cured product when heated at 200 ° C. for 1000 hours in an air atmosphere.
- the reduction rate is 0.3% or less.
- a sealing resin composition comprising a phenol resin curing agent, an epoxy resin, and a release agent having a 5% weight loss temperature of 240 ° C. or higher, wherein the sealing resin composition
- the cured product has a glass transition temperature (Tg) of 200 ° C. or higher, and a weight reduction rate of the cured product when heated at 200 ° C. for 1000 hours in an air atmosphere is 0.3% or less.
- Tg glass transition temperature
- a stopping resin composition is provided.
- the phenol resin curing agent is a phenol resin curing agent represented by the formula (1A), and the epoxy resin is represented by the formula (2A). It is an epoxy resin represented by
- an electronic device including an electronic component sealed with the resin composition is provided.
- the present invention relates to a sealing resin composition capable of realizing both an improvement in glass transition temperature (Tg) and a reduction in weight reduction rate due to thermal decomposition, and a cured product obtained from the resin composition, to a semiconductor element.
- Tg glass transition temperature
- a cured product obtained from the resin composition to a semiconductor element.
- the electronic device of the present invention will be described.
- an electronic device using the resin composition of the present invention (electronic device of the present invention) will be described in a form applied to a semiconductor device.
- the semiconductor package given below is an example, and a preferred embodiment of the semiconductor chip is a semiconductor chip using silicon carbide (SiC) and gallium nitride (GaN).
- FIG. 1 is a longitudinal sectional view showing an example in which an electronic device using the resin composition of the present invention is applied to a semiconductor device. That is, in the following description, the upper side in FIG. 1 is described as “upper” and the lower side is described as “lower”.
- a semiconductor device 1 shown in FIG. 1 is a QFP (Quad Flat Package) type semiconductor package, and includes a semiconductor chip (semiconductor element) 2, a die pad 5 that supports the semiconductor chip 2 via an adhesive layer 8, and a semiconductor chip 2. And leads 6 electrically connected to each other and a mold part (sealing part) 7 for sealing the semiconductor chip 2.
- QFP Quad Flat Package
- Examples of the semiconductor chip 2 include a semiconductor chip using SiC (silicon carbide) or GaN (gallium nitride).
- the die pad 5 is made of a metal substrate and functions as a support for supporting the semiconductor chip 2.
- This die pad 5 is made of, for example, a metal substrate made of Cu, Fe, Ni, or an alloy thereof (for example, Cu-based alloy, iron-nickel-based alloy such as Fe-42Ni), and silver on the surface of the metal substrate. It may be a substrate on which plating or Ni—Pd plating is applied, or a substrate in which a gold plating (gold flash) layer for improving the stability of the Pd layer is provided on the surface of this Ni—Pd plating.
- a metal substrate made of Cu, Fe, Ni, or an alloy thereof (for example, Cu-based alloy, iron-nickel-based alloy such as Fe-42Ni), and silver on the surface of the metal substrate. It may be a substrate on which plating or Ni—Pd plating is applied, or a substrate in which a gold plating (gold flash) layer for improving the stability of the Pd layer is provided on the surface of this Ni—Pd plating.
- the planar view shape of the die pad 5 usually corresponds to the planar view shape of the semiconductor chip 2 and is, for example, a square such as a square or a rectangle.
- a plurality of leads 6 are provided radially on the outer periphery of the die pad 5.
- the end of the lead 6 opposite to the die pad 5 protrudes (exposes) from the mold part 7.
- the lead 6 is made of a conductive material, and for example, the same material as that of the die pad 5 described above can be used.
- the lead 6 may be tin-plated on the surface thereof, thereby improving the adhesion between the solder and the lead 6 when the semiconductor device 1 is connected to the terminals provided on the mother board via the solder. Can be made.
- the semiconductor chip 2 is fixed (fixed) to the die pad 5 via the adhesive layer 8.
- the adhesive layer 8 is not particularly limited, and is formed of, for example, an epoxy adhesive, an acrylic adhesive, a polyimide adhesive, and a cyanate adhesive.
- the semiconductor chip 2 includes an electrode pad 3, and the electrode pad 3 and the lead 6 are electrically connected by a wire 4. Thereby, the semiconductor chip 2 and each lead 6 are electrically connected.
- a material which comprises this wire 4 For example, Au wire, Al wire, Cu wire, Ag wire is mentioned.
- the die pad 5, each member provided on the upper surface side of the die pad 5, and the inner part of the lead 6 are sealed with a mold part 7. As a result, the outer end portion of the lead 6 protrudes from the mold portion 7.
- the mold part 7 is composed of a cured product of the resin composition of the present invention.
- the mold portion 7 is formed by sealing each member with the resin composition of the present invention as described above using a molding method such as transfer molding, and then at a temperature of about 80 ° C. to 200 ° C. for 10 minutes. It is formed by completely curing the resin composition taking about 10 hours.
- the mold part 7 has adhesiveness, electrical stability, flame retardancy. And heat resistance (particularly in terms of heat resistance, both high Tg and reduced weight loss) and high temperature reliability are required.
- the resin composition of this invention contains the phenol resin hardening
- two Y's each independently represent a hydroxyphenyl group represented by Formula (1B) or Formula (1C), and X represents Formula (1D) or Formula (1E).
- R 1 represents each independently a hydrocarbon group having 1 to 5 carbon atoms
- a represents an integer of 0 to 4
- R 2 and R 3 each independently represent a hydrocarbon group having 1 to 5 carbon atoms
- b is an integer of 0 to 4
- c is an integer of 0 to 3.
- n a number of 0 or more, and when n is 2 or more, two or more Xs may be the same or different from each other independently of each other.
- R 1 each independently represent a hydrocarbon group having 1 to 5 carbon atoms, and a represents an integer of 0 to 4.
- R 2 and R 3 each independently represent a hydrocarbon group having 1 to 5 carbon atoms, b is an integer of 0 to 4, and c is an integer of 0 to 3.
- An integer, d represents an integer of 0 to 3, and e represents an integer of 0 to 2.
- Such a phenol resin curing agent has a function of curing the resin composition by crosslinking the epoxy resins with each other.
- two Y's each independently represent a hydroxyphenyl group represented by Formula (1B) or Formula (1C), and X represents Formula (1D) or Formula (1E).
- R 2 and R 3 each independently represent a hydrocarbon group having 1 to 5 carbon atoms
- b is an integer of 0 to 4
- c is an integer of 0 to 3.
- An integer, d represents an integer of 0 to 3, and e represents an integer of 0 to 2.
- n is an average value, preferably 0 to 6, more preferably 0 to 3, and still more preferably 0 to 1.
- the number average molecular weight of the phenol resin curing agent represented by the formula (1A) is preferably 390 or more and 1000 or less, more preferably 400 or more and 600 or less, further preferably 400 or more and 550 or less, and particularly preferably 400 or more and 500 or less.
- Such a phenolic resin curing agent has an aromatic ring substituted with a plurality of hydroxyl groups, and therefore has a strong interaction between molecules derived from hydrogen bonds, and has a moldability, especially filling during continuous molding, compared to conventional resins.
- n can be calculated from the number average molecular weight, the above X and Y, and the structure of the biphenyl skeleton and the composition ratio.
- R 1 , R 2 and R 3 in the formulas (1A) to (1E) each independently represent a hydrocarbon group having 1 to 5 carbon atoms.
- R 1 , R 2 and R 3 if the number of carbons is 5 or less, it is possible to reliably prevent the reactivity of the resulting resin composition from being lowered and the moldability from being impaired.
- the substituents R 1 , R 2 and R 3 include, for example, a methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, 2-methylbutyl And alkyl groups such as a 3-methylbutyl group and a t-pentyl group.
- a methyl group is preferable. Thereby, the balance between curability and hydrophobicity of the resin composition can be made particularly excellent.
- A represents the number of substituents R 1 bonded to the same benzene ring in the formula (1A), a is independently an integer of 0 to 4, and b and d are the formulas In (1B) and (1D), this represents the number of substituents R 2 bonded to the same benzene ring, b is independently of each other an integer of 0 to 4, and d is independently of each other, And an integer of 0 to 3, and c and e represent the number of substituents R 3 bonded to the same benzene ring in formulas (1C) and (1E), and c are independently of each other, 0 And e is independently an integer from 0 to 2, a is preferably an integer from 0 to 2, and b, c, d, e are preferably integers from 0 or 1. .
- a monovalent hydroxyphenyl group represented by the formula (1B) (hereinafter, the monovalent hydroxyphenyl group means a hydroxyphenyl group having one hydroxyl group).
- a monovalent hydroxyphenylene group represented by the formula (1D) (hereinafter, the monovalent hydroxyphenylene group is described as a hydroxyphenylene group having one hydroxyl group), and the formula A divalent hydroxyphenyl group represented by (1C) (hereinafter, divalent hydroxyphenyl group is described as a hydroxyphenyl group having two hydroxyl groups) and a divalent hydroxyphenylene group represented by formula (1E) (Hereinafter, the divalent hydroxyphenylene group is described as the meaning of a hydroxyphenylene group having two hydroxyl groups).
- the resin composition obtained by using a phenol resin curing agent containing a monovalent hydroxyphenyl group represented by the formula (1B) and a monovalent hydroxyphenylene group represented by the formula (1D) is an excellent difficulty. Has flammability, low water absorption, and solder resistance.
- the phenol resin curing agent containing the divalent hydroxyphenyl group represented by the formula (1C) and the divalent hydroxyphenylene group represented by the formula (1E) is obtained because the density of the phenolic hydroxyl group is high.
- the cured product of the resulting resin composition has a high glass transition temperature (Tg).
- Tg glass transition temperature
- a polymer having a phenolic hydroxyl group such as a phenol resin curing agent represented by the formula (1A) has a higher weight reduction rate as the density of the phenolic hydroxyl group increases.
- an increase in the weight reduction rate accompanying an increase in Tg is suppressed. The reason for this is not necessarily clear, but it is considered that the methylene group portion that links the biphenyl skeleton of the crosslinked product and the divalent phenol is protected by steric bulk and is relatively resistant to thermal decomposition.
- k is the sum of the number of hydroxyphenyl groups represented by the formula (1B) and the number of hydroxyphenylene groups represented by the formula (1D), and the average of k
- the value is k0
- the sum of the number of hydroxyphenyl groups represented by formula (1C) and the number of hydroxyphenylene groups represented by formula (1E) is m
- the average value of m is m0, k0 /
- the value of m0 is preferably 0/100 to 82/18, more preferably 20/80 to 80/20, and even more preferably 25/75 to 75/25.
- the values of k0 and m0 can be obtained by calculating the relative intensity ratio measured by field desorption mass spectrometry (FD-MS) as a mass ratio. Alternatively, it can be determined by H-NMR or C-NMR measurement.
- FD-MS field desorption mass spectrometry
- the phenol resin curing agent represented by the formula (1A) can be produced by the following method.
- the phenol resin curing agent represented by the formula (1A) is represented by, for example, a biphenylene compound represented by the formula (3), a monohydric phenol compound represented by the formula (4), and a formula (5). It can be produced by reacting a dihydric phenol compound with an acidic catalyst.
- Z represents a hydroxyl group, a halogen atom, or an alkoxy group having 1 to 6 carbon atoms
- R 1 represents a hydrocarbon group having 1 to 5 carbon atoms
- a represents an integer of 0 to 4
- R 2 represents a hydrocarbon group having 1 to 5 carbon atoms, and b represents an integer of 0 to 4)
- R 3 represents a hydrocarbon group having 1 to 5 carbon atoms, and c represents an integer of 0 to 3)
- examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
- examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, t-butoxy group, n-pentoxy group, 2-methylbutoxy group, 3-methylbutoxy group.
- Examples of the hydrocarbon group having 1 to 5 carbon atoms in R 1 include a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, and a 2-methylbutyl group.
- Alkyl groups such as 3-methylbutyl group and t-pentyl group.
- Such a compound represented by formula (3) include 4,4′-bischloromethylbiphenyl, 4,4′-bisbromomethylbiphenyl, and 4,4′-bisiodomethyl.
- Biphenyl, 4,4′-bishydroxymethylbiphenyl, 4,4′-bismethoxymethylbiphenyl and the like can be mentioned, and one or more of these can be used in combination.
- 4 4,4′-bismethoxymethylbiphenyl or 4,4′-bischloromethylbiphenyl is preferably used.
- 4,4'-bismethoxymethylbiphenyl is preferably used from the viewpoint that it can be synthesized at a relatively low temperature, and that reaction by-products can be easily distilled off and handled.
- 4,4'-bischloromethylbiphenyl Is preferably used from the viewpoint that hydrogen halide generated due to the presence of a small amount of moisture can be used as an acid catalyst.
- Examples of the monohydric phenol compound represented by the formula (4) include phenol, o-cresol, p-cresol, m-cresol, phenylphenol, ethylphenol, n-propylphenol, isopropylphenol, t-butylphenol, and xylenol. , Methylpropylphenol, methylbutylphenol, dipropylphenol, dibutylphenol, nonylphenol, mesitol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, and the like. Two or more kinds may be used in combination. Among these, phenol and o-cresol are preferable, and phenol is particularly preferably used from the viewpoint of excellent reactivity with the epoxy resin.
- Examples of the dihydric phenol compound represented by the formula (5) include resorcinol, catechol, hydroquinone and the like, and these may be used alone or in combination of two or more.
- resorcinol and hydroquinone are preferably used from the viewpoint of the reactivity of the resin composition, and resorcinol is more preferably used from the viewpoint that the phenol resin curing agent can be synthesized at a relatively low temperature.
- the acidic catalyst is not particularly limited, and examples thereof include formic acid, oxalic acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, trifluoromethanesulfonic acid, and Lewis acid. Among these, One kind or a combination of two or more kinds can be used.
- the number average molecular weight of the obtained phenol resin curing agent is preferably 390 or more and 1000 or less, more preferably 400 or more and 600 or less, further preferably 400 or more and 550 or less, and particularly preferably 400.
- the reaction conditions can be adjusted to be 500 or less. For example, a total of 1 mol of the monohydric phenol compound and the dihydric phenol compound is reacted with 0.01 to 0.8 mol of a biphenylene compound and optionally 0.01 to 0.05 mol of an acidic catalyst, Thereafter, the reaction product is reacted at a temperature of 80 to 170 ° C.
- curing agent obtained, and the dihydric phenol of Formula (1C) and (1E) The reaction conditions are adjusted so that the compounding ratio (k0 / m0) of the compound is preferably 0/100 to 82/18, more preferably 20/80 to 80/20, still more preferably 25/75 to 75/25. Can be adjusted.
- the amount of the monohydric phenol compound is preferably 15 to 85 mol%, more preferably 20 to 80 mol%, still more preferably 20 to 75 mol% with respect to the total of 100 mol% of the monohydric phenol compound and the dihydric phenol compound. Can be reacted. If the blending ratio of the monohydric phenol compound is equal to or higher than the above lower limit, an increase in raw material costs can be suppressed, and the resulting resin composition can be excellent in fluidity. If the blending ratio of the monohydric phenol compound is not more than the above upper limit, the resulting resin composition is excellent in flow characteristics, solder resistance and flame retardancy, and has sufficient toughness at the molding temperature, so that it is excellent in moldability. Can be. As described above, by setting the blending ratio of the two phenol compounds within the above range, the resin composition has an excellent balance of flow characteristics, solder resistance, flame resistance, heat resistance, and moldability, particularly continuous moldability. Things can be obtained economically.
- the number average molecular weight, the hydroxyl group equivalent, and the value of k0 / m0 of the phenol resin curing agent represented by the formula (1A) can be adjusted by using a method for synthesizing a phenol resin known to those skilled in the art.
- the value of k0 / m0 of the phenol resin curing agent can be adjusted by the blending ratio of the monohydric phenol compound and the dihydric phenol compound used for the synthesis.
- the amount of the biphenylene compound with respect to the total amount of the monohydric phenol compound and the dihydric phenol compound used for the synthesis of the phenol resin curing agent is made close to 1: 1 by a molar ratio, and the high molecular weight and A phenol resin curing agent having a high viscosity can be obtained.
- the reaction proceeds by hydrogen halide or alcohol gas by-produced by the reaction of the biphenylene compound of formula (3) with the monohydric phenol compound of formula (4) and the dihydric phenol compound of formula (5). It can be confirmed by measuring the occurrence state of this or the molecular weight of the product during the reaction by gel permeation chromatography.
- the resin composition may contain other curing agents as long as the effect of using the phenol resin curing agent represented by the formula (1A) is not impaired, preferably in the entire curing agent. It is preferable to contain a phenol resin curing agent represented by the formula (1A) at 50% by mass or more.
- curing agent which can be used together, For example, a polyaddition type hardening
- 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 Polyamine compounds such as: hexahydrophthalic anhydride, alicyclic acid anhydrides such as methyltetrahydrophthalic anhydride; trimellitic anhydride, pyromellitic anhydride, aromatic acid anhydrides such as benzophenone tetracarboxylic acid, etc.
- aliphatic polyamines such as diethylenetriamine, triethylenetetramine and metaxylenediamine
- aromatic polyamines such as diaminodiphenylmethane, m-phenylenediamine and diaminodiphenylsulfone
- Acid anhydrides included those known to those skilled in the art in the field of semiconductor encapsulants such as novolak type phenolic resins, polyphenolic compounds such as phenolic polymers represented by polyvinylphenol; Risarufaido, thioester, polymercaptan compounds such as thioethers; isocyanate prepolymer, an isocyanate compound such as blocked isocyanate; organic acids such as carboxylic acid-containing polyester resins.
- catalyst-type curing agent examples include tertiary amine compounds such as benzyldimethylamine and 2,4,6-trisdimethylaminomethylphenol; imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole. Compound; Lewis acid such as BF 3 complex can be used.
- condensation type curing agent examples include a phenol resin curing agent such as a resol type phenol resin; a urea resin such as a methylol group-containing urea resin; and a melamine resin such as a methylol group-containing melamine resin.
- a phenol resin curing agent is preferable from the viewpoint of balance between flame retardancy, moisture resistance, electrical characteristics, curability, storage stability, and the like.
- phenol resin curing agents include, for example, novolak type resins such as phenol novolak resin, cresol novolak resin, naphthol novolak resin; polyfunctional phenol resin such as triphenolmethane type phenol resin; terpene modified phenol resin, Modified phenolic resin such as dicyclopentadiene modified phenolic resin; phenol aralkyl resin having phenylene skeleton and / or biphenylene skeleton, aralkyl type resin such as naphthol aralkyl resin having phenylene and / or biphenylene skeleton; bisphenol A, bisphenol F Such bisphenol compounds may be used, and these may be used alone or in combination of two or more.
- the hydroxyl equivalent is preferably 90 g / eq or more and 250 g / eq or less from the viewpoint of curability.
- the blending amount of the total curing agent including the phenol resin curing agent in the resin composition of the present invention is preferably 1% by mass or more and 20% by mass or less, and preferably 2% by mass or more and 15% by mass or less. More preferably, it is 3 mass% or more and 10 mass% or less. If it is in the said range, the obtained resin composition is excellent in balance of sclerosis
- Y's each independently represent a glycidylated phenyl group represented by Formula (2B) or Formula (2C), and X represents Formula (2D) or Formula (2E).
- n represents a number of 0 or more, and when n is 2 or more, two or more Xs may be the same or different from each other independently of each other.
- R 1 each independently represent a hydrocarbon group having 1 to 5 carbon atoms, and a represents an integer of 0 to 4.
- R 2 and R 3 each independently represent a hydrocarbon group having 1 to 5 carbon atoms
- b is an integer of 0 to 4
- c is an integer of 0 to 3.
- An integer, d represents an integer of 0 to 3
- e represents an integer of 0 to 2.
- n is an average value, preferably 0 to 6, more preferably 0 to 3, and still more preferably 0 to 1.
- the number average molecular weight of the epoxy resin represented by the formula (2A) is preferably 450 or more and 2000 or less, more preferably 500 or more and 1000 or less, further preferably 500 or more and 800 or less, and most preferably 500 or more and 700 or less.
- Such an epoxy resin is strongly affected by the interaction of hydrogen bonds derived from a phenol resin curing agent containing an aromatic ring having a plurality of hydroxyl groups in the curing process, and has a moldability, particularly compared to conventional resins.
- n can be calculated from the number average molecular weight, the above X and Y, and the structure of the biphenyl skeleton and the composition ratio thereof.
- R 1 in the formula (2A) each independently represents a hydrocarbon group having 1 to 5 carbon atoms.
- R 2 and R 3 in the formulas (2B) to (2E) each independently represent a hydrocarbon group having 1 to 5 carbon atoms.
- R 1 , R 2 and R 3 if the number of carbons is 5 or less, it is possible to reliably prevent the reactivity of the resulting resin composition from being lowered and the moldability from being impaired.
- substituents R 1 , R 2 and R 3 include, for example, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, 2-methylbutyl group, Examples thereof include alkyl groups such as 3-methylbutyl group and t-pentyl group. Among these, a methyl group is preferable. Thereby, the balance between curability and hydrophobicity of the resin composition can be made particularly excellent.
- a represents the number of substituents R 1 bonded on the same benzene ring, and a is an integer of 0 to 4 independently of each other.
- b and d represent the number of substituents R 2 bonded to the same benzene ring, b is independently an integer of 0 to 4, and d is Independently of each other, they are integers of 0 to 3.
- C and e in formula (2C) and formula (2E) represent the number of substituents R 3 bonded to the same benzene ring, c is independent of each other and is 0 to 3, and e is independent of each other And an integer of 0-2.
- B, c, d and e are preferably integers of 0 or 1.
- the epoxy resin represented by the formula (2A) is represented by the glycidylated phenyl group having one glycidyl ether group represented by the formula (2B) and the formula (2D).
- a glycidylated phenylene group having one glycidyl ether group, a glycidylated phenyl group having two glycidyl ether groups represented by formula (2C), and two glycidyl ether groups represented by formula (2E) Contains a glycidylated phenylene group.
- the resulting resin composition has excellent flame retardancy, low water absorption, and solder resistance.
- an epoxy resin containing a glycidylated phenyl group having two glycidyl ether groups represented by the formula (2C) and a glycidylated phenylene group having two glycidyl ether groups represented by the formula (2E) is glycidyl Since the density of the ether group is high, the cured product of the obtained resin composition has a high glass transition temperature (Tg). Generally, in the epoxy resin represented by the formula (2A), the weight reduction rate increases as the density of glycidyl ether groups increases.
- the epoxy resin represented by the formula (2A) can be produced by the following method.
- the epoxy resin represented by the formula (2A) is obtained by, for example, reacting the phenol resin curing agent represented by the formula (1A) with epichlorohydrin to replace the hydroxyl group of the phenol resin curing agent with a glycidyl ether group. Can be manufactured. At that time, selection of the phenol resin curing agent represented by the formula (1A) of the raw material to be used can adopt a preferred embodiment as the curing agent.
- a phenol resin curing agent represented by the formula (1A) and excess epichlorohydrin are mixed. Thereafter, the mixture is preferably subjected to a temperature of 50 to 150 ° C., more preferably 60 to 120 ° C., preferably 1 to 10 hours in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. React for a certain amount of time. Then, after the reaction is completed, excess epichlorohydrin is distilled off, the residue is dissolved in an organic solvent such as methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the organic solvent is distilled off to remove the epoxy. Obtain a resin.
- an organic solvent such as methyl isobutyl ketone
- the amount of epichlorohydrin added is preferably set to about 2 to 15 times mol, more preferably about 2 to 10 times mol relative to the hydroxyl group equivalent of the raw material phenol resin curing agent.
- the addition amount of the alkali metal hydroxide is preferably set to about 0.8 to 1.2 times mol, preferably 0.9 to 1.1 times mol, based on the hydroxyl group equivalent of the phenol resin curing agent. More preferably, the degree is set.
- the resin composition may contain other epoxy resins as long as the effect of using the epoxy resin represented by the formula (2A) is not impaired, and preferably 50 masses in all epoxy resins. % Or more of the epoxy resin represented by the formula (2A) is preferably included.
- epoxy resins include, for example, biphenyl type epoxy resins, bisphenol type epoxy resins, stilbene type epoxy resins, sulfide type epoxy resins, crystalline hydroxy resins such as dihydroxyanthracene type epoxy resins; methoxynaphthalene skeleton-containing novolak type epoxy resins , Novolac epoxy resins such as phenol novolac epoxy resins and cresol novolac epoxy resins; phenol modified aromatics obtained by denaturing and then epoxidizing resins obtained by condensing aromatic hydrocarbons with formaldehyde Hydrocarbon-formaldehyde resin type epoxy resin; triphenolmethane type epoxy resin, alkyl modified triphenolmethane type epoxy resin, tetrakishydroxyphenylethane type epoxy resin
- Polyfunctional epoxy resins such as: phenol aralkyl type epoxy resins having a phenylene skeleton, aralkyl type epoxy resins such as phenol aralkyl type epoxy resins having a biphen
- the crystalline epoxy resin is preferable in terms of excellent fluidity, and the polyfunctional epoxy resin is excellent in heat resistance and in that the contamination of the mold in continuous molding is mild.
- the phenolphthalein type epoxy resin is preferable in that it has an excellent balance of flame retardancy and solder resistance even when the inorganic filler content described below is low, and a phenol aralkyl type epoxy resin having a phenylene skeleton and a biphenylene skeleton.
- An epoxy resin such as an aralkyl type epoxy resin such as a phenol aralkyl type epoxy resin and a phenol-modified aromatic hydrocarbon-formaldehyde resin type epoxy resin is preferable in terms of excellent solder resistance, and includes a naphthol type epoxy resin and a methoxynaphthalene skeleton. Containing molecules such as novolak-type epoxy resin Epoxy resins having a naphthalene skeleton is preferable from the viewpoint of excellent balance of flame retardancy and heat resistance.
- the resin composition does not contain Na ions and Cl ions which are ionic impurities as much as possible from the viewpoint of moisture resistance reliability.
- the epoxy equivalent of the epoxy resin is preferably 100 g / eq or more and 500 g / eq or less.
- the amount of the total epoxy resin in the resin composition is preferably 1% by mass or more and 20% by mass or less, and more preferably 2% by mass or more and 15% by mass or less with respect to the entire resin composition. More preferably, it is 3 mass% or more and 10 mass% or less.
- the resin composition comprises a polymer represented by the formula (1A) as a phenol resin curing agent and a polymer represented by the formula (2A) as an epoxy resin.
- a polymer represented by the formula (1A) has at least one of a divalent hydroxyphenyl group represented by the formula (1C) and a divalent hydroxyphenylene group represented by the formula (1E).
- the polymer represented by the general formula (2A) has a glycidylated phenyl group having two glycidyl ether groups represented by the formula (2C) and two glycidyl ether groups represented by the formula (2E). It has at least one of glycidylated phenylene groups.
- the functional group density of both the polymer represented by the formula (1A) as the phenol resin curing agent and the polymer represented by the formula (2A) as the epoxy resin is improved. Therefore, the crosslinked density of the cured product formed by crosslinking the epoxy resins with each other via the phenol resin curing agent is increased. As a result, the glass transition temperature (Tg) of the cured product is improved.
- the polymer represented by the formula (1A) and the polymer represented by the formula (2A) may have the same main skeleton. That is, in the polymer represented by formula (1A), a hydroxyl group is introduced into the phenyl group constituting the main skeleton, and in the polymer represented by formula (2A), glycidyl is incorporated into the phenyl group constituting the main skeleton. It can be set as the aspect which has the same structural unit except the ether group being introduce
- the functional group density is increased in order to improve the glass transition temperature (Tg) of the cured product of the resin composition, it is formed by the reaction between an epoxy group (glycidyl ether group) and a hydroxyl group.
- the weight reduction rate increases due to the thermal decomposition of the cross-linked points (connecting portions).
- both the polymer represented by the formula (1A) and the polymer represented by the formula (2A) contain a structural unit having a common main skeleton.
- the methylene group present in the cross-linked product of the phenol resin curing agent and the epoxy resin is protected by the steric bulk of these polymers and secondary decomposition is suppressed. Is done.
- the resin composition contains, as main components, the polymer represented by the formula (1A) as a phenol resin curing agent and the polymer represented by the formula (2A) as an epoxy resin. Both improvement of Tg of the cured product of the resin composition and reduction of the weight reduction rate of the cured product can be realized. As a result, a cured product obtained by curing the resin composition is excellent in adhesiveness, electrical stability, flame retardancy, moldability, particularly continuous moldability and heat resistance, and particularly has high Tg in heat resistance. And a reduction in weight reduction can be achieved at the same time.
- the glass transition temperature (Tg) of the cured product is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, 300 ° C. or lower, and further preferably 220 ° C. As mentioned above, it can be set as 250 degrees C or less. Further, the weight loss rate when the cured product is heated at 200 ° C. for 1000 hours in an air atmosphere is preferably 0.3% or less, more preferably 0.07% or more and 0.25% or less, and still more preferably. May be 0.07% or more and 0.2% or less. If the Tg and weight reduction rate of the cured product can be set within such ranges, the resin cured product is unlikely to deteriorate even at high temperatures. Therefore, it can be used as a semiconductor sealing material for a package equipped with a semiconductor element such as SiC or GaN. .
- the weight reduction rate of the cured product can be measured, for example, by the following method. First, a disk-shaped test piece of the resin composition is formed, this test piece is cured at 175 ° C. for 4 hours, then dried at 125 ° C. for 20 hours, the weight after cooling is measured, and the initial weight is obtained. Next, this test piece is put into a high-temperature bath at 200 ° C. in an air atmosphere, heated for 1000 hours, the weight after cooling is measured, and the weight after treatment is obtained. The weight reduction rate can be calculated by obtaining the ratio of the treated weight to the initial weight.
- the content of the phenol resin curing agent represented by the formula (1A) in the resin composition is A1 (mass%), and the resin of the epoxy resin represented by the formula (2A)
- the value of A1 / (A1 + A2) is preferably 0.2 or more and 0.9 or less, more preferably 0.3 or more, 0 .7 or less.
- the lower limit of the hydroxyl group equivalent of the phenol resin curing agent represented by the formula (1A) is preferably set to 90 g / eq or more, more preferably 100 g / eq or more.
- the upper limit of the hydroxyl equivalent is preferably set to 190 g / eq or less, more preferably 180 g / eq or less, and still more preferably 170 g / eq or less.
- the upper limit value and the lower limit value of the epoxy equivalent of the epoxy resin represented by the formula (2A) are the glycidyl ether of the hydroxyl group of the phenol resin curing agent represented by the above formula (1A).
- the theoretical value when substituted with a group is preferred.
- the epoxy equivalent of such an epoxy resin is preferably 50% or more, more preferably 70% or more of the theoretical value, the effects of the present invention can be exhibited.
- the lower limit of the epoxy equivalent of the epoxy resin represented by the formula (2A) is preferably set to 150 g / eq or more, more preferably 160 g / eq or more, and even more preferably 170 g / eq or more. Yes.
- the upper limit of the epoxy equivalent is preferably 290 g / eq or less, more preferably 260 g / eq or less, and still more preferably 240 g / eq or less.
- the resin composition characterized by including the epoxy resin represented by Formula (2A), and the mold release agent whose 5% weight reduction temperature is 240 degreeC or more is also a hardening
- an appropriate phenol resin curing agent such as a monomer, oligomer, polymer or the like having two or more phenolic hydroxyl groups in one molecule, it is harsh as represented by an element (semiconductor element) using SiC or GaN. It can be used as a resin composition suitable for sealing an element operable in a situation.
- phenol resin curing agent examples include: novolak resin such as phenol novolak resin, cresol novolak resin, naphthol novolak resin; polyfunctional phenol resin such as triphenolmethane phenol resin; terpene modified phenol resin, dicyclo Modified phenolic resin such as pentadiene modified phenolic resin; phenol aralkyl resin having phenylene skeleton and / or biphenylene skeleton, aralkyl type resin such as naphthol aralkyl resin having phenylene and / or biphenylene skeleton; bisphenol A, bisphenol F, etc. A bisphenol compound etc. are mentioned, These may be used individually by 1 type, or may use 2 or more types together. Among these, the hydroxyl equivalent is preferably 90 g / eq or more and 250 g / eq or less from the viewpoint of curability.
- the 5% weight loss temperature means that the release agent is heated from room temperature in a nitrogen stream at a rate of temperature increase of 10 ° C./min using a differential thermal / thermogravimetric measurement device (TG / DTA). It means the temperature when 5% of the initial weight is lost.
- the 5% weight loss temperature of 240 ° C. or higher means that the temperature when 5% of the initial weight of the release agent is lost is 240 ° C. or higher when the above measurement conditions are used.
- the mold release agent refers to a substance having a function of releasing a molded product from a mold when molding with a transfer molding machine or the like.
- a resin composition comprising an epoxy resin represented by formula (2A) and a release agent having a 5% weight loss temperature of 240 ° C. or higher, or a phenol resin cured by formula (1A)
- a resin composition containing an agent, an epoxy resin represented by the formula (2A), and a release agent having a 5% weight reduction temperature of 240 ° C. or higher is extremely useful in high-temperature storage and high-temperature operation characteristic testing of electronic devices. Expresses excellent reliability. The reason for this is not clear, but at a high temperature, a release agent having a 5% weight loss temperature of 240 ° C.
- a phenol resin curing agent represented by the formula (1A), and an epoxy represented by the formula (2A) Resin and complex influence, the synergistic effect, the interface between the semiconductor element and the cured product of the resin composition, or the interface between the bonding pad or bonding wire and the cured product of the resin composition is affected, This is presumed to improve the reliability of the electronic device.
- the mold release agent having a 5% weight reduction temperature of 240 ° C. or higher according to the present invention is a mold release agent known to those skilled in the art in a resin composition for semiconductor encapsulation, and has a 5% weight reduction temperature of 240 ° C. or higher. If it is a thing, it will not specifically limit.
- Examples include polyolefin waxes (eg, polyethylene or polypropylene polymerized with olefins such as ethylene or propylene); polyolefin copolymers (eg, copolymers of maleic anhydride and 1-alkene having 28-60 carbon atoms, A copolymer of olefin and maleic anhydride, and an esterified product or derivative thereof, and an oxidized polyolefin wax or a derivative thereof (for example, oxidized polyethylene obtained by oxidizing a terminal double bond of polyethylene, etc.) Wax, urethane-modified polyethylene wax obtained by modifying the oxidized polyethylene with an isocyanate group-containing compound); higher fatty acid ester (for example, montanic acid ester); higher fatty acid amide (for example, higher fatty acid amine containing ammonia) Compound is amidated with compound) include, but are not limited to.
- the higher fatty acid ester is preferably a synthetic higher fatty acid
- the lower limit of the ratio of the release agent in the total resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more in the total resin composition. It is. If the lower limit of the mixing ratio of the release agent is within the above range, the cured product can be released from the mold during molding. Further, the upper limit value of the mixing ratio of the release agent is preferably 1.0% by mass or less, more preferably 0.8% by mass or less, and particularly preferably 0.5% by mass or less in the total resin composition. . If the upper limit of the mixing ratio of the release agent is within the above range, it has a conventionally known effect that it is possible to suppress soiling due to the release agent oozing out on the surface of the molded product.
- the electronic device It has a remarkable effect on high-temperature storage and high-temperature operating characteristics.
- the resin composition of the present invention is necessary in addition to a phenol resin curing agent represented by the formula (1A), an epoxy resin represented by the formula (2A), and a release agent having a 5% weight loss temperature of 240 ° C. or higher. Depending on the, it may contain the components shown below.
- the inorganic filler has a function of reducing an increase in moisture absorption and a decrease in strength due to the curing of the resin composition, and an inorganic filler generally used in this field can be used.
- the average particle diameter of the inorganic filler is preferably 0.01 ⁇ m or more and 150 ⁇ m or less from the viewpoint of filling properties into the mold cavity.
- the average particle size can be measured using a laser diffraction / scattering particle size distribution meter.
- the lower limit of the amount of the inorganic filler in the resin composition is preferably 75% by mass or more, more preferably 80% by mass or more, and further preferably 85% by mass with respect to the total mass of the resin composition. That's it.
- the lower limit is within the above range, a cured product having good solder crack resistance can be obtained, and since the resin content is relatively reduced, the weight reduction rate can be suppressed. It is possible to give moderate hardness to the interface of the cured product of the resin composition of the present invention that is in contact with the semiconductor element, and obtain not only the excellent high-temperature storage characteristics that are the main points of the present invention but also high-temperature operating characteristics.
- the upper limit of the amount of the inorganic filler in the resin composition is preferably 93% by mass or less, more preferably 91% by mass or less, and still more preferably 90% with respect to the total mass of the resin composition. It is below mass%.
- the upper limit is within the above range, the resulting resin composition exhibits good fluidity and moldability and can impart appropriate flexibility, not only the excellent high-temperature storage characteristics that are the main points of the present invention. Also, high temperature operating characteristics can be obtained.
- the average particle size of the inorganic filler is preferably 0.01 ⁇ m or more and 150 ⁇ m or less from the viewpoint of filling into the mold cavity, and more preferably the average particle size is 7 ⁇ m or more and 50 ⁇ m or less.
- the spherical silica is preferably contained in an amount of 60% by mass to 85% by mass, and more preferably 65% by mass to 83% by mass with respect to the composition. In the above range, the semiconductor device is sufficiently adhered to the semiconductor device at a high temperature and does not give a large stress to the device, so that not only the excellent high-temperature storage characteristics which are the main points of the present invention but also the high-temperature operating characteristics can be obtained. .
- spherical silica having an average particle size of 0.1 ⁇ m or more and 6 ⁇ m or less is preferably contained in an amount of 1% by mass or more and 25% by mass or less, and more preferably 3% by mass or more and 20% by mass or less.
- the semiconductor device is sufficiently adhered to the semiconductor device at a high temperature and does not give a large stress to the device, so that not only the excellent high-temperature storage characteristics which are the main points of the present invention but also the high-temperature operating characteristics can be obtained. .
- spherical silica having an average particle size of 7 ⁇ m or more and 50 ⁇ m or less in the composition 60% by mass or more and 85% by mass or less is included, and in addition, the composition of spherical silica having an average particle size of 0.1 ⁇ m or more and 6 ⁇ m or less When it is contained in an amount of 1% by mass or more and 25% by mass or less, it adheres sufficiently to a semiconductor device at a high temperature and does not give a large stress to the device. Also, high temperature operating characteristics can be obtained.
- inorganic flame retardants such as metal hydroxides such as aluminum hydroxide and magnesium hydroxide, zinc borate, zinc molybdate and antimony trioxide described later, these inorganic flame retardants and the above
- the total amount of inorganic filler is preferably within the above range.
- a hardening accelerator has a function which accelerates
- the curing accelerator include phosphorus atom-containing compounds such as organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, adducts of phosphonium compounds and silane compounds; -Amidines and tertiary amines exemplified by diazabicyclo (5,4,0) undecene-7, benzyldimethylamine, 2-methylimidazole and the like, and further nitrogen-containing compounds such as the quaternary salts of amidines and amines mentioned above Of these, one or two or more of these can be used in combination.
- phosphorus atom-containing compounds such as organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, adducts of phosphonium compounds and silane compounds
- a phosphorus atom-containing compound is preferable from the viewpoint of curability, and an adduct of a phosphobetaine compound, a phosphine compound and a quinone compound is particularly preferable from the viewpoint of solder resistance and fluidity.
- Phosphorus atom-containing compounds such as tetra-substituted phosphonium compounds and adducts of phosphonium compounds and silane compounds are particularly preferred from the viewpoint that contamination of these is mild.
- Examples of the organic phosphine that can be used in the resin composition include a first phosphine such as ethylphosphine and phenylphosphine; a second phosphine such as dimethylphosphine and diphenylphosphine; a trimethylphosphine, triethylphosphine, tributylphosphine, and triphenylphosphine. Tertiary phosphine.
- Examples of the tetra-substituted phosphonium compound that can be used in the resin composition include a compound represented by the formula (6).
- P represents a phosphorus atom
- R 4 , R 5 , R 6 and R 7 represent an aromatic group or an alkyl group
- A represents at least selected from a hydroxyl group, a carboxyl group, and a thiol group.
- AH represents an aromatic organic acid having an aromatic ring to which at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group is bonded.
- X and y are numbers from 1 to 3
- z is a number from 0 to 3
- x y.
- the compound represented by Formula (6) is obtained as follows, for example, it is not limited to this. 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 (6) can be precipitated.
- R 4 , R 5 , R 6 and R 7 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 preferably an anion of the phenol.
- phenols in the present invention include monocyclic phenols such as phenol, cresol, resorcin, and catechol, condensed polycyclic phenols such as naphthol, dihydroxynaphthalene, and anthraquinol, bisphenol A, bisphenol F, and bisphenol S.
- monocyclic phenols such as phenol, cresol, resorcin, and catechol
- condensed polycyclic phenols such as naphthol, dihydroxynaphthalene, and anthraquinol
- bisphenol A bisphenol F
- bisphenol S bisphenol S
- polycyclic phenols such as bisphenols, phenylphenol, and biphenol.
- Examples of the phosphobetaine compound include a compound represented by the formula (7).
- R 8 represents an alkyl group having 1 to 3 carbon atoms
- R 9 represents a hydroxyl group
- f is an integer of 0 to 5
- g is an integer of 0 to 3.
- the compound represented by the formula (7) 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
- the present invention is not limited to this.
- Examples of the adduct of a phosphine compound and a quinone compound include a compound represented by the formula (8).
- R 10 , R 11 and R 12 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
- R 13 , R 14 and R 15 each represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and may be the same or different from each other, and R 14 and R 15 are bonded to each other.
- a cyclic group may be formed.
- Examples of the phosphine compound used as an adduct of a phosphine compound and a quinone compound include an aromatic ring such as triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, and tris (benzyl) phosphine.
- aromatic ring 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, triphenyl
- examples of the quinone compound used for the adduct of the phosphine compound and the quinone compound include 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.
- the solvent is preferably a ketone such as acetone or methyl ethyl ketone, which has low solubility in the adduct.
- the present invention is not limited to this.
- R 10 , R 11 and R 12 bonded to the phosphorus atom are phenyl groups, and R 13 , R 14 and R 15 are hydrogen atoms, ie, 1, 4 -A compound in which benzoquinone and triphenylphosphine are added is preferred in that it reduces the thermal modulus of the cured product of the resin composition.
- Examples of the adduct of the phosphonium compound and the silane compound include a compound represented by the formula (9).
- P represents a phosphorus atom
- Si represents a silicon atom
- R 16 , R 17 , R 18 and R 19 are each an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group.
- R 20 is an organic group bonded to the groups Y 2 and Y 3
- R 21 is an organic group bonded to the groups Y 4 and Y 5 .
- Y 2 and Y 3 represent a group formed by releasing a proton from a proton donating group, and groups Y 2 and Y 3 in the same molecule are bonded to a silicon atom to form a chelate structure
- Y 4 and Y 3 5 represents a group formed by releasing a proton from a proton donating group, and groups Y 4 and Y 5 in the same molecule are combined with a silicon atom to form a chelate structure
- R 20 and R 21 are identical to each other.
- Y 2 , Y 3 , Y 4 and Y 5 may be the same or different from each other
- Z 1 is an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group.
- examples of R 16 , R 17 , R 18 and R 19 include a phenyl group, a methylphenyl group, a methoxyphenyl group, a hydroxyphenyl group, a naphthyl group, a hydroxynaphthyl group, a benzyl group, a methyl group, And an ethyl group, an n-butyl group, an n-octyl group, and a cyclohexyl group.
- an alkyl group such as a phenyl group, a methylphenyl group, a methoxyphenyl group, a hydroxyphenyl group, and a hydroxynaphthyl group, an alkoxy group
- An aromatic group having a substituent such as a hydroxyl group or an unsubstituted aromatic group is more preferable.
- R 20 is an organic group bonded to Y 2 and Y 3.
- R 21 is an organic group that binds to groups Y 4 and Y 5 .
- Y 2 and Y 3 are groups formed by proton-donating groups releasing protons, and groups Y 2 and Y 3 in the same molecule are combined with a silicon atom to form a chelate structure.
- Y 4 and Y 5 are groups formed by proton-donating groups releasing protons, and groups Y 4 and Y 5 in the same molecule are combined with a silicon atom to form a chelate structure.
- the groups R 20 and R 21 may be the same or different from each other, and the groups Y 2 , Y 3 , Y 4 , and Y 5 may be the same or different from each other.
- the group represented by —Y 2 —R 20 —Y 3 — and Y 4 —R 21 —Y 5 — in formula (9) is a group in which the proton donor releases two protons.
- the proton donor is preferably an organic acid having at least two carboxyl groups or hydroxyl groups in the molecule, and further having at least two carboxyl groups or hydroxyl groups on adjacent carbons constituting the aromatic ring.
- Aromatic compounds are preferable, and aromatic compounds having at least two hydroxyl groups on adjacent carbons constituting the aromatic ring are more preferable.
- catechol pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2, 2′-biphenol, 1,1′-bi-2-naphthol, salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-
- examples include phthalic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol, and glycerin.
- catechol, 1,2-dihydroxynaphthalene, 2 1,3-dihydroxynaphthalene is more preferred.
- Z 1 in the formula (9) represents an organic group or an aliphatic group having an aromatic ring or a heterocyclic ring. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group.
- aliphatic hydrocarbon groups such as octyl groups, aromatic hydrocarbon groups such as phenyl groups, benzyl groups, naphthyl groups and biphenyl groups, glycidyloxy groups such as glycidyloxypropyl groups, mercaptopropyl groups, aminopropyl groups, Examples include a mercapto group, an alkyl group having an amino group, and a reactive substituent such as a vinyl group.
- a methyl group, an ethyl group, a phenyl group, a naphthyl group, and a biphenyl group are from the viewpoint of thermal stability. More preferred.
- 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.
- curing accelerators of the present invention there are compounds represented by formulas (6) to (9). From the viewpoint of sufficiently adhering to a semiconductor element at a high temperature, particularly addition of a phosphine compound and a quinone compound. And adducts of phosphonium compounds and silane compounds are preferred.
- the phenol resin curing agent represented by the formula (1A) and the aromatic group having a plurality of hydroxyl groups contained in the epoxy resin represented by the formula (2A) and the curing accelerator It is considered that by exhibiting a unique behavior at the interface of the semiconductor element at the time of curing or at high temperature operation of the element, not only excellent high-temperature storage characteristics but also high-temperature operation characteristics are obtained in the obtained semiconductor element.
- the blending ratio of the curing accelerator is preferably 0.1% by mass or more and 1% by mass or less in the total resin composition.
- the blending ratio of the curing accelerator is within the above range, sufficient curability can be obtained.
- liquidity can be acquired as the mixture ratio of a hardening accelerator is in the said range.
- the resin composition of the present invention has a curing accelerator content of 0.11% by mass or more and 0.70% by mass or less, most preferably 0.8%.
- the content is 12% by mass or more and 0.65% by mass or less, not only excellent high temperature storage characteristics but also high temperature operation characteristics are exhibited.
- the resin composition characterized by containing a release agent having a temperature of 240 ° C. or higher the present invention is most often used in the combination in which the release agent, the inorganic filler, and the curing accelerator are the above-mentioned preferred embodiments.
- high-temperature operating characteristics are the best characteristics.
- a compound (A) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring (hereinafter sometimes simply referred to as “compound (A)”) can be obtained by using phenol Even when a phosphorus atom-containing curing accelerator having no latent property is used as a curing accelerator that promotes the crosslinking reaction between the resin curing agent and the epoxy resin, the reaction during melt-kneading of the resin composition is suppressed. be able to.
- the compound (A) has the effect of lowering the melt viscosity of the resin composition and improving the fluidity, and also has the effect of improving the solder resistance, although the detailed mechanism is unknown.
- a monocyclic compound represented by the formula (10) or a polycyclic compound represented by the formula (11) can be used, and these compounds have a substituent other than a hydroxyl group. You may do it.
- R 22 and R 26 when one of R 22 and R 26 is a hydroxyl group and one is a hydroxyl group, the other is a hydrogen atom, a hydroxyl group or a substituent other than a hydroxyl group, and R 23 , R 24 and R 25 Is a hydrogen atom, a hydroxyl group or a substituent other than a hydroxyl group.
- one of R 27 and R 33 is a hydroxyl group, and when one is a hydroxyl group, the other is a hydrogen atom, a hydroxyl group or a substituent other than a hydroxyl group, and R 28 , R 29 , R 30. , R 31 and R 32 are a hydrogen atom, a hydroxyl group or a substituent other than a hydroxyl group.
- monocyclic compound represented by the formula (10) examples include catechol, pyrogallol, gallic acid, gallic acid ester, and derivatives thereof.
- polycyclic compound represented by the formula (11) examples 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 (A) can be a compound having a naphthalene ring such as 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene and derivatives thereof.
- These compounds (A) may be used individually by 1 type, or may be used in combination of 2 or more type.
- the compounding ratio of the compound (A) 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 or less in the total resin composition. Especially preferably, it is 0.05 mass% or more and 0.5 mass% or less.
- the resin composition can be sufficiently lowered in viscosity and improved in fluidity.
- the upper limit of the compounding ratio of the compound (A) is within the above range, there is little possibility of causing a decrease in the curability of the resin composition and a decrease in the physical properties of the cured product.
- the coupling agent When the inorganic filler is contained in the resin composition, the coupling agent has a function of improving the adhesion between the epoxy resin and the inorganic filler.
- a silane coupling agent or the like is used.
- silane coupling agent various types such as mercaptosilane can be used.
- the lower limit of the blending ratio of the coupling agent such as a silane coupling agent is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass in the total resin composition. That's it. If the lower limit of the blending ratio of the coupling agent such as a silane coupling agent 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 electronic device is achieved. Obtainable.
- 1 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%.
- the blending ratio of the coupling agent such as a silane coupling agent 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 apparatus is obtained. be able to. Further, when the blending ratio of the coupling agent such as a silane coupling agent is within the above range, the water absorption of the cured product of the resin composition does not increase, and good solder crack resistance in an electronic device can be obtained. Can do.
- An inorganic flame retardant has a function which improves the flame retardance of a resin composition, and the generally used inorganic flame retardant is used.
- a metal hydroxide that inhibits the combustion reaction by dehydrating and absorbing heat during combustion, or a composite metal hydroxide that can shorten the combustion time is preferably used.
- metal hydroxide examples include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, and zirconia hydroxide.
- the composite metal hydroxide is a hydrotalcite compound containing two or more metal elements, wherein at least one metal element is magnesium, and the other metal elements are calcium, aluminum, tin, titanium, iron Any metal element selected from cobalt, nickel, copper, or zinc may be used, and as such a composite metal hydroxide, a magnesium hydroxide / zinc solid solution is commercially available.
- aluminum hydroxide and magnesium hydroxide / zinc solid solution are preferable from the viewpoint of the balance between solder resistance and continuous formability.
- Inorganic flame retardants may be used alone or in combination of two or more. Further, for the purpose of reducing the influence on the continuous moldability, a surface treatment may be performed with a silicon compound such as a silane coupling agent or an aliphatic compound such as wax.
- the inorganic flame retardant may be used.
- the inorganic flame retardant is preferably dried at 125 ° C. for 20 hours, and the weight after cooling in the desiccator is set to 200 ° C. as the initial weight.
- the phenol resin curing agent represented by the formula (1A) and the epoxy resin represented by the formula (2A) both have a flame retardant biphenyl skeleton. It has high flame retardancy and also functions as a flame retardant. Therefore, water is released at a high temperature of 200 ° C. or higher, and as a result, even if the blending of metal hydroxide flame retardant that may increase the weight reduction rate of the cured product is omitted, the flame retardant is added. The same characteristics as those obtained can be imparted to the resin composition.
- components known to those skilled in the art such as colorants such as carbon black, bengara, and titanium oxide may be appropriately blended.
- the resin composition of the present invention as described above is prepared by mixing a phenol resin curing agent, an epoxy resin, and other components uniformly at room temperature using, for example, a mixer, and then as necessary. It is possible to adjust to a desired degree of dispersion, fluidity, etc. by melt-kneading using a kneader such as a heating roll, a kneader or an extruder, followed by cooling and pulverization as necessary.
- a kneader such as a heating roll, a kneader or an extruder
- the electronic device of the present invention is not limited to the case described in the above description, and can be applied to various types of semiconductor packages.
- a dual in-line package DIP
- Chip Carrier with Plastic Lead PLCC
- Quad Flat Package QFP
- Low Profile Quad Flat Package LQFP
- Small Outline Package SOP
- Small Outline J Lead Package SOJ
- Thin Small Outline Package SOJ
- Thin Quad Flat Package TQFP
- Tape Carrier Package TCP
- BGA Ball Grid Array
- CSP Chip Size Package
- Matric ⁇ TO which mounts power system elements such as power transistors as well as packages applicable to memory and logic system elements such as array, package, ball grid array (MAPBGA), chip, stacked chip size, and package It can be preferably applied to packages such as ⁇ 220.
- the resin composition of the present invention may contain an optional component that can exhibit the same function.
- each part of the electronic device of the present invention can be replaced with an arbitrary one that can exhibit the same function, or an arbitrary configuration can be added.
- reaction was carried out for 3 hours while maintaining the system temperature in the range of 110 to 130 ° C., followed by heating and reaction for 3 hours while maintaining the temperature in the range of 140 to 160 ° C.
- the hydrochloric acid gas generated in the system by the above reaction was discharged out of the system by a nitrogen stream.
- a hydroxyl group is a repeating unit of one structural unit obtained by arithmetic calculation by regarding the relative intensity ratio measured and analyzed by field desorption mass spectrometry (FD-MS) as a mass ratio.
- the ratio k0 / m0 of the average value k0 of the number k, the average value m0 of the repeating number m of the structural unit having two hydroxyl groups was 0.98 / 1, and the number average molecular weight was 460.
- the number average molecular weight is an alliance manufactured by Waters (2695 Separations Module, 2414 Refractive Index Detector, TSK Gel GMHHR-Lx2 + TSK Guard Column HHR-Lx1, mobile phase: THF, 0.5 ml / min), column temperature 40
- the number average molecular weight was measured by gel permeation chromatography (GPC) under the conditions of 0.0 ° C., differential refractometer internal temperature 40.0 ° C. and sample injection amount 100 ⁇ l.
- the average value k0 of the repeating number k of the structural unit with one hydroxyl group obtained by calculating the relative intensity ratio measured and analyzed by the field desorption mass spectrometry as the mass ratio, and the hydroxyl group is 2
- the ratio k0 / m0 of the average value m0 of the number m of repeating structural units was 0.51 / 1, and the number average molecular weight was 480.
- triphenylmethane type phenolic resin (MEH-7500, manufactured by Meiwa Kasei Co., Ltd., hydroxyl group equivalent 97 g / eq) was prepared.
- the epoxy resin 1 (epoxy equivalent 200g / eq) containing the compound to be obtained was obtained.
- the number average molecular weight of this epoxy resin was 560.
- epoxy resin 2 (Epoxy resin 2; synthesis of MFBA type epoxy) Except for using phenol resin curing agent 2 (120 parts by mass), synthesis is performed in the same manner as for epoxy resin 1 to obtain epoxy resin 2 (epoxy equivalent 185 g / eq) containing the compound represented by formula (13A). It was. The number average molecular weight of the obtained epoxy resin 2 was 670.
- Epoxy resin 3 preparation of BA type epoxy
- a phenol aralkyl resin type epoxy resin having a biphenylene skeleton (an epoxy resin made from a phenol aralkyl resin having a biphenylene skeleton having one phenolic hydroxyl group) (Nippon Kayaku Co., Ltd., NC3000, epoxy equivalent 276 g / eq, softening point) 58 ° C.).
- Td5 5% weight loss temperature
- TG / DTA thermogravimetric simultaneous measurement device
- urethane-modified polyethylene oxide wax manufactured by Nippon Seiwa Co., Ltd., “NSP-6010P”, Td5 262 ° C.
- a montanic acid ester manufactured by Clariant Japan, “Recolbe WE4”, Td5 285 ° C.
- a compound prepared by esterifying a copolymer of maleic anhydride and 1-alkene (carbon number 28-60) with stearyl alcohol was prepared.
- Td5 was 270 ° C.
- stearic acid manufactured by NOF Corporation, “SR-Sakura”, Td5 220 ° C.
- Inorganic filler 1 As the inorganic filler 1, fused spherical silica (“FB560” manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 30 ⁇ m) was prepared. The average particle size of the present invention was measured using a laser diffraction / scattering particle size distribution analyzer SALD-7000 manufactured by Shimadzu Corporation.
- SALD-7000 laser diffraction / scattering particle size distribution analyzer
- Inorganic filler 2 As the inorganic filler 2, fused spherical silica (“SO-25R” manufactured by Admatechs, average particle diameter of 0.5 ⁇ m) was prepared.
- the hardening accelerator shown by Formula (14) was prepared.
- Method for synthesizing curing accelerator 1 A separable flask equipped with a stirrer was charged with 37.5 g (0.15 mol) of 4,4′-bisphenol S and 100 ml of methanol, dissolved by stirring at room temperature, and 4.0 g of sodium hydroxide in 50 ml of methanol in advance while stirring. A solution in which (0.1 mol) was dissolved was added. Next, a solution in which 41.9 g (0.1 mol) of tetraphenylphosphonium bromide was previously dissolved in 150 ml of methanol was added.
- a curing accelerator represented by the formula (15) was prepared.
- Method for synthesizing curing accelerator 2 A separable flask equipped with a condenser and a stirrer was charged with 12.81 g (0.080 mol) of 2,3-dihydroxynaphthalene, 16.77 g (0.040 mol) of tetraphenylphosphonium bromide and 100 ml of methanol, and dissolved uniformly. It was.
- a compound in which 1,4-benzoquinone represented by the formula (17) and triphenylphosphine were added was prepared.
- Method for synthesizing curing accelerator 4 A separable flask equipped with a condenser and a stirrer was charged with 6.49 g (0.060 mol) of benzoquinone, 17.3 g (0.066 mol) of triphenylphosphine and 40 ml of acetone, and reacted at room temperature with stirring. The precipitated crystals were washed with acetone, filtered and dried to obtain dark green crystal curing accelerator 4.
- triphenylphosphine manufactured by Wako Pure Chemical Industries
- silane coupling agent 1 As silane coupling agent 1, 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-803) was prepared.
- Carbon black As a colorant, carbon black (“MA600” manufactured by Mitsubishi Chemical Corporation) was prepared.
- Examples 2 to 13, Comparative Examples 1 to 4 Resin compositions of Examples 2 to 13 and Comparative Examples 1 to 4 were obtained in the same manner as in Example 1 except that the types and blending amounts of raw materials were changed as shown in Table 1.
- Td5 1.5% weight loss temperature
- Spiral flow is a parameter of fluidity. The larger the value, the better the fluidity.
- the unit is cm. In order to seal the module by applying it to a SiC or GaN power semiconductor package, it is preferably 60 cm or more.
- a test piece of 80 mm ⁇ 10 mm ⁇ 4 mm was molded using a transfer molding machine at a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 90 seconds. And post-cured at 175 ° C. for 4 hours, and measured for dynamic viscoelasticity (“DDV-25GP”, manufactured by A & D) (heating rate: 5 ° C./min, frequency: 10 Hz, load: 800 g) The tan ⁇ peak temperature was read as the glass transition temperature.
- DDV-25GP dynamic viscoelasticity
- the disk-shaped test piece was thrown into the 200 degreeC high temperature tank in air
- Table 1 the weight reduction rate before and after the heat treatment is shown as a percentage.
- Table 1 shows the fire resistance rank (class) after the determination.
- HTSL high-temperature storage characteristics
- HTOL high-temperature operating characteristics
- each example achieves both an improvement in the glass transition temperature (Tg) and a reduction in the weight reduction rate of the cured product while maintaining the flame resistance and fluidity characteristics of the cured product.
- Tg glass transition temperature
- I was able to.
- the high temperature storage characteristics and high temperature operation characteristics were also good.
- extremely excellent reliability was obtained in a semiconductor device equipped with an element capable of operating under severe conditions represented by an element (semiconductor element) using SiC or GaN.
- Comparative Example 1 since the phenol resin curing agent represented by the formula (1A) and the epoxy resin represented by the formula (2A) are used, the characteristics of high Tg and low weight loss are Although having a 5% weight loss temperature of less than 240 ° C., a release agent was used, and the high temperature storage characteristics and high temperature operation characteristics were inferior to those of the examples.
- Comparative Example 2 only the phenol resin curing agent represented by the general formula (1A) was used, and the Tg was slightly lower than that of the example and the weight reduction was slightly larger than that of the example. Also, the high temperature storage characteristics and high temperature operation characteristics were inferior to those of the examples.
- a phenol aralkyl resin having a biphenylene skeleton (a phenol aralkyl resin having a single phenol hydroxyl group) and a phenol aralkyl resin type epoxy resin having a biphenylene skeleton (a phenol having one biphenylene skeleton)
- Epoxy resin made from phenol aralkyl resin as a raw material although the weight reduction rate is good, Tg is much lower than 200 ° C., and the high-temperature storage characteristics and high-temperature operation characteristics were also inferior.
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Abstract
Description
(式(1A)中、2つのYは、それぞれ互いに独立して、式(1B)または式(1C)で表されるヒドロキシフェニル基を表し、Xは、式(1D)または式(1E)で表されるヒドロキシフェニレン基を表し、nは0以上の数を表し、nが2以上の場合、2つ以上のXは、それぞれ互いに独立して、同一であっても異なっていてもよく、R1は、それぞれ互いに独立して、炭素数1~5の炭化水素基を表し、aは0~4の整数を表す。)
(式(1B)~(1E)中、R2およびR3は、それぞれ互いに独立して、炭素数1~5の炭化水素基を表し、bは0~4の整数、cは0~3の整数、dは0~3の整数、eは0~2の整数を表す。)
(式(2A)中、2つのYは、それぞれ互いに独立して、式(2B)または式(2C)で表されるグリシジル化フェニル基を表し、Xは、式(2D)または式(2E)で表されるグリシジル化フェニレン基を表し、nは0以上の数を表し、nが2以上の場合、2つ以上のXは、それぞれ互いに独立して、同一であっても異なっていてもよく、R1は、それぞれ互いに独立して、炭素数1~5の炭化水素基を表し、aは0~4の整数を表す。)
(式(2B)~(2E)中、R2およびR3は、それぞれ互いに独立して、炭素数1~5の炭化水素基を表し、bは0~4の整数、cは0~3の整数、dは0~3の整数、eは0~2の整数を表す。)
(式(6)において、Pはリン原子を表し、R4、R5、R6およびR7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、チオール基から選ばれる少なくとも1つの官能基が結合した芳香環を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、チオール基から選ばれる少なくとも1つの官能基が結合した芳香環を有する芳香族有機酸を表し、x、yは1~3、zは0~3であり、かつx=yである。)
(式(7)において、R8は炭素数1~3のアルキル基を表し、R9はヒドロキシル基を表し、fは0~5であり、gは0~3である。)
(式(8)において、Pはリン原子を表し、R10、R11およびR12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、R13、R14およびR15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、R14とR15が結合して環式基を形成してもよい。)
(式(9)において、Pはリン原子を表し、Siは珪素原子を表し、R16、R17、R18およびR19は、それぞれ、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、R20は、基Y2およびY3と結合する有機基であり、R21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し、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し、R20およびR21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(2A)中、2つのYは、それぞれ互いに独立して、式(2B)または式(2C)で表されるグリシジル化フェニル基を表し、Xは、式(2D)または式(2E)で表されるグリシジル化フェニレン基を表し、nは0以上の数を表し、nが2以上の場合、2つ以上のXは、それぞれ互いに独立して、同一であっても異なっていてもよく、R1は、それぞれ互いに独立して、炭素数1~5の炭化水素基を表し、aは0~4の整数を表す。)
(式(2B)~(2E)中、R2およびR3は、それぞれ互いに独立して、炭素数1~5の炭化水素基を表し、bは0~4の整数、cは0~3の整数、dは0~3の整数、eは0~2の整数を表す。)
図1は、本発明の樹脂組成物を用いた電子装置を、半導体装置に適用した場合の例を示す縦断面図である。すなわち、なお、以下の説明では、図1中の上側を「上」、下側を「下」と記載する。
(樹脂組成物)
本発明の樹脂組成物は、式(1A)で表されるフェノール樹脂硬化剤と、式(2A)で表されるエポキシ樹脂と、5%重量減少温度が240℃以上の離型剤とを含む。
(式(1A)中、2つのYは、それぞれ互いに独立して、式(1B)または式(1C)で表されるヒドロキシフェニル基を表し、Xは、式(1D)または式(1E)で表されるヒドロキシフェニレン基を表し、nは0以上の数を表し、nが2以上の場合、2つ以上のXは、それぞれ互いに独立して、同一であっても異なっていてもよく、R1は、それぞれ互いに独立して、炭素数1~5の炭化水素基を表し、aは0~4の整数を表す。)
(式(1B)~(1E)中、R2およびR3は、それぞれ互いに独立して、炭素数1~5の炭化水素基を表し、bは0~4の整数、cは0~3の整数、dは0~3の整数、eは0~2の整数を表す。)
(式(2A)中、2つのYは、それぞれ互いに独立して、式(2B)または式(2C)で表されるグリシジル化フェニル基を表し、Xは、式(2D)または式(2E)で表されるグリシジル化フェニレン基を表し、nは0以上の数を表し、nが2以上の場合、2つ以上のXは、それぞれ互いに独立して、同一であっても異なっていてもよく、R1は、それぞれ互いに独立して、炭素数1~5の炭化水素基を表し、aは0~4の整数を表す。)
(式(2B)~(2E)中、R2およびR3は、それぞれ互いに独立して、炭素数1~5の炭化水素基を表し、bは0~4の整数、cは0~3の整数、dは0~3の整数、eは0~2の整数を表す。)
(フェノール樹脂硬化剤)
本発明の樹脂組成物に用いられるフェノール樹脂硬化剤は、式(1A)で表される重合体である。なお、本明細書において、重合体とは、式(1A)においてn=0である化合物も含む。
(式(1A)中、2つのYは、それぞれ互いに独立して、式(1B)または式(1C)で表されるヒドロキシフェニル基を表し、Xは、式(1D)または式(1E)で表されるヒドロキシフェニレン基を表し、nは0以上の数を表し、nが2以上の場合、2つ以上のXは、それぞれ互いに独立して、同一であっても異なっていてもよく、R1は、それぞれ互いに独立して、炭素数1~5の炭化水素基を表し、aは0~4の整数を表す。)
式(1A)で表されるフェノール樹脂硬化剤は、以下の方法で製造することができる。
本発明の樹脂組成物に用いられるエポキシ樹脂は、式(2A)で表される重合体である。なお、本明細書中で、重合体とは、式(2A)においてn=0である化合物も含む。
(式(2A)中、2つのYは、それぞれ互いに独立して、式(2B)または式(2C)で表されるグリシジル化フェニル基を表し、Xは、式(2D)または式(2E)で表されるグリシジル化フェニレン基を表し、nは0以上の数を表し、nが2以上の場合、2つ以上のXは、それぞれ互いに独立して、同一であっても異なっていてもよく、R1は、それぞれ互いに独立して、炭素数1~5の炭化水素基を表し、aは0~4の整数を表す。)
式(2A)で表されるエポキシ樹脂は、以下の方法で製造することができる。
既に説明したように、式(1A)で表されるフェノール樹脂硬化剤と、式(2A)で表されるエポキシ樹脂を用いることにより、得られる樹脂組成物の高Tgと重量減少の低減化を両立させることができるが、高温保管特性と高温動作特性をいずれも極めて優れたものとする態様としては、式(2A)で表されるエポキシ樹脂と、5%重量減少温度が240℃以上の離型剤とを含有する樹脂組成物、または5%重量減少温度が240℃以上の離型剤と式(1A)で表されるフェノール樹脂硬化剤と、式(2A)で表されるエポキシ樹脂を含有することを特徴とする樹脂組成物が挙げられる。ここで、5%重量減少温度とは、示差熱・熱重量同時測定装置(TG・DTA)を使用して、窒素気流下、10℃/分の昇温速度で、離型剤を室温から加熱していき、初期重量の5%が失われた時の温度をいう。5%重量減少温度が240℃以上とは、上記測定条件を用いた場合、離型剤の初期重量の5%が失われた時の温度が240℃以上であることをいう。
本発明の樹脂組成物は、式(1A)で表されるフェノール樹脂硬化剤、式(2A)で表されるエポキシ樹脂、および5%重量減少温度が240℃以上の離型剤に加え、必要に応じて以下に示す成分を含み得る。
無機充填材は、樹脂組成物の硬化に伴う吸湿量の増加や、強度の低下を低減する機能を有するものであり、当該分野で一般的に用いられる無機充填材を使用することができる。
硬化促進剤は、エポキシ樹脂のエポキシ基とフェノール樹脂硬化剤の水酸基との反応を促進する機能を有するものであり、当該分野で一般に使用される硬化促進剤が用いられる。
(式(6)において、Pはリン原子を表し、R4、R5、R6およびR7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、チオール基から選ばれる少なくとも1つの官能基が結合した芳香環を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、チオール基から選ばれる少なくとも1つの官能基が結合した芳香環を有する芳香族有機酸を表し、xおよびyは1~3の数であり、zは0~3の数であり、かつx=yである。)
(式(8)において、Pはリン原子を表し、R10、R11およびR12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、R13、R14およびR15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、R14とR15が結合して環式基を形成してもよい。)
(式(9)において、Pはリン原子を表し、Siは珪素原子を表し、R16、R17、R18およびR19は、それぞれ、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、R20は、基Y2およびY3と結合する有機基であり、R21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し、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し、R20およびR21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。)
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(A)(以下、単に、「化合物(A)」と言うことがある。)は、これを用いることにより、フェノール樹脂硬化剤とエポキシ樹脂との架橋反応を促進させる硬化促進剤として、潜伏性を有しないリン原子含有硬化促進剤を用いた場合であっても、樹脂組成物の溶融混練中での反応を抑えることができる。
(式(10)において、R22およびR26はどちらか一方が水酸基であり、一方が水酸基のとき、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(11)において、R27およびR33はどちらか一方が水酸基であり、一方が水酸基のとき、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、R28、R29、R30、R31およびR32は水素原子、水酸基または水酸基以外の置換基である。)
カップリング剤は、樹脂組成物中に無機充填材が含まれる場合に、エポキシ樹脂と無機充填材との密着性を向上させる機能を有するものであり、例えば、シランカップリング剤等が用いられる。
無機難燃剤は、樹脂組成物の難燃性を向上させる機能を有するものであり、一般に使用される無機難燃剤が用いられる。
なお、本発明はこれらの実施例の記載に何ら限定されるものではない。
まず、各実施例および各比較例の樹脂組成物で用いた原材料を以下に示す。
なお、特に記載しない限り、各成分の配合量は、質量部とする。
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、1,3-ジヒドロキシベンゼン(東京化成工業社製、「レゾルシノール」、融点111℃、分子量110、純度99.4%)291質量部、フェノール(関東化学社製特級試薬、「フェノール」、融点41℃、分子量94、純度99.3%)235質量部、あらかじめ粒状に砕いた4,4'-ビスクロロメチルビフェニル(和光純薬工業社製、「4,4'-ビスクロロメチルビフェニル」、融点126℃、純度95%、分子量251)125質量部を、セパラブルフラスコに秤量し、窒素置換しながら加熱し、フェノールの溶融の開始に併せて攪拌を開始した。
(式(12A)中、2つのYは、それぞれ互いに独立して、式(12B)または式(12C)で表されるヒドロキシフェニル基を表し、Xは、式(12D)または式(12E)で表されるヒドロキシフェニレン基を表す。)
前記(フェノール樹脂硬化剤1;MFBA型フェノールの合成)において、レゾルシノールを374質量部、フェノールを141質量部、4,4'-ビスクロロメチルビフェニル100質量部とした以外はすべてフェノール樹脂硬化剤1の合成と同様の操作を行い、式(12A)で表されるフェノール樹脂硬化剤2(重合体)を得た。なお、このフェノール樹脂硬化剤2における水酸基当量は120であった。
ビフェニレン骨格を有するフェノール(フェノールの水酸基が1個のもの)アラルキル樹脂(明和化成株式会社製、MEH-7851SS。水酸基当量203g/eq)を用意した。
トリフェニルメタン型フェノール樹脂(明和化成株式会社製、MEH-7500。水酸基当量97g/eq)を用意した。
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、前述のフェノール樹脂硬化剤1を100質量部、エピクロルヒドリン(東京化成工業(株)製)400質量部を秤量し、100℃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)60質量部を4時間かけて徐々に添加し、さらに3時間反応させた。次にトルエン200質量部を加えて溶解させた後、蒸留水150質量部を加えて振とうし、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300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(13A)で表される化合物を含むエポキシ樹脂1(エポキシ当量200g/eq)を得た。このエポキシ樹脂の数平均分子量は560であった。
(式(13A)中、2つのYは、それぞれ互いに独立して、式(13B)または式(13C)で表されるグリシジル化フェニル基を表し、Xは、式(13D)または式(13E)で表されるグリシジル化フェニレン基を表す。)
フェノール樹脂硬化剤2(120質量部)を用いること以外はエポキシ樹脂1の手順と同様に合成を行い、式(13A)で表される化合物を含むエポキシ樹脂2(エポキシ当量185g/eq)を得た。得られたエポキシ樹脂2の数平均分子量は670であった。
ビフェニレン骨格を有するフェノールアラルキル樹脂型エポキシ樹脂(フェノールの水酸基が1個のビフェニレン骨格を有するフェノールアラルキル樹脂を原料とするエポキシ樹脂)(日本化薬株式会社製、NC3000。エポキシ当量276g/eq、軟化点58℃)を用意した。
トリフェニルメタン型エポキシ樹脂(三菱化学株式会社製、1032H-60。エポキシ当量171g/eq、軟化点60℃)を用意した。
離型剤1としては、酸化ポリエチレンワックス(クラリアントジャパン社製、「リコワックスPED191」、Td5 305℃)を用意した。なお本明細書中において「Td5(5%重量減少温度)」とは、示差熱・熱重量同時測定装置(以下TG・DTA)にて窒素気流下、30℃から400℃までの昇温速度10℃/分の条件で、離型剤を加熱したとき、離型剤の初期重量の5%が減少した時点の温度のことである。
離型剤2としては、ウレタン変性酸化ポリエチレンワックス(日本精蝋社製、「NSP-6010P」、Td5 262℃)を用意した。
離型剤3としては、モンタン酸エステル(クラリアントジャパン社製、「リコルブWE4」、Td5 285℃)を用意した。
離型剤4としては、無水マレイン酸と1-アルケン(炭素数28-60)の共重合体をステアリルアルコールでエステル化した化合物を用意した。
(離型剤4の合成方法)
1-オクタコセン、1-トリアコンテン、1-テトラコンテン、1-ペンタコンテン、1-ヘキサコンテン等の混合物と無水マレイン酸との共重合物(三菱化学株式会社製商品名ダイヤカルナ(登録商標)30)300g、ステアリルアルコール(東京化成製)141gを100℃で溶解させ、トリフルオロメタンスルホン酸(東京化成製)の10%水溶液5gを滴下して160℃で8時間反応させた後、減圧下160℃で2時間反応を行うことにより436gの離型剤4を得た。TG/DTA測定からTd5は270℃であった。
離型剤5としては、ステアリン酸(日本油脂社製、「SR-サクラ」、Td5 220℃)を用意した。
無機充填材1としては、溶融球状シリカ(電気化学工業社製「FB560」、平均粒径30μm)を用意した。なお、本発明の平均粒径は島津製作所製レーザー回折散乱式粒度分布計SALD-7000を使用して測定した。
無機充填材2としては、溶融球状シリカ(アドマテックス社製「SO-25R」、平均粒径0.5μm)を用意した。
硬化促進剤1としては、式(14)で示される硬化促進剤を用意した。
(硬化促進剤1の合成方法)
撹拌装置付きのセパラブルフラスコに4,4'-ビスフェノールS37.5g(0.15モル)、メタノール100mlを仕込み、室温で撹拌溶解し、更に攪拌しながら予め50mlのメタノールに水酸化ナトリウム4.0g(0.1モル)を溶解した溶液を添加した。次いで予め150mlのメタノールにテトラフェニルホスホニウムブロマイド41.9g(0.1モル)を溶解した溶液を加えた。しばらく攪拌を継続し、300mlのメタノールを追加した後、フラスコ内の溶液を大量の水に撹拌しながら滴下し、白色沈殿を得た。沈殿を濾過、乾燥し、白色結晶の硬化促進剤1を得た。
硬化促進剤2としては、式(15)で示される硬化促進剤を用意した。
(硬化促進剤2の合成方法)
冷却管及び攪拌装置付きのセパラブルフラスコに2,3-ジヒドロキシナフタレン12.81g(0.080mol)、テトラフェニルホスホニウムブロミド16.77g(0.040mol)およびメタノール100mlを仕込み攪拌し、均一に溶解させた。予め水酸化ナトリウム1.60g(0.04ml)を10mlのメタノールに溶解した水酸化ナトリウム溶液をフラスコ内に徐々に滴下すると結晶が析出した。析出した結晶をろ過、水洗、真空乾燥し、硬化促進剤2を得た。
硬化促進剤3としては、式(16)で示される硬化促進剤を用意した。
(硬化促進剤3の合成方法)
メタノール1800gを入れたフラスコに、フェニルトリメトキシシラン249.5g、2,3-ジヒドロキシナフタレン384.0gを加えて溶かし、次に室温攪拌下28%ナトリウムメトキシド-メタノール溶液231.5gを滴下した。さらにそこへ予め用意したテトラフェニルホスホニウムブロマイド503.0gをメタノール600gに溶かした溶液を室温攪拌下滴下すると結晶が析出した。析出した結晶を濾過、水洗、真空乾燥し、桃白色結晶の硬化促進剤3を得た。
硬化促進剤4としては、式(17)で示される1,4-ベンゾキノンとトリフェニルホスフィンを付加させた化合物を用意した。
(硬化促進剤4の合成方法)
冷却管及び攪拌装置付きのセパラブルフラスコにベンゾキノン6.49g(0.060mol)、トリフェニルホスフィン17.3g(0.066mol)およびアセトン40mlを仕込み、攪拌下、室温で反応した。析出した結晶をアセトンで洗浄後、ろ過、乾燥し暗緑色結晶の硬化促進剤4を得た。
硬化促進剤5としては、トリフェニルホスフィン(和光純薬製)を用意した。
シランカップリング剤1としては、3-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)製、KBM-803)を用意した。
着色剤としては、カーボンブラック(三菱化学社製、「MA600」)を用意した。
[実施例1]
エポキシ樹脂1(8.75質量部)、フェノール樹脂硬化剤1(5.14質量部)、無機充填材1(75.00質量部)、無機充填材2(10.00質量部)、硬化促進剤3(0.32質量部)、シランカップリング剤1(0.20質量部)、離型剤1(0.20質量部)、着色剤1(0.40質量部)をそれぞれ秤量し、これらをミキサーを用いて混合した後、表面温度が95℃と25℃の2本ロールを用いて混練することにより混練物を得た。次いで、この混練物を、冷却後粉砕することで実施例1の樹脂組成物を得た。
原材料の種類および配合量を表1に示すように変更したこと以外は前記実施例1と同様にして、実施例2~13、比較例1~4の樹脂組成物を得た。
使用した離型剤及び得られた各実施例および各比較例の樹脂組成物を、以下の方法で評価した。
サンプル(離型剤)をPtパンに10mg入れ、窒素気流下10℃/分で30℃から400℃までの熱重量減少量をTG・DTA測定装置(セイコーインスツル株式会社、EXSTAR7000)を用いて測定し、サンプルの初期重量の5%が失われた時の温度(Td5)を測定した。
低圧トランスファー成形機(コータキ精機社製、「KTS-15」)を用いて、ANSI/ASTM D 3123-72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秒の条件で、各実施例および各比較例の樹脂組成物を注入し、流動長を測定し、これをスパイラルフローとした。
各実施例および各比較例の樹脂組成物のガラス転移温度は、JIS K 7244-3に準じて測定した。
低圧トランスファー成形機(コータキ精機社製、「KTS-30」)を用いて、金型温度175℃、注入圧力9.8MPa、硬化時間120sの条件で、各実施例および各比較例の樹脂組成物から、直径50mm、厚さ3mmの円盤状試験片を成形し、175℃で4時間、後硬化した。その後、125℃で20時間乾燥処理し、冷却後の重量を初期重量とした。次いで、大気雰囲気下200℃の高温槽に円盤状試験片を投入し、1000時間加熱処理、冷却後の重量を処理後重量とした。
なお、表1には、熱処理前後の重量減少率を百分率で示した。
低圧トランスファー成形機(コータキ精機社製、「KTS-30」)を用いて、金型温度175℃、注入時間15秒、硬化時間120秒、注入圧力9.8MPaの条件で、各実施例および各比較例の樹脂組成物を注入成形して、175℃、4時間で後硬化することで、3.2mm厚の耐燃試験片を作製した。
なお、表1には、判定後の耐燃ランク(クラス)を示した。
トランスファー成形機を用いて、金型温度175℃、圧力9.8MPa、硬化時間2分で、チップサイズ3.5mm×3.5mmの16pSOPを成形し、175℃、4時間で硬化した後、175℃での高温保管試験を行った。配線間の電気抵抗値が初期値の20%増加したパッケージを不良と判定し、不良になるまでの時間を測定した。不良時間はn=4個の平均値。単位は時間である。
トランスファー成形機を用いて、金型温度175℃、圧力9.8MPa、硬化時間2分で、チップサイズ3.5mm×3.5mmの16pSOPを成形し、175℃、4時間で硬化した後、デイジーチェーンにつないだ両端に0.5Aの直流電流を流し、この状態で175℃での高温保管を行った。配線間の電気抵抗値が初期値の20%増加したパッケージを不良と判定し、不良になるまでの時間を測定した。不良時間はn=4個の平均値。単位は時間である。
Claims (13)
- 式(1A)で表されるフェノール樹脂硬化剤と、式(2A)で表されるエポキシ樹脂と、5%重量減少温度が240℃以上の離型剤とを含む封止用樹脂組成物。
(式(1A)中、2つのYは、それぞれ互いに独立して、式(1B)または式(1C)で表されるヒドロキシフェニル基を表し、Xは、式(1D)または式(1E)で表されるヒドロキシフェニレン基を表し、nは0以上の数を表し、nが2以上の場合、2つ以上のXは、それぞれ互いに独立して、同一であっても異なっていてもよく、R1は、それぞれ互いに独立して、炭素数1~5の炭化水素基を表し、aは0~4の整数を表す。)
(式(1B)~(1E)中、R2およびR3は、それぞれ互いに独立して、炭素数1~5の炭化水素基を表し、bは0~4の整数、cは0~3の整数、dは0~3の整数、eは0~2の整数を表す。)
(式(2A)中、2つのYは、それぞれ互いに独立して、式(2B)または式(2C)で表されるグリシジル化フェニル基を表し、Xは、式(2D)または式(2E)で表されるグリシジル化フェニレン基を表し、nは0以上の数を表し、nが2以上の場合、2つ以上のXは、それぞれ互いに独立して、同一であっても異なっていてもよく、R1は、それぞれ互いに独立して、炭素数1~5の炭化水素基を表し、aは0~4の整数を表す。)
(式(2B)~(2E)中、R2およびR3は、それぞれ互いに独立して、炭素数1~5の炭化水素基を表し、bは0~4の整数、cは0~3の整数、dは0~3の整数、eは0~2の整数を表す。) - 前記樹脂組成物中における、前記フェノール樹脂硬化剤の含有率をA1(質量%)、前記エポキシ樹脂の含有率をA2(質量%)としたとき、A1/(A1+A2)の値が0.2以上、0.9以下である、請求項1に記載の封止用樹脂組成物。
- 前記フェノール樹脂硬化剤の水酸基当量が90g/eq以上、190g/eq以下である、請求項1または2に記載の封止用樹脂組成物。
- 前記エポキシ樹脂のエポキシ当量が160g/eq以上、290g/eq以下である、請求項1~3のいずれか1項に記載の封止用樹脂組成物。
- 無機充填材をさらに含む、請求項1~4のいずれか1項に記載の封止用樹脂組成物。
- 式(6)~式(9)で表される硬化促進剤の少なくとも1種をさらに含む、請求項1~5のいずれか1項に記載の封止用樹脂組成物。
(式(6)において、Pはリン原子を表し、R4、R5、R6およびR7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、チオール基から選ばれる少なくとも1つの官能基が結合した芳香環を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、チオール基から選ばれる少なくとも1つの官能基が結合した芳香環を有する芳香族有機酸を表し、x、yは1~3、zは0~3であり、かつx=yである。)
(式(7)において、R8は炭素数1~3のアルキル基を表し、R9はヒドロキシル基を表し、fは0~5であり、gは0~3である。)
(式(8)において、Pはリン原子を表し、R10、R11およびR12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、R13、R14およびR15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、R14とR15が結合して環式基を形成してもよい。)
(式(9)において、Pはリン原子を表し、Siは珪素原子を表し、R16、R17、R18およびR19は、それぞれ、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、R20は、基Y2およびY3と結合する有機基であり、R21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し、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し、R20およびR21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。) - カップリング剤をさらに含む、請求項1~6のいずれか1項に記載の封止用樹脂組成物。
- 前記樹脂組成物の硬化物のガラス転移温度(Tg)が、200℃以上であり、前記硬化物の、大気雰囲気下、200℃で1000時間加熱したときの重量減少率が、0.3%以下である、請求項1~7のいずれか1項に記載の封止用樹脂組成物。
- 式(2A)で表されるエポキシ樹脂と、5%重量減少温度が240℃以上の離型剤とを含む封止用樹脂組成物。
(式(2A)中、2つのYは、それぞれ互いに独立して、式(2B)または式(2C)で表されるグリシジル化フェニル基を表し、Xは、式(2D)または式(2E)で表されるグリシジル化フェニレン基を表し、nは0以上の数を表し、nが2以上の場合、2つ以上のXは、それぞれ互いに独立して、同一であっても異なっていてもよく、R1は、それぞれ互いに独立して、炭素数1~5の炭化水素基を表し、aは0~4の整数を表す。)
(式(2B)~(2E)中、R2およびR3は、それぞれ互いに独立して、炭素数1~5の炭化水素基を表し、bは0~4の整数、cは0~3の整数、dは0~3の整数、eは0~2の整数を表す。) - 前記樹脂組成物の硬化物のガラス転移温度(Tg)が、200℃以上であり、前記硬化物の、大気雰囲気下、200℃で1000時間加熱したときの重量減少率が、0.3%以下である、請求項9に記載の封止用樹脂組成物。
- フェノール樹脂硬化剤と、エポキシ樹脂と、5%重量減少温度が240℃以上の離型剤とを含む封止用樹脂組成物であって、
前記樹脂組成物の硬化物のガラス転移温度(Tg)が、200℃以上であり、前記硬化物の、大気雰囲気下、200℃で1000時間加熱したときの重量減少率が、0.3%以下である、封止用樹脂組成物。 - 前記フェノール樹脂硬化剤が、式(1A)で表されるフェノール樹脂硬化剤であり、前記エポキシ樹脂が、式(2A)で表されるエポキシ樹脂である、請求項11に記載の封止用樹脂組成物。
(式(1A)中、2つのYは、それぞれ互いに独立して、式(1B)または式(1C)で表されるヒドロキシフェニル基を表し、Xは、式(1D)または式(1E)で表されるヒドロキシフェニレン基を表し、nは0以上の数を表し、nが2以上の場合、2つ以上のXは、それぞれ互いに独立して、同一であっても異なっていてもよく、R1は、それぞれ互いに独立して、炭素数1~5の炭化水素基を表し、aは0~4の整数を表す。)
(式(1B)~(1E)中、R2およびR3は、それぞれ互いに独立して、炭素数1~5の炭化水素基を表し、bは0~4の整数、cは0~3の整数、dは0~3の整数、eは0~2の整数を表す。)
(式(2A)中、2つのYは、それぞれ互いに独立して、式(2B)または式(2C)で表されるグリシジル化フェニル基を表し、Xは、式(2D)または式(2E)で表されるグリシジル化フェニレン基を表し、nは0以上の数を表し、nが2以上の場合、2つ以上のXは、それぞれ互いに独立して、同一であっても異なっていてもよく、R1は、それぞれ互いに独立して、炭素数1~5の炭化水素基を表し、aは0~4の整数を表す。)
(式(2B)~(2E)中、R2およびR3は、それぞれ互いに独立して、炭素数1~5の炭化水素基を表し、bは0~4の整数、cは0~3の整数、dは0~3の整数、eは0~2の整数を表す。) - 請求項1~12のいずれか1項に記載の封止用樹脂組成物で封止された電子部品を備える、電子装置。
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CN201380010695.5A CN104136480B (zh) | 2012-03-16 | 2013-03-12 | 封装用树脂组合物和使用该封装用树脂组合物的电子装置 |
SG11201403635SA SG11201403635SA (en) | 2012-03-16 | 2013-03-12 | Resin composition for encapsulation and electronic device using the same |
KR1020147022340A KR101639927B1 (ko) | 2012-03-16 | 2013-03-12 | 밀봉용 수지 조성물 및 이것을 사용하는 전자 장치 |
JP2014504696A JP5842995B2 (ja) | 2012-03-16 | 2013-03-12 | 封止用樹脂組成物およびこれを用いる電子装置 |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015174975A (ja) * | 2014-03-18 | 2015-10-05 | 新日鉄住金化学株式会社 | エポキシ樹脂の製造方法とその製造方法で得られたエポキシ樹脂を含む組成物及び硬化物 |
JP2016047919A (ja) * | 2014-08-25 | 2016-04-07 | 日本化薬株式会社 | 新規反応性エポキシカルボキシレート化合物、その誘導体、それを含有する樹脂組成物及びその硬化物 |
JP2016084413A (ja) * | 2014-10-27 | 2016-05-19 | 味の素株式会社 | 樹脂組成物 |
JP2017179185A (ja) * | 2016-03-31 | 2017-10-05 | 住友ベークライト株式会社 | 半導体封止用エポキシ樹脂組成物および半導体装置 |
JP2019021800A (ja) * | 2017-07-19 | 2019-02-07 | 住友ベークライト株式会社 | 半導体装置およびその製造方法ならびに封止用樹脂組成物 |
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US10483175B2 (en) * | 2015-12-04 | 2019-11-19 | Mitsubishi Electric Corporation | Power semiconductor device |
JP6588346B2 (ja) * | 2016-01-14 | 2019-10-09 | 日本化薬株式会社 | エポキシ樹脂、反応性カルボキシレート化合物、それを用いた硬化型樹脂組成物、およびその用途 |
JP6520872B2 (ja) * | 2016-09-01 | 2019-05-29 | 信越化学工業株式会社 | 半導体封止用熱硬化性樹脂組成物 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007009180A (ja) * | 2005-05-31 | 2007-01-18 | Sumitomo Bakelite Co Ltd | エポキシ樹脂組成物及び半導体装置 |
WO2007007827A1 (ja) * | 2005-07-13 | 2007-01-18 | Ube Industries, Ltd. | ビフェニレン架橋フェノールノボラック樹脂ならびにその用途 |
JP2012052090A (ja) * | 2010-08-05 | 2012-03-15 | Sumitomo Bakelite Co Ltd | 機能性粒子およびその製造方法、充填剤、電子部品用樹脂組成物、電子部品および半導体装置 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7157313B2 (en) * | 2003-01-17 | 2007-01-02 | Sumitomo Bakelite Co., Ltd. | Epoxy resin composition and semiconductor device using thereof |
JP2005167035A (ja) | 2003-12-03 | 2005-06-23 | Kansai Electric Power Co Inc:The | 炭化珪素半導体素子およびその製造方法 |
-
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007009180A (ja) * | 2005-05-31 | 2007-01-18 | Sumitomo Bakelite Co Ltd | エポキシ樹脂組成物及び半導体装置 |
WO2007007827A1 (ja) * | 2005-07-13 | 2007-01-18 | Ube Industries, Ltd. | ビフェニレン架橋フェノールノボラック樹脂ならびにその用途 |
JP2012052090A (ja) * | 2010-08-05 | 2012-03-15 | Sumitomo Bakelite Co Ltd | 機能性粒子およびその製造方法、充填剤、電子部品用樹脂組成物、電子部品および半導体装置 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015174975A (ja) * | 2014-03-18 | 2015-10-05 | 新日鉄住金化学株式会社 | エポキシ樹脂の製造方法とその製造方法で得られたエポキシ樹脂を含む組成物及び硬化物 |
JP2016047919A (ja) * | 2014-08-25 | 2016-04-07 | 日本化薬株式会社 | 新規反応性エポキシカルボキシレート化合物、その誘導体、それを含有する樹脂組成物及びその硬化物 |
JP2016084413A (ja) * | 2014-10-27 | 2016-05-19 | 味の素株式会社 | 樹脂組成物 |
JP2017179185A (ja) * | 2016-03-31 | 2017-10-05 | 住友ベークライト株式会社 | 半導体封止用エポキシ樹脂組成物および半導体装置 |
JP2019021800A (ja) * | 2017-07-19 | 2019-02-07 | 住友ベークライト株式会社 | 半導体装置およびその製造方法ならびに封止用樹脂組成物 |
JP7155502B2 (ja) | 2017-07-19 | 2022-10-19 | 住友ベークライト株式会社 | 半導体装置およびその製造方法ならびに封止用樹脂組成物 |
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KR20140123065A (ko) | 2014-10-21 |
JP5842995B2 (ja) | 2016-01-13 |
US20150152258A1 (en) | 2015-06-04 |
TWI576364B (zh) | 2017-04-01 |
JPWO2013136769A1 (ja) | 2015-08-03 |
CN104136480B (zh) | 2017-05-31 |
CN104136480A (zh) | 2014-11-05 |
TW201343703A (zh) | 2013-11-01 |
KR101639927B1 (ko) | 2016-07-14 |
SG11201403635SA (en) | 2014-10-30 |
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