WO2020130097A1 - Sealing composition and semiconductor device - Google Patents
Sealing composition and semiconductor device Download PDFInfo
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- WO2020130097A1 WO2020130097A1 PCT/JP2019/049923 JP2019049923W WO2020130097A1 WO 2020130097 A1 WO2020130097 A1 WO 2020130097A1 JP 2019049923 W JP2019049923 W JP 2019049923W WO 2020130097 A1 WO2020130097 A1 WO 2020130097A1
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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
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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
- C08G59/68—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 catalysts used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
Definitions
- the present disclosure relates to a sealing composition and a semiconductor device.
- a semiconductor encapsulation in which (A) an epoxy resin, (B) a curing agent, and (D) an inorganic filler containing spherical alumina and spherical silica are essential components
- An epoxy resin composition for use wherein the spherical alumina is (d1) a first spherical alumina having an average particle diameter of 40 ⁇ m or more and 70 ⁇ m or less, and (d2) a second spherical alumina having an average particle diameter of 10 ⁇ m or more and 15 ⁇ m or less.
- the spherical silica includes (d3) a first spherical silica having an average particle diameter of 4 ⁇ m or more and 8 ⁇ m or less and (d4) a second spherical silica having an average particle diameter of 0.05 ⁇ m or more and 1.0 ⁇ m or less.
- Patent Document 1 Japanese Patent Laid-Open No. 2006-273920
- a sealing composition and a sealing composition which can obtain a cured product having a high elastic modulus at room temperature (ie, 25°C) and a low elastic modulus at high temperature (ie, 260°C) while obtaining high thermal conductivity.
- a semiconductor device using the antistatic composition is provided.
- the present invention includes the following embodiments.
- a first epoxy resin having an epoxy group equivalent of 300 g/eq or more and having a glass transition temperature of 40° C. or less when cured using a polyfunctional phenol resin curing agent and a phosphorus-based curing accelerator;
- a curing agent An inorganic filler,
- the content rate of the said inorganic filler is a sealing composition as described in ⁇ 1> which is 78 volume% or more with respect to the whole sealing composition.
- ⁇ 4> The encapsulating composition according to any one of ⁇ 1> to ⁇ 3>, in which the content of the first epoxy resin is 20% by mass or more based on the total amount of the epoxy resins contained in the encapsulating composition.
- Stuff. ⁇ 5> The encapsulating composition according to any one of ⁇ 1> to ⁇ 4>, in which the content of the first epoxy resin is 50% by mass or less based on the total amount of the epoxy resin contained in the encapsulating composition.
- Stuff. ⁇ 6> The first epoxy resin is the encapsulating composition as described in any one of ⁇ 1> to ⁇ 5>, which has two epoxy groups in the molecule.
- ⁇ 7> The sealing composition according to any one of ⁇ 1> to ⁇ 6>, wherein the first epoxy resin has a divalent linking group represented by the following structural formula (1) in the molecule.
- a semiconductor device comprising: a semiconductor element; and a cured product of the encapsulating composition according to any one of ⁇ 1> to ⁇ 7>, which is obtained by encapsulating the semiconductor element.
- a sealing composition and a sealing composition which can obtain a cured product having a high elastic modulus at room temperature (ie, 25°C) and a low elastic modulus at high temperature (ie, 260°C) while obtaining high thermal conductivity.
- a semiconductor device using the antistatic composition is provided.
- each component may include a plurality of types of corresponding substances. When there are multiple types of substances corresponding to each component in the composition, the content rate or content of each component is the total content rate or content of the multiple types of substances present in the composition unless otherwise specified. Means quantity.
- a plurality of types of particles corresponding to each component may be included.
- the particle size of each component means a value for a mixture of the plurality of types of particles present in the composition unless otherwise specified.
- the sealing composition of the present disclosure has an epoxy group equivalent of 300 g/eq or more, and a glass transition temperature of 40° C. or less when cured using a polyfunctional phenol resin curing agent and a phosphorus-based curing accelerator. 1 epoxy resin, a curing agent, and an inorganic filler. Since the encapsulating composition of the present disclosure contains the first epoxy resin described above, while obtaining high thermal conductivity, the elastic modulus at room temperature (that is, 25° C.) (hereinafter also referred to as “room temperature elastic modulus”) and the high temperature ( That is, a cured product having a low elastic modulus at 260° C. (hereinafter also referred to as “high temperature elastic modulus”) can be obtained.
- room temperature elastic modulus that is, 25° C.
- high temperature elastic modulus a cured product having a low elastic modulus at 260° C.
- the "multifunctional phenol resin curing agent” is a curing agent that is a phenol resin having three or more functional groups (that is, hydroxyl groups) in one molecule
- the "phosphorus curing accelerator” is a curing accelerator having a phosphorus atom. Is.
- the above "glass transition temperature when cured using a polyfunctional phenol resin curing agent and a phosphorus-based curing accelerator” is measured as follows. First, a mixture of an epoxy resin to be measured, a triphenylmethane type phenolic resin which is a polyfunctional phenolic resin curing agent, and a quinone adduct of an organic phosphine compound which is a phosphorus-based curing accelerator is mixed at 175°C. A cured product for measurement is obtained by heating for 6 hours. The polyfunctional phenol resin curing agent is added so that the number of epoxy groups (that is, the total number) of the epoxy resin that is the measurement target and the number of hydroxyl groups (that is, the total number) of the phenol resin are approximately the same.
- the phosphorus-based curing accelerator is added such that the content of the phosphorus-based curing accelerator is 3 parts by mass to 6 parts by mass with respect to 100 parts by mass in total of the epoxy resin and the polyfunctional phenol resin curing agent.
- the obtained cured product for measurement is cut, 10 mg is weighed, and DSC (Differential scanning calorimetry) measurement is performed. Specifically, a differential scanning calorimeter (TA Instruments Japan Co., Ltd., product name “DSC Q100”) was used to measure the temperature rise rate of 10° C./min, and the obtained chart was changed. The intersection of the tangents before and after the bending point is the glass transition temperature.
- triphenylmethane type phenol resin which is a polyfunctional phenol resin curing agent
- HE910-09 Air Water Co., Ltd., hydroxyl group equivalent: 92 to 104 g/eq, softening point: 75 to 85° C.
- the type and amount of the curing agent contained in the encapsulating composition of the present disclosure may be the same as or different from the type and amount of the curing agent used to obtain the cured product for measurement.
- the quinone adduct of the above organic phosphine compound which is a phosphorus-based curing accelerator
- an adduct of tributylphosphine and benzoquinone can be used.
- the type and the addition amount of the curing accelerator contained in the encapsulating composition are the curing acceleration used for obtaining the cured product for measurement.
- the type and the addition amount of the agent may be the same or different.
- the "glass transition temperature when cured using a polyfunctional phenol resin curing agent and a phosphorus-based curing accelerator” may be referred to as "glass transition temperature after curing".
- epoxy group equivalent is measured as follows. Specifically, “epoxy group equivalent” is measured by dissolving the epoxy resin to be measured in a solvent such as methyl ethyl ketone, adding acetic acid and tetraethylammonium bromide acetic acid solution, and then measuring with perchloric acid acetic acid standard solution. It is measured by potentiometric titration. An indicator may be used for this titration.
- the sealing composition of the present disclosure contains an epoxy resin, a curing agent, and an inorganic filler, and may contain other components as necessary.
- the epoxy resin is generally selected from the group consisting of phenol compounds (phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, etc.) and naphthol compounds ( ⁇ -naphthol, ⁇ -naphthol, dihydroxynaphthalene, etc.).
- phenol compounds phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, etc.
- naphthol compounds ⁇ -naphthol, ⁇ -naphthol, dihydroxynaphthalene, etc.
- At least one of the above and an aldehyde compound (formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde, etc.) are condensed or co-condensed under an acidic catalyst to obtain an epoxidized novolak resin (phenol novolac
- the sealing composition of the present disclosure is the first epoxy resin having an epoxy group equivalent of 300 g/eq or more and a glass transition temperature after curing of 40° C. or less as described above. Contains at least. Further, the sealing composition of the present disclosure may contain an epoxy resin other than the first epoxy resin as necessary, and the melting point or softening point of 50° C. or higher as the resin other than the first epoxy resin. It is preferable to further contain a certain second epoxy resin.
- the encapsulating composition of the present disclosure may contain an epoxy resin other than the first epoxy resin and the second epoxy resin (hereinafter, also referred to as “other epoxy resin”), if necessary.
- the total content of the first epoxy resin and the second epoxy resin is preferably 90% by mass or more based on the total amount of all epoxy resins contained in the encapsulating composition. Is more preferably 95 mass% or more, further preferably 98 mass% or more.
- the first epoxy resin is not particularly limited as long as it has an epoxy group equivalent of 300 g/eq or more and a glass transition temperature after curing of 40° C. or less.
- the epoxy group equivalent in the first epoxy resin is 300 g/eq or more, preferably 350 g/eq or more, and more preferably 400 g/eq or more from the viewpoint of reducing the high temperature elastic modulus.
- the epoxy group equivalent in the first epoxy resin is preferably 600 g/eq or less, more preferably 570 g/eq or less, and more preferably 540 g/eq or less from the viewpoint of ensuring the hardness during heating. Is more preferable.
- the epoxy group equivalent in the first epoxy resin is preferably 300 g/eq to 600 g/eq, and is 350 g/eq to 570 g/eq, from the viewpoint of simultaneously achieving a reduction in high temperature elastic modulus and a guarantee of hardness during heating. More preferably, it is more preferably 400 g/eq to 540 g/eq.
- the glass transition temperature after curing in the first epoxy resin is 40° C. or lower, preferably 35° C. or lower, and more preferably 20° C. or lower from the viewpoint of reducing room temperature elastic modulus and high temperature elastic modulus. Further, the lower limit of the glass transition temperature after curing in the first epoxy resin is not particularly limited.
- the glass transition temperature after curing of the first epoxy resin is preferably ⁇ 100° C. or higher, more preferably ⁇ 85° C. or higher, and ⁇ 75 from the viewpoint of ensuring the hardness during heating and reducing the thermal expansion coefficient. It is more preferable that the temperature is not lower than °C.
- the glass transition temperature after curing of the first epoxy resin is from ⁇ 100° C. to 40° C.
- the temperature is preferably ⁇ 85° C. to 30° C., more preferably ⁇ 75° C. to 20° C.
- the first epoxy resin has at least two epoxy groups in the molecule.
- the number of epoxy groups contained in one molecule of the first epoxy resin is not particularly limited as long as the epoxy group equivalent in the first epoxy resin is in the above range, and may be 2-8, 2-6. Is preferable, 2 to 3 is more preferable, and 2 is particularly preferable.
- the epoxy group is at least one selected from the group consisting of glycidyl group, glycidyloxy group, glycidyloxycarbonyl group, and epoxycycloalkyl group (epoxycyclopentyl group, epoxycyclohexyl group, epoxycyclooctyl group, etc.). As a part, it may be contained in the molecule of the first epoxy resin.
- the first epoxy resin preferably has a divalent linking group represented by the following structural formula (1) in the molecule, in addition to two or more epoxy groups.
- a divalent linking group represented by the following structural formula (1) in the molecule, in addition to two or more epoxy groups.
- * indicates a bonding part.
- the first epoxy resin preferably has, in the molecule, at least one selected from the group consisting of a rubber elastic skeleton and a flexible skeleton, in addition to two or more epoxy groups.
- the first epoxy resin may have at least one kind selected from the group consisting of a rubber elastic skeleton and a flexible skeleton in the molecule, or may have two or more kinds.
- the rubber elastic skeleton is a partial structure that imparts rubber elasticity to the epoxy resin, and specific examples of the rubber elastic skeleton include alkyleneoxy groups and the like.
- the flexible skeleton is a partial structure that imparts flexibility to the epoxy resin, and specific examples of the flexible skeleton include an alkyleneoxy group, a long-chain alkyl group, and a siloxane skeleton.
- the first epoxy resin may have a skeleton containing an aromatic ring in addition to two or more epoxy groups in the molecule.
- the skeleton containing an aromatic ring include a benzene ring skeleton, a naphthalene skeleton, a biphenyl skeleton, a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol AD skeleton, and a bisphenol S skeleton.
- a commercially available product may be used as the first epoxy resin.
- the first epoxy resin may be used alone or in combination of two or more.
- the content of the first epoxy resin with respect to the total amount of all epoxy resins contained in the encapsulating composition is preferably 10% by mass or more and 20% by mass or more from the viewpoint of reducing the room temperature elastic modulus and the high temperature elastic modulus. Is more preferable and 25% by mass or more is further preferable.
- the content of the first epoxy resin with respect to the total amount of all epoxy resins contained in the encapsulating composition is preferably 50% by mass or less and 45% by mass or less from the viewpoint of moldability of the encapsulating composition. Is more preferable, and 40% by mass or less is further preferable.
- the content of the first epoxy resin with respect to the total amount of all epoxy resins contained in the encapsulating composition is 10% by mass from the viewpoint of achieving both reduction in room temperature elastic modulus and high temperature elastic modulus and moldability of the encapsulating composition. It is preferably ⁇ 50% by mass, more preferably 20% by mass to 45% by mass, and further preferably 25% by mass to 40% by mass.
- the content of the first epoxy resin in the whole sealing composition is preferably 0.2% by mass to 3% by mass, more preferably 0.4% by mass to 1.5% by mass. More preferably, it is from 0.6% by mass to 1.1% by mass.
- the second epoxy resin is not particularly limited as long as it is an epoxy resin other than the first epoxy resin and has a melting point or a softening point of 50° C. or higher.
- the melting point of the epoxy resin is a value measured by differential scanning calorimetry (DSC)
- the softening point of the epoxy resin is a value measured by a method (ring and ball method) according to JIS K 7234:1986.
- the melting point or softening point of the second epoxy resin is preferably 50° C. or higher, more preferably 60° C. or higher, and 70° C. or higher from the viewpoint of moldability of the sealing composition. Is more preferable.
- the melting point or softening point of the second epoxy resin is preferably 150° C.
- the melting point or softening point of the second epoxy resin is preferably 50° C. to 150° C., and more preferably 60° C. to 130° C. from the viewpoint of moldability of the sealing composition and kneading property during production. It is preferably 70° C. to 120° C., further preferably.
- the epoxy group equivalent in the second epoxy resin is not particularly limited and is preferably less than 300 g/eq, and is 120 g/eq to 270 g/eq from the viewpoint of both moldability and reduction of high temperature elastic modulus. More preferably, it is more preferably 150 g/eq to 240 g/eq.
- the glass transition temperature after curing in the second epoxy resin is not particularly limited and is preferably higher than 40° C., and from the viewpoint of achieving both moldability and reduction of room temperature elastic modulus, it is from 80° C. to 200° C. More preferably, it is more preferably 120°C to 180°C.
- the second epoxy resin has at least two epoxy groups in the molecule.
- the number of epoxy groups contained in one molecule of the second epoxy resin is not particularly limited and may be 2-8, preferably 2-6, more preferably 2-3, and particularly preferably 2.
- the epoxy group is at least one selected from the group consisting of glycidyl group, glycidyloxy group, glycidyloxycarbonyl group, and epoxycycloalkyl group (epoxycyclopentyl group, epoxycyclohexyl group, epoxycyclooctyl group, etc.). As a part, it may be contained in the molecule of the first epoxy resin.
- the second epoxy resin preferably has a divalent linking group represented by the following general formula (2) in the molecule, in addition to two or more epoxy groups.
- a divalent linking group represented by the following general formula (2) in the molecule, in addition to two or more epoxy groups.
- * represents a bond
- R 1 to R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aromatic group having 4 to 18 carbon atoms. Indicates.
- R 1 to R 4 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, and further preferably a methyl group.
- R 5 to R 8 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.
- the content of the second epoxy resin with respect to the total amount of all epoxy resins contained in the encapsulating composition is 50% by mass to 90% by mass from the viewpoint of achieving both room temperature elastic modulus and high temperature elastic modulus reduction and moldability. It is preferably in the range of 55% by mass to 80% by mass, and more preferably in the range of 60% by mass to 75% by mass. Further, the content ratio of the second epoxy resin to the entire sealing composition is preferably 1% by mass to 5% by mass, more preferably 1.5% by mass to 4% by mass, and 1.7. More preferably, it is from 3% by mass to 3% by mass.
- the total epoxy resin content in the encapsulating composition is preferably 2.0% by mass to 6% by mass, more preferably 3.0% by mass to 5.5% by mass, and 3.0 It is more preferable that the content is from 5.0% by mass to 5.0% by mass.
- the content of the total epoxy resin in the sealing composition excluding the inorganic filler is preferably 40% by mass to 70% by mass, more preferably 45% by mass to 64% by mass, and 48% by mass to It is more preferably 55% by mass.
- the sealing composition contains a curing agent.
- the type of curing agent is not particularly limited, and known curing agents can be used.
- the curing agent include a phenol curing agent, an amine curing agent, an acid anhydride curing agent, a polymercaptan curing agent, a polyaminoamide curing agent, an isocyanate curing agent, and a blocked isocyanate curing agent.
- the curing agent is preferably a phenol curing agent, an amine curing agent, and an acid anhydride curing agent, and more preferably a phenol curing agent, from the viewpoint of obtaining a sealing composition having excellent reflow resistance while maintaining fluidity.
- the curing agent may be used alone or in combination of two or more.
- phenol curing agents include phenol resins having two or more phenolic hydroxyl groups in one molecule, polyhydric phenol compounds, and the like.
- Specific examples of the phenol curing agent include resorcin, catechol, bisphenol A, bisphenol F, polyphenol compounds such as substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, At least one phenolic compound selected from the group consisting of phenol compounds such as phenylphenol and aminophenol and naphthol compounds such as ⁇ -naphthol, ⁇ -naphthol and dihydroxynaphthalene; and aldehyde compounds such as formaldehyde, acetaldehyde and propionaldehyde, An aralkyl-type phenol resin (phenol aralkyl resin, which is synthesized from the above-mentioned phenolic compound, dimethoxyparaxy
- the phenol curing agent is preferably a polyfunctional phenol resin, of which a novolac type phenol resin, an aralkyl type phenol resin, and a triphenylmethane type phenol resin are preferable, and a triphenylmethane type phenol resin is more preferable.
- triphenylmethane type phenol resin examples include a phenol resin represented by the following general formula (3).
- R 11 to R 15 each independently represent a monovalent organic group having 1 to 18 carbon atoms
- b 1 to b 2 each independently represent an integer of 0 to 4
- b3 represents an integer of 0 to 3
- b4 to b5 each independently represents an integer of 0 to 4
- n represents 0 to 10.
- the monovalent organic group having 1 to 18 carbon atoms represented by R 11 to R 15 in the general formula (3) includes a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted Examples thereof include an aryl group and a substituted or unsubstituted aralkyl group.
- B1 to b5 in the general formula (3) are preferably integers of 0 to 1, more preferably 0, and n in the general formula (3) is preferably 1 to 7. More preferably, it is -5.
- the functional group equivalent of the curing agent is not particularly limited and is preferably 70 g/eq to 500 g/eq, more preferably 70 g/eq to 300 g/eq, and more preferably 80 g/eq to 250 g from the viewpoint of moldability. /Eq is more preferable.
- the functional group equivalent of the curing agent is a value measured according to JIS K0070:1992.
- the softening point or melting point of the curing agent is preferably 40° C. to 180° C. from the viewpoint of moldability and reflow resistance, and the softening point or melting point from the viewpoint of handleability during production of the sealing composition. Is more preferably 50° C. to 130° C., further preferably 55° C. to 100° C.
- the melting point or softening point of the curing agent is a value measured in the same manner as the melting point or softening point of the epoxy resin.
- the mixing ratio of the epoxy resin and the curing agent is such that the equivalent of the functional group of the curing agent (for example, a phenolic hydroxyl group in the case of a phenol resin) is equal to one equivalent of the epoxy group of the epoxy resin from the viewpoint of suppressing each unreacted component.
- the curing agent so as to be 0.5 equivalent to 1.5 equivalents, and particularly preferable to add the curing agent so as to be 0.7 equivalent to 1.2 equivalents. ..
- the inorganic filler may be used alone or in combination of two or more. Examples of the case where two or more kinds of inorganic fillers are used in combination include a case where two or more kinds of inorganic fillers having different components, average particle diameters, shapes, etc. are used.
- the shape of the inorganic filler is not particularly limited, and examples thereof include powder, sphere, and fiber.
- the shape of the inorganic filler is preferably spherical from the viewpoints of fluidity during molding of the encapsulating composition and mold wear resistance.
- the inorganic filler preferably contains alumina from the viewpoint of high thermal conductivity. All the inorganic fillers may be alumina, or alumina and other inorganic fillers may be used in combination. Other inorganic fillers that can be used in combination with alumina include spherical silica, silica such as crystalline silica, zircon, magnesium oxide, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, boron nitride, beryllia and zirconia. Are listed. Furthermore, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide and zinc borate.
- silica is preferably used as the other inorganic filler from the viewpoint of fluidity.
- the content of alumina in the inorganic filler is preferably 50% by mass or more, more preferably 70% by mass or more, and 85% by mass or more. Is more preferable, and 95% by mass or more is particularly preferable. Further, the content rate of alumina in the inorganic filler may be 99.6% by mass or less.
- the content of the inorganic filler is preferably 60% by volume or more, and 70% by volume with respect to the entire sealing composition. More preferably, it is more preferably 75% by volume or more. From the viewpoint of high thermal conductivity, the content of the inorganic filler is preferably 78% by volume or more, more preferably 80% by volume or more, based on the whole sealing composition. From the viewpoint of moldability and fluidity of the sealing composition, the content of the inorganic filler is preferably 95% by volume or less, and more preferably 90% by volume or less with respect to the entire sealing composition. It is preferably 85% by volume or less, and more preferably 85% by volume or less.
- the content of the inorganic filler is preferably 78% by volume to 90% by volume, more preferably 78% by volume to 85% by volume, from the viewpoint of achieving both high thermal conductivity and moldability and fluidity of the sealing composition. 80% by volume to 85% by volume is more preferable.
- the average particle size of the inorganic filler is preferably 4 ⁇ m to 100 ⁇ m, more preferably 7 ⁇ m to 70 ⁇ m, and further preferably 7 ⁇ m to 40 ⁇ m.
- the average particle diameter of the inorganic filler is the average particle diameter of alumina when alumina is used alone as the inorganic filler, and alumina and other inorganic fillers are used as the inorganic filler in combination. In this case, the average particle size of the whole inorganic filler is referred to.
- the thermal conductivity of the cured product of the sealing composition tends to increase as the average particle size of the inorganic filler increases.
- the average particle size of the inorganic filler can be measured by the following method.
- the inorganic filler to be measured is added to the solvent (pure water) together with 1% to 8% by mass of the surfactant within the range of 1% to 5% by mass, and the ultrasonic cleaning machine of 110 W is used for 30 seconds to 5%. Vibrate for minutes to disperse the inorganic filler. About 3 mL of the dispersion liquid is injected into the measuring cell and measurement is performed at 25°C. A laser diffraction type particle size distribution meter (LA920, Horiba, Ltd.) is used as a measuring device, and the particle size distribution based on volume is measured. The average particle diameter is obtained as the particle diameter (D50%) when the accumulation from the small diameter side is 50% in the volume-based particle size distribution.
- the refractive index of alumina is used as the refractive index. When the inorganic filler is a mixture of alumina and another inorganic filler, the refractive index of alumina is used as the refractive index.
- the specific surface area of the inorganic filler is preferably from 0.7m 2 /g ⁇ 4.0m 2 / g, with 0.9m 2 /g ⁇ 3.0m 2 / g more preferably in, still more preferably 1.0m 2 /g ⁇ 2.5m 2 / g.
- the fluidity of the sealing composition tends to increase as the specific surface area of the inorganic filler decreases.
- the specific surface area of the inorganic filler is the specific surface area of alumina when, for example, alumina is used alone as the inorganic filler, and alumina and other inorganic fillers are used in combination as the inorganic filler.
- the specific surface area (BET specific surface area) of the inorganic filler can be measured from the nitrogen adsorption capacity according to JIS Z 8830:2013.
- QUANTACHROME company: AUTOSORB-1 (trade name) can be used.
- AUTOSORB-1 trade name
- the measurement cell charged with 0.05 g of the measurement sample was depressurized to 10 Pa or less by a vacuum pump, heated at 110° C., held for 3 hours or more, and then kept at room temperature (vacuum) while maintaining the depressurized state. Cool naturally to 25°C).
- the evaluation temperature is set to 77K, and the evaluation pressure range is measured as relative pressure (equilibrium pressure to saturated vapor pressure) of less than 1.
- the sealing composition may further contain a curing accelerator.
- the type of curing accelerator is not particularly limited, and known curing accelerators can be used. Specific examples of the curing accelerator include 1,8-diaza-bicyclo[5.4.0]undecene-7, 1,5-diaza-bicyclo[4.3.0]nonene and 5,6-dibutyl.
- Cycloamidine compounds such as amino-1,8-diaza-bicyclo[5.4.0]undecene-7; cycloamidine compounds with maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone Compounds having an intramolecular polarization formed by adding a compound having a ⁇ bond such as a quinone compound such as diazophenylmethane or phenol resin; benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, etc.
- a quinone compound such as diazophenylmethane or phenol resin
- Tertiary amine compounds Tertiary amine compounds; derivatives of tertiary amine compounds; imidazole compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole; derivatives of imidazole compounds; tributylphosphine, methyldiphenylphosphine, triphenyl Organic phosphine compounds such as phosphine, tris(4-methylphenyl)phosphine, diphenylphosphine and phenylphosphine; Maleic anhydride, the above quinone compound, diazophenylmethane, compounds having a ⁇ bond such as phenol resin are added to the organic phosphine compound.
- imidazole compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole
- derivatives of imidazole compounds tributylphosphine, methyldiphenylphos
- a phosphorus compound having an intramolecular polarization tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, tetraphenylboron salt such as N-methylmorpholine tetraphenylborate; Derivatives of tetraphenylboron salts; adducts of phosphine compounds such as triphenylphosphonium-triphenylborane, N-methylmorpholine tetraphenylphosphonium-tetraphenylborate and tetraphenylboron salts; and the like.
- the curing accelerator may be used alone or in combination of two or more.
- the curing accelerator is preferably a phosphorus-based curing accelerator, and among them, an organic phosphine compound, an adduct of an organic phosphine compound, and an adduct of a phosphine compound and a tetraphenylboron salt are more preferable, and an organic phosphine compound and An adduct of an organic phosphine compound is more preferable, and a compound obtained by adding a quinone compound to an organic phosphine compound is particularly preferable.
- the content of the curing accelerator is preferably 0.1% by mass to 8% by mass based on the total amount of the epoxy resin and the curing agent.
- the sealing composition may further contain an ion trap agent.
- the ion trap agent that can be used in the present disclosure is not particularly limited as long as it is an ion trap agent that is generally used in the encapsulating material used for manufacturing semiconductor devices.
- Examples of the ion trapping agent include compounds represented by the following general formula (4) or the following general formula (5).
- Ion trap agents are available as commercial products.
- DHT-4A Chemical Industry Co., Ltd., trade name
- IXE500 Toagosei Co., Ltd., trade name
- ion trapping agents other than those mentioned above include hydrous oxides of elements selected from the group consisting of magnesium, aluminum, titanium, zirconium, antimony and the like.
- the ion trap agents may be used alone or in combination of two or more.
- the content of the ion trap agent is preferably 1 part by mass or more based on 100 parts by mass of the epoxy resin from the viewpoint of realizing sufficient moisture resistance reliability. .. From the viewpoint of sufficiently exerting the effect of other components, the content of the ion trap agent is preferably 15 parts by mass or less with respect to 100 parts by mass of the epoxy resin.
- the average particle size of the ion trap agent is preferably 0.1 ⁇ m to 3.0 ⁇ m, and the maximum particle size is preferably 10 ⁇ m or less.
- the average particle size of the ion trap agent can be measured in the same manner as in the case of the inorganic filler.
- the sealing composition may further contain a coupling agent.
- the type of coupling agent is not particularly limited, and known coupling agents can be used. Examples of the coupling agent include silane coupling agents and titanium coupling agents. As the coupling agent, one type may be used alone, or two or more types may be used in combination.
- silane coupling agents include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris( ⁇ -methoxyethoxy)silane, ⁇ -methacryloxypropyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, ⁇ -(3,4- Epoxycyclohexyl)ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -[bis( ⁇ -hydroxyethyl)] Aminopropyltriethoxysilane, N- ⁇ -(aminoethyl)- ⁇ -aminopropyltrimethoxysilane, ⁇ -( ⁇ -aminoethyl)aminopropyldimethoxymethylsi
- Titanium coupling agents include isopropyl triisostearoyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(2,2).
- the sealing composition may contain, as the coupling agent, a silane compound having a structure in which a chain hydrocarbon group having 6 or more carbon atoms is bonded to a silicon atom (hereinafter also referred to as “specific silane compound”). Good.
- the chain hydrocarbon group may be branched or may have a substituent.
- carbon number of a chain hydrocarbon group means carbon number which does not contain carbon of a branch or a substituent.
- the chain hydrocarbon group may or may not contain an unsaturated bond, and preferably does not contain an unsaturated bond.
- the number of chain hydrocarbon groups bonded to a silicon atom in the specific silane compound may be 1 to 4, preferably 1 to 3, more preferably 1 or 2, and 1 Is more preferable.
- the atom or atomic group other than the chain hydrocarbon group bonded to the silicon atom is not particularly limited and is independent of each other. Further, it may be a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, an aryl group, an aryloxy group or the like. Among them, it is preferable that one or more alkoxys are bonded to the silicon atom in the specific silane compound in addition to the chain hydrocarbon group, and one chain hydrocarbon group and three alkoxy groups Is more preferably bonded to a silicon atom.
- the carbon number of the chain hydrocarbon group of the specific silane compound is 6 or more, preferably 7 or more, and more preferably 8 or more from the viewpoint of suppressing the viscosity.
- the upper limit of the number of carbon atoms of the chain hydrocarbon group of the specific silane compound is not particularly limited, and is preferably 12 or less, and more preferably 11 or less from the viewpoint of dispersibility in resin, physical property balance of the cured product, and the like. More preferably, it is even more preferably 10 or less.
- the substituent is not particularly limited.
- the substituent may be present at the end of the chain hydrocarbon group or may be present at the side chain of the chain hydrocarbon group.
- the chain hydrocarbon group preferably has at least one functional group (hereinafter, also referred to as “specific functional group”) selected from the group consisting of (meth)acryloyl group, epoxy group, and alkoxy group, ) It is more preferable to have at least one functional group selected from the group consisting of an acryloyl group and an epoxy group, and it is more preferable to have a (meth)acryloyl group.
- the specific functional group may be present at the end of the chain hydrocarbon group or may be present in the side chain of the chain hydrocarbon group. From the viewpoint of suppressing the viscosity, the specific functional group is preferably present at the end of the chain hydrocarbon group.
- the (meth)acryloyl group may be directly bonded to the chain hydrocarbon group or may be bonded via another atom or atomic group. ..
- the chain hydrocarbon group may have a (meth)acryloyloxy group.
- the chain hydrocarbon group preferably has a methacryloyloxy group.
- the chain hydrocarbon group has an epoxy group
- the epoxy group may be bonded directly to the chain hydrocarbon group or may be bonded via another atom or atomic group.
- the chain hydrocarbon group may have a glycidyloxy group, an alicyclic epoxy group, or the like.
- the chain hydrocarbon group preferably has a glycidyloxy group.
- the alkoxy group may be directly bonded to the chain hydrocarbon group, or may be bonded via another atom or atomic group, and the chain hydrocarbon group may be bonded. It is preferred that it is directly bonded to.
- the alkoxy group is not particularly limited and may be a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group and the like.
- the chain hydrocarbon group preferably has a methoxy group from the viewpoint of easy availability.
- the equivalent (molecular weight/number of functional groups) of at least one functional group selected from the group consisting of (meth)acryloyl group, epoxy group, and alkoxy group in the specific silane compound is not particularly limited. From the viewpoint of lowering the viscosity of the sealing composition, it is preferably 200 g/eq to 420 g/eq, more preferably 210 g/eq to 405 g/eq, and further preferably 230 g/eq to 390 g/eq. More preferable.
- silane compounds include hexyltrimethoxysilane, heptyltrimethoxysilane, octyltrimethoxysilane, hexyltriethoxysilane, heptyltriethoxysilane, octyltriethoxysilane, 6-glycidoxyhexyltrimethoxysilane, 7-glycid Xyheptyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane, 6-(meth)acryloxyhexyltrimethoxysilane, 7-(meth)acryloxyheptyltrimethoxysilane, 8-(meth)acryloxyoctyltrimethoxysilane Examples thereof include silane and decyltrimethoxysilane.
- 8-glycidoxyoctyltrimethoxysilane and 8-methacryloxyoctyltrimethoxysilane are preferable as the specific silane compound from the viewpoint of lowering the viscosity of the sealing composition.
- the specific silane compounds may be used alone or in combination of two or more.
- the specific silane compound may be synthesized or a commercially available one may be used.
- Specific commercially available silane compounds include Shin-Etsu Chemical Co., Ltd. KBM-3063 (hexyltrimethoxysilane), KBE-3063 (hexyltriethoxysilane), KBE-3083 (octyltriethoxysilane), KBM-4803 ( 8-glycidoxyoctyltrimethoxysilane), KBM-5803 (8-methacryloxyoctyltrimethoxysilane), KBM-3103C (decyltrimethoxysilane) and the like can be mentioned.
- the content of the coupling agent is preferably 3% by mass or less, more preferably 2% by mass or less, and more preferably 1% by mass, based on the entire sealing composition. % Or less is more preferable, and from the viewpoint of exerting the effect, it is preferably 0.1% by mass or more, more preferably 0.15% by mass or more, and further preferably 0.2% by mass or more.
- the content of the coupling agent may be 0.01 parts by mass or more, and may be 0.02 parts by mass or more, based on 100 parts by mass of the inorganic filler.
- the content of the coupling agent is preferably 5 parts by mass or less, and more preferably 2.5 parts by mass or less with respect to 100 parts by mass of the inorganic filler.
- the content of the coupling agent is preferably 0.05 parts by mass to 2.0 parts by mass, and 0.1 parts by mass with respect to 100 parts by mass of the inorganic filler, from the viewpoint of achieving both fluidity and moldability of the package. It is more preferably to 1.5 parts by mass, still more preferably 0.2 parts to 1.0 parts by mass.
- the sealing composition may further contain a release agent.
- the type of release agent is not particularly limited, and known release agents can be used. Specifically, examples of the release agent include higher fatty acids, carnauba wax, montan wax, polyethylene wax and the like.
- the release agent may be used alone or in combination of two or more.
- the content of the release agent is preferably 10% by mass or less based on the total amount of the epoxy resin and the curing agent, and from the viewpoint of exerting the effect. Is preferably 0.5% by mass or more.
- the sealing composition may contain a colorant (carbon black or the like). Further, the sealing composition may contain a modifier (silicone, silicone rubber, etc.). Each of the colorant and the modifier may be used alone or in combination of two or more.
- the conductive particles When conductive particles such as carbon black are used as the colorant, the conductive particles preferably have a content of particles having a particle diameter of 10 ⁇ m or more of 1% by mass or less.
- the content of the conductive particles is preferably 3% by mass or less based on the total amount of the epoxy resin and the curing agent.
- the sealing composition may further contain other additives, if necessary.
- Other additives include flame retardants, anion exchangers, plasticizers and the like. Further, various additives well known in the art may be added to the composition, if necessary.
- the method for producing the sealing composition is not particularly limited, and a known method can be used.
- a sealing composition can be prepared by thoroughly mixing a mixture of raw materials in a predetermined amount with a mixer or the like, kneading the mixture with a heat roll, an extruder, or the like, and then cooling, pulverizing, or the like.
- the state of the sealing composition is not particularly limited and may be powdery, solid, liquid or the like.
- a semiconductor device of the present disclosure includes a semiconductor element and a cured product of the sealing composition of the present disclosure obtained by sealing the semiconductor element.
- the method of sealing the semiconductor element with the sealing composition is not particularly limited, and a known method can be applied.
- a transfer molding method or the like is generally used, but a compression molding method, an injection molding method, a compression molding method or the like may be used.
- the semiconductor device of the present disclosure is suitable as an IC (Integrated Circuit, integrated circuit), an LSI (Large-Scale Integration, large-scale integrated circuit), or the like.
- Examples 1 to 5 and Comparative Example 1 The components shown below were premixed (dry blended) at the blending ratio (parts by mass) shown in Table 1, kneaded with a biaxial kneader, and cooled and pulverized to produce a powdery sealing composition.
- the details of the components shown in Table 1 are as follows.
- Epoxy resin Epoxy resin A1-1 First epoxy resin, Mitsubishi Chemical Corporation, epoxy group equivalent “440 g/eq”, glass transition temperature after curing “ ⁇ 57° C.”, two epoxy groups in the molecule, Epoxy Resin Having Rubber Elastic Skeleton and Divalent Linking Group Represented by Structural Formula (1)
- Epoxy Resin A1-2 First Epoxy Resin, Mitsubishi Chemical Co., Epoxy Group Equivalent “489 g/eq”, Epoxy resin having a glass transition temperature after curing “31° C.”, two epoxy groups in the molecule, a flexible skeleton, a skeleton containing an aromatic ring, and a divalent linking group represented by the structural formula (1).
- Epoxy resin A1 -3 First epoxy resin, Mitsubishi Chemical Corporation, epoxy group equivalent "501 g/eq", glass transition temperature after curing "19°C”, epoxy resin having two epoxy groups in the molecule
- Epoxy resin A2 second Epoxy resin, Mitsubishi Chemical Corporation, product name "YX4000H”, epoxy group equivalent "192 g/eq”, glass transition temperature after curing "150°C”, softening point "107°C”, biphenyl type epoxy resin
- the value of the glass transition temperature after curing in the epoxy resin is the epoxy resin to be measured, "HE910-09” (Air Water Co., Ltd.) which is a polyfunctional phenol resin curing agent, and phosphorus-based curing acceleration. It is the value of the glass transition temperature in the cured product for measurement, which was obtained by heating the mixture obtained by mixing the agent "addition product of tributylphosphine and benzoquinone" at 175°C for 6 hours.
- the number of epoxy groups (that is, the total number) of the epoxy resin that is the measurement target of the polyfunctional phenol resin curing agent and the number of the hydroxyl groups (that is, the total number) of the phenol resin are approximately the same.
- the phosphorus-based curing accelerator is added so that the content of the phosphorus-based curing accelerator is 3 to 6 parts by mass with respect to 100 parts by mass of the epoxy resin and the polyfunctional phenol resin curing agent in total. did. Further, the glass transition temperature is measured by cutting the obtained cured product for measurement, weighing 10 mg, and using a differential scanning calorimeter (TA Instruments Japan Co., product name "DSC Q100"). The temperature was raised at a rate of 10° C./min, and the glass transition temperature was defined as the intersection of tangents before and after the inflection point of the obtained chart.
- Hardener Hardener B1 Triphenylmethane type phenol resin, Air Water Co., Ltd., product name "HE910-09", hydroxyl group equivalent "92 to 104 g/eq", softening point "75 to 85°C"
- Curing accelerator C1 Phosphorus curing accelerator (addition product of tributylphosphine and benzoquinone)
- D Coupling agent Coupling agent D1:8-methacryloxyoctyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd., product name "KBM-5803"
- E Release Agent Release Agent E1: Montan Wax, Clariant Company, Product Name “HW-E”
- Colorant Pigment F1 Carbon black, Mitsubishi Chemical Corporation, trade name “MA600”
- Additive Additive G1 Triphenylphosphine oxide
- Modifier Modifier H1 Silicone, Toray Dow Corning Co., Ltd., product name "BY16-876"
- Inorganic filler filler I1 silica particles, spherical, specific surface area "190 m 2 /g to 230 m 2 /g”
- Filler I2 Alumina particles, spherical, average particle size “0.7 ⁇ m”
- Filler I3 Alumina particles, spherical, average particle size “10 ⁇ m”
- a test piece having a shape of 127 mm ⁇ 12.7 mm ⁇ 4 mm was formed by a transfer molding machine under the conditions of a mold temperature of 175° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Was produced. Then, post-curing was performed at 175° C. for 6 hours.
- Tensilon (A&D Co.) as an evaluation device a three-point support type bending test based on JIS-K-7171 (2016) was carried out at 25° C. and 260° C., and the bending elastic modulus of the test piece was obtained.
- the flexural modulus E is defined by the following formula, and the flexural modulus obtained by measurement at 25° C. is referred to as “room temperature modulus” and the flexural modulus obtained at 260° C. is referred to as “high temperature modulus”. To do.
- E is a bending elastic modulus (MPa)
- P is a load cell value (N)
- y is a displacement amount (mm)
- Thermal conductivity Using the above-obtained sealing composition, a transfer molding machine was used to prepare a test piece for thermal conductivity evaluation under the conditions of a mold temperature of 175° C. to 180° C., a molding pressure of 7 MPa, and a curing time of 300 seconds. Next, the thermal diffusivity of the molded test piece in the thickness direction was measured. The thermal diffusivity was measured by the laser flash method (apparatus: LFA467 nanoflash, NETZSCH). The pulsed light irradiation was performed under the conditions of a pulse width of 0.31 (ms) and an applied voltage of 247V. The measurement was performed at an ambient temperature of 25°C ⁇ 1°C.
- average particle size of filler means the volume-based average particle size of the whole inorganic filler used
- fill content is the content of the whole inorganic filler used with respect to the entire sealing composition.
Abstract
Description
一方で、半導体パッケージに使用される部材には、温度サイクルテストに対する耐久性も求められる。
例えば無機充填材を高充填させると、封止材の高熱伝導化が可能になるものの、弾性率が高くなることで温度サイクルテストに対する耐久性が低下する場合があり、封止材の高熱伝導化と低弾性率化とはトレードオフの関係にある。そのため、高熱伝導化と低弾性率化とを両立することが難しい場合がある。 In recent years, with the miniaturization and high integration, there is concern about heat generation inside the semiconductor package. High heat conductivity is required for members used for the semiconductor package because heat generation may cause a deterioration in performance of an electric component or an electronic component having the semiconductor package. Therefore, it is required that the sealing material of the semiconductor package has high thermal conductivity.
On the other hand, members used for semiconductor packages are also required to have durability against a temperature cycle test.
For example, if the inorganic filler is highly filled, the thermal conductivity of the encapsulant can be increased, but the durability of the encapsulant may decrease due to the high elastic modulus. There is a trade-off relationship between low elasticity and low elasticity. Therefore, it may be difficult to achieve both high thermal conductivity and low elastic modulus.
<1>
エポキシ基当量が300g/eq以上であり、多官能フェノール樹脂硬化剤及びリン系硬化促進剤を用いて硬化させたときのガラス転移温度が40℃以下である第1のエポキシ樹脂と、
硬化剤と、
無機充填材と、
を含有する封止組成物。
<2>
前記無機充填材の含有率は、封止組成物全体に対して78体積%以上である<1>に記載の封止組成物。
<3>
融点又は軟化点が50℃以上である第2のエポキシ樹脂をさらに含有する<1>又は<2>に記載の封止組成物。
<4>
前記第1のエポキシ樹脂の含有率は、封止組成物に含有されるエポキシ樹脂の総量に対して20質量%以上である<1>~<3>のいずれか1つに記載の封止組成物。
<5>
前記第1のエポキシ樹脂の含有率は、封止組成物に含有されるエポキシ樹脂の総量に対して50質量%以下である<1>~<4>のいずれか1つに記載の封止組成物。
<6>
前記第1のエポキシ樹脂は、分子内に2つのエポキシ基を有する<1>~<5>のいずれか1つに記載の封止組成物。
<7>
前記第1のエポキシ樹脂は、分子内に下記構造式(1)で表される2価の連結基を有する<1>~<6>のいずれか1つに記載の封止組成物。 The present invention includes the following embodiments.
<1>
A first epoxy resin having an epoxy group equivalent of 300 g/eq or more and having a glass transition temperature of 40° C. or less when cured using a polyfunctional phenol resin curing agent and a phosphorus-based curing accelerator;
A curing agent,
An inorganic filler,
A sealing composition containing:
<2>
The content rate of the said inorganic filler is a sealing composition as described in <1> which is 78 volume% or more with respect to the whole sealing composition.
<3>
The encapsulating composition according to <1> or <2>, further containing a second epoxy resin having a melting point or a softening point of 50° C. or higher.
<4>
The encapsulating composition according to any one of <1> to <3>, in which the content of the first epoxy resin is 20% by mass or more based on the total amount of the epoxy resins contained in the encapsulating composition. Stuff.
<5>
The encapsulating composition according to any one of <1> to <4>, in which the content of the first epoxy resin is 50% by mass or less based on the total amount of the epoxy resin contained in the encapsulating composition. Stuff.
<6>
The first epoxy resin is the encapsulating composition as described in any one of <1> to <5>, which has two epoxy groups in the molecule.
<7>
The sealing composition according to any one of <1> to <6>, wherein the first epoxy resin has a divalent linking group represented by the following structural formula (1) in the molecule.
<8>
半導体素子と、前記半導体素子を封止してなる<1>~<7>のいずれか1つに記載の封止組成物の硬化物と、を含む半導体装置。 In the above structural formula (1), * indicates a binding part.
<8>
A semiconductor device comprising: a semiconductor element; and a cured product of the encapsulating composition according to any one of <1> to <7>, which is obtained by encapsulating the semiconductor element.
本開示中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本開示中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本開示において各成分は該当する物質を複数種含んでいてもよい。組成物中に各成分に該当する物質が複数種存在する場合、各成分の含有率又は含有量は、特に断らない限り、組成物中に存在する当該複数種の物質の合計の含有率又は含有量を意味する。
本開示において各成分に該当する粒子は複数種含んでいてもよい。組成物中に各成分に該当する粒子が複数種存在する場合、各成分の粒子径は、特に断らない限り、組成物中に存在する当該複数種の粒子の混合物についての値を意味する。 In the present disclosure, the numerical ranges indicated by using “to” include the numerical values before and after “to” as the minimum value and the maximum value, respectively.
In the numerical ranges described stepwise in the present disclosure, the upper limit or the lower limit described in one numerical range may be replaced with the upper limit or the lower limit of the numerical range described in other stages. .. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present disclosure, each component may include a plurality of types of corresponding substances. When there are multiple types of substances corresponding to each component in the composition, the content rate or content of each component is the total content rate or content of the multiple types of substances present in the composition unless otherwise specified. Means quantity.
In the present disclosure, a plurality of types of particles corresponding to each component may be included. When a plurality of types of particles corresponding to each component are present in the composition, the particle size of each component means a value for a mixture of the plurality of types of particles present in the composition unless otherwise specified.
本開示の封止組成物は、エポキシ基当量が300g/eq以上であり、多官能フェノール樹脂硬化剤及びリン系硬化促進剤を用いて硬化させたときのガラス転移温度が40℃以下である第1のエポキシ樹脂と、硬化剤と、無機充填材と、を含有する。
本開示の封止組成物は、上記第1のエポキシ樹脂を含有するため、高い熱伝導性を得つつ、室温(すなわち25℃)における弾性率(以下「室温弾性率」ともいう)及び高温(すなわち260℃)における弾性率(以下「高温弾性率」ともいう)の低い硬化物が得られる。
ここで、「多官能フェノール樹脂硬化剤」は1分子中に官能基(すなわち水酸基)を3以上有するフェノール樹脂である硬化剤であり、「リン系硬化促進剤」はリン原子を有する硬化促進剤である。 <Sealing composition>
The sealing composition of the present disclosure has an epoxy group equivalent of 300 g/eq or more, and a glass transition temperature of 40° C. or less when cured using a polyfunctional phenol resin curing agent and a phosphorus-based curing accelerator. 1 epoxy resin, a curing agent, and an inorganic filler.
Since the encapsulating composition of the present disclosure contains the first epoxy resin described above, while obtaining high thermal conductivity, the elastic modulus at room temperature (that is, 25° C.) (hereinafter also referred to as “room temperature elastic modulus”) and the high temperature ( That is, a cured product having a low elastic modulus at 260° C. (hereinafter also referred to as “high temperature elastic modulus”) can be obtained.
Here, the "multifunctional phenol resin curing agent" is a curing agent that is a phenol resin having three or more functional groups (that is, hydroxyl groups) in one molecule, and the "phosphorus curing accelerator" is a curing accelerator having a phosphorus atom. Is.
まず、測定対象であるエポキシ樹脂と、多官能フェノール樹脂硬化剤であるトリフェニルメタン型フェノール樹脂と、リン系硬化促進剤である有機ホスフィン化合物のキノン付加物と、を混合した混合物を175℃で6時間加熱することで、測定用硬化物を得る。なお、多官能フェノール樹脂硬化剤は、測定対象であるエポキシ樹脂のエポキシ基の数(すなわち総数)とフェノール樹脂の水酸基の数(すなわち総数)とが同程度になるように添加する。また、リン系硬化促進剤は、エポキシ樹脂と多官能フェノール樹脂硬化剤との合計100質量部に対しリン系硬化促進剤の含有量が3質量部~6質量部になるように添加する。
次に、得られた測定用硬化物を切断して10mgをはかり取り、DSC(Differential scanning calorimetry、示差走査熱量計)測定を行う。具体的には、示差走査熱量計(ティー・エイ・インスツルメント・ジャパン社、品名「DSC Q100」)を用いて昇温速度10℃/分の条件にて測定し、得られたチャートの変曲点前後における接線の交点をガラス転移温度とする。 The above "glass transition temperature when cured using a polyfunctional phenol resin curing agent and a phosphorus-based curing accelerator" is measured as follows.
First, a mixture of an epoxy resin to be measured, a triphenylmethane type phenolic resin which is a polyfunctional phenolic resin curing agent, and a quinone adduct of an organic phosphine compound which is a phosphorus-based curing accelerator is mixed at 175°C. A cured product for measurement is obtained by heating for 6 hours. The polyfunctional phenol resin curing agent is added so that the number of epoxy groups (that is, the total number) of the epoxy resin that is the measurement target and the number of hydroxyl groups (that is, the total number) of the phenol resin are approximately the same. Further, the phosphorus-based curing accelerator is added such that the content of the phosphorus-based curing accelerator is 3 parts by mass to 6 parts by mass with respect to 100 parts by mass in total of the epoxy resin and the polyfunctional phenol resin curing agent.
Next, the obtained cured product for measurement is cut, 10 mg is weighed, and DSC (Differential scanning calorimetry) measurement is performed. Specifically, a differential scanning calorimeter (TA Instruments Japan Co., Ltd., product name “DSC Q100”) was used to measure the temperature rise rate of 10° C./min, and the obtained chart was changed. The intersection of the tangents before and after the bending point is the glass transition temperature.
また、リン系硬化促進剤である上記有機ホスフィン化合物のキノン付加物としては、例えばトリブチルホスフィンとベンゾキノンの付加物を用いることができる。なお、本開示の封止組成物が硬化促進剤を含有する場合、封止組成物に含有される硬化促進剤の種類及び添加量は、それぞれ、上記測定用硬化物を得るために用いる硬化促進剤の種類及び添加量と同じであってもよく、異なっていてもよい。
以下、「多官能フェノール樹脂硬化剤及びリン系硬化促進剤を用いて硬化させたときのガラス転移温度」を、「硬化後ガラス転移温度」と称する場合がある。 Here, as the above-mentioned triphenylmethane type phenol resin which is a polyfunctional phenol resin curing agent, for example, “HE910-09” (Air Water Co., Ltd., hydroxyl group equivalent: 92 to 104 g/eq, softening point: 75 to 85° C.) ) Can be used. The type and amount of the curing agent contained in the encapsulating composition of the present disclosure may be the same as or different from the type and amount of the curing agent used to obtain the cured product for measurement. May be
As the quinone adduct of the above organic phosphine compound, which is a phosphorus-based curing accelerator, for example, an adduct of tributylphosphine and benzoquinone can be used. When the encapsulating composition of the present disclosure contains a curing accelerator, the type and the addition amount of the curing accelerator contained in the encapsulating composition are the curing acceleration used for obtaining the cured product for measurement. The type and the addition amount of the agent may be the same or different.
Hereinafter, the "glass transition temperature when cured using a polyfunctional phenol resin curing agent and a phosphorus-based curing accelerator" may be referred to as "glass transition temperature after curing".
エポキシ樹脂としては、一般的に、フェノール化合物(フェノール、クレゾール、キシレノール、レゾルシン、カテコール、ビスフェノールA、ビスフェノールF等)及びナフトール化合物(α-ナフトール、β-ナフトール、ジヒドロキシナフタレン等)からなる群より選択される少なくとも1種と、アルデヒド化合物(ホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ベンズアルデヒド、サリチルアルデヒド等)と、を酸性触媒下で縮合又は共縮合させて得られるノボラック樹脂をエポキシ化したもの(フェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂等);ビスフェノール(ビスフェノールA、ビスフェノールAD、ビスフェノールF、ビスフェノールS等)及びビフェノール(アルキル置換又は非置換のビフェノール等)からなる群より選択される少なくとも1種のジグリシジルエーテル;フェノール・アラルキル樹脂のエポキシ化物;フェノール化合物とジシクロペンタジエン及びテルペン化合物からなる群より選択される少なくとも1種との付加物又は重付加物のエポキシ化物;多塩基酸(フタル酸、ダイマー酸等)とエピクロルヒドリンの反応により得られるグリシジルエステル型エポキシ樹脂;ポリアミン(ジアミノジフェニルメタン、イソシアヌル酸等)とエピクロルヒドリンとの反応により得られるグリシジルアミン型エポキシ樹脂;オレフィン結合を過酸(過酢酸等)で酸化して得られる線状脂肪族エポキシ樹脂;脂環族エポキシ樹脂;などが挙げられる。エポキシ樹脂は、1種類を単独で使用しても、2種類以上を併用してもよい。 -Epoxy resin-
The epoxy resin is generally selected from the group consisting of phenol compounds (phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, etc.) and naphthol compounds (α-naphthol, β-naphthol, dihydroxynaphthalene, etc.). At least one of the above and an aldehyde compound (formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde, etc.) are condensed or co-condensed under an acidic catalyst to obtain an epoxidized novolak resin (phenol novolac type epoxy). Resin, ortho-cresol novolac type epoxy resin, etc.); at least one dicarboxylic acid selected from the group consisting of bisphenol (bisphenol A, bisphenol AD, bisphenol F, bisphenol S, etc.) and biphenol (alkyl-substituted or unsubstituted biphenol, etc.) Glycidyl ether; epoxidized product of phenol/aralkyl resin; epoxidized product of addition product or polyaddition product of phenol compound and at least one selected from dicyclopentadiene and terpene compound; polybasic acid (phthalic acid, dimer Glycidyl ester type epoxy resin obtained by the reaction of epichlorohydrin with acid; glycidyl amine type epoxy resin obtained by the reaction of polyamine (diaminodiphenylmethane, isocyanuric acid, etc.) with epichlorohydrin; olefinic bond with peracid (peracetic acid, etc.) Examples thereof include linear aliphatic epoxy resins obtained by oxidation; alicyclic epoxy resins and the like. The epoxy resins may be used alone or in combination of two or more.
本開示の封止組成物は、必要に応じて、第1のエポキシ樹脂及び第2のエポキシ樹脂以外のエポキシ樹脂(以下「その他のエポキシ樹脂」ともいう)を含有してもよい。ただし、第1のエポキシ樹脂及び必要に応じて含有される第2のエポキシ樹脂の合計含有率は、封止組成物に含まれる全エポキシ樹脂の総量に対し、90質量%以上であることが好ましく、95質量%以上であることがより好ましく、98質量%以上であることがさらに好ましい。 Among these epoxy resins, the sealing composition of the present disclosure is the first epoxy resin having an epoxy group equivalent of 300 g/eq or more and a glass transition temperature after curing of 40° C. or less as described above. Contains at least. Further, the sealing composition of the present disclosure may contain an epoxy resin other than the first epoxy resin as necessary, and the melting point or softening point of 50° C. or higher as the resin other than the first epoxy resin. It is preferable to further contain a certain second epoxy resin.
The encapsulating composition of the present disclosure may contain an epoxy resin other than the first epoxy resin and the second epoxy resin (hereinafter, also referred to as “other epoxy resin”), if necessary. However, the total content of the first epoxy resin and the second epoxy resin, which is optionally contained, is preferably 90% by mass or more based on the total amount of all epoxy resins contained in the encapsulating composition. Is more preferably 95 mass% or more, further preferably 98 mass% or more.
第1のエポキシ樹脂は、エポキシ基当量が300g/eq以上であり、かつ、硬化後ガラス転移温度が40℃以下であるエポキシ樹脂であれば特に限定されるものではない。
第1のエポキシ樹脂におけるエポキシ基当量は、300g/eq以上であり、高温弾性率を低減させる観点から350g/eq以上であることが好ましく、400g/eq以上であることがより好ましい。また、第1のエポキシ樹脂におけるエポキシ基当量は、熱時硬度の担保の観点から、600g/eq以下であることが好ましく、570g/eq以下であることがより好ましく、540g/eq以下であることがさらに好ましい。第1のエポキシ樹脂におけるエポキシ基当量は、高温弾性率の低減と熱時硬度の担保を両立する観点から、300g/eq~600g/eqであることが好ましく、350g/eq~570g/eqであることがより好ましく、400g/eq~540g/eqであることがさらに好ましい。 (First epoxy resin)
The first epoxy resin is not particularly limited as long as it has an epoxy group equivalent of 300 g/eq or more and a glass transition temperature after curing of 40° C. or less.
The epoxy group equivalent in the first epoxy resin is 300 g/eq or more, preferably 350 g/eq or more, and more preferably 400 g/eq or more from the viewpoint of reducing the high temperature elastic modulus. Further, the epoxy group equivalent in the first epoxy resin is preferably 600 g/eq or less, more preferably 570 g/eq or less, and more preferably 540 g/eq or less from the viewpoint of ensuring the hardness during heating. Is more preferable. The epoxy group equivalent in the first epoxy resin is preferably 300 g/eq to 600 g/eq, and is 350 g/eq to 570 g/eq, from the viewpoint of simultaneously achieving a reduction in high temperature elastic modulus and a guarantee of hardness during heating. More preferably, it is more preferably 400 g/eq to 540 g/eq.
なお、上記エポキシ基は、グリシジル基、グリシジルオキシ基、グリシジルオキシカルボニル基、及びエポキシシクロアルキル基(エポキシシクロペンチル基、エポキシシクロヘキシル基、エポキシシクロオクチル基等)からなる群より選択される少なくとも一種の一部として、第1のエポキシ樹脂の分子中に含まれていてもよい。 The first epoxy resin has at least two epoxy groups in the molecule. The number of epoxy groups contained in one molecule of the first epoxy resin is not particularly limited as long as the epoxy group equivalent in the first epoxy resin is in the above range, and may be 2-8, 2-6. Is preferable, 2 to 3 is more preferable, and 2 is particularly preferable.
The epoxy group is at least one selected from the group consisting of glycidyl group, glycidyloxy group, glycidyloxycarbonyl group, and epoxycycloalkyl group (epoxycyclopentyl group, epoxycyclohexyl group, epoxycyclooctyl group, etc.). As a part, it may be contained in the molecule of the first epoxy resin.
なお、下記構造式(1)中、*は結合部を示す。 The first epoxy resin preferably has a divalent linking group represented by the following structural formula (1) in the molecule, in addition to two or more epoxy groups.
In the structural formula (1) below, * indicates a bonding part.
ここで、ゴム弾性骨格は、エポキシ樹脂にゴム弾性を付与する部分構造であり、ゴム弾性骨格の具体例としては、アルキレンオキシ基等が挙げられる。
また、柔軟骨格は、エポキシ樹脂の柔軟性を付与する部分構造であり、柔軟骨格の具体例としては、アルキレンオキシ基、長鎖アルキル基、シロキサン骨格等が挙げられる。 The first epoxy resin preferably has, in the molecule, at least one selected from the group consisting of a rubber elastic skeleton and a flexible skeleton, in addition to two or more epoxy groups. The first epoxy resin may have at least one kind selected from the group consisting of a rubber elastic skeleton and a flexible skeleton in the molecule, or may have two or more kinds.
Here, the rubber elastic skeleton is a partial structure that imparts rubber elasticity to the epoxy resin, and specific examples of the rubber elastic skeleton include alkyleneoxy groups and the like.
The flexible skeleton is a partial structure that imparts flexibility to the epoxy resin, and specific examples of the flexible skeleton include an alkyleneoxy group, a long-chain alkyl group, and a siloxane skeleton.
芳香環を含む骨格としては、ベンゼン環骨格、ナフタレン骨格のほか、ビフェニル骨格、ビスフェノールA骨格、ビスフェノールF骨格、ビスフェノールAD骨格、ビスフェノールS骨格等が挙げられる。 The first epoxy resin may have a skeleton containing an aromatic ring in addition to two or more epoxy groups in the molecule.
Examples of the skeleton containing an aromatic ring include a benzene ring skeleton, a naphthalene skeleton, a biphenyl skeleton, a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol AD skeleton, and a bisphenol S skeleton.
また、封止組成物全体に対する第1のエポキシ樹脂の含有率は、0.2質量%~3質量%であることが好ましく、0.4質量%~1.5質量%であることがより好ましく、0.6質量%~1.1質量%であることがさらに好ましい。 The content of the first epoxy resin with respect to the total amount of all epoxy resins contained in the encapsulating composition is preferably 10% by mass or more and 20% by mass or more from the viewpoint of reducing the room temperature elastic modulus and the high temperature elastic modulus. Is more preferable and 25% by mass or more is further preferable. The content of the first epoxy resin with respect to the total amount of all epoxy resins contained in the encapsulating composition is preferably 50% by mass or less and 45% by mass or less from the viewpoint of moldability of the encapsulating composition. Is more preferable, and 40% by mass or less is further preferable. The content of the first epoxy resin with respect to the total amount of all epoxy resins contained in the encapsulating composition is 10% by mass from the viewpoint of achieving both reduction in room temperature elastic modulus and high temperature elastic modulus and moldability of the encapsulating composition. It is preferably ˜50% by mass, more preferably 20% by mass to 45% by mass, and further preferably 25% by mass to 40% by mass.
The content of the first epoxy resin in the whole sealing composition is preferably 0.2% by mass to 3% by mass, more preferably 0.4% by mass to 1.5% by mass. More preferably, it is from 0.6% by mass to 1.1% by mass.
第2のエポキシ樹脂は、第1のエポキシ樹脂以外のエポキシ樹脂であり、かつ、融点又は軟化点が50℃以上であるエポキシ樹脂であれば特に限定されるものではない。
ここで、エポキシ樹脂の融点は示差走査熱量測定(DSC)で測定される値とし、エポキシ樹脂の軟化点はJIS K 7234:1986に準じた方法(環球法)で測定される値とする。
なお、第2のエポキシ樹脂における融点又は軟化点は、封止組成物の成形性の観点から、50℃以上であることが好ましく、60℃以上であることがより好ましく、70℃以上であることがさらに好ましい。また、第2のエポキシ樹脂における融点又は軟化点は、製造時の混練性の観点から、150℃以下であることが好ましく、130℃以下であることがより好ましく、120℃以下であることがさらに好ましい。第2のエポキシ樹脂における融点又は軟化点は、封止組成物の成形性と製造時の混練性の観点から、50℃~150℃であることが好ましく、60℃~130℃であることがより好ましく、70℃~120℃であることがさらに好ましい。 (Second epoxy resin)
The second epoxy resin is not particularly limited as long as it is an epoxy resin other than the first epoxy resin and has a melting point or a softening point of 50° C. or higher.
Here, the melting point of the epoxy resin is a value measured by differential scanning calorimetry (DSC), and the softening point of the epoxy resin is a value measured by a method (ring and ball method) according to JIS K 7234:1986.
The melting point or softening point of the second epoxy resin is preferably 50° C. or higher, more preferably 60° C. or higher, and 70° C. or higher from the viewpoint of moldability of the sealing composition. Is more preferable. In addition, the melting point or softening point of the second epoxy resin is preferably 150° C. or lower, more preferably 130° C. or lower, and further preferably 120° C. or lower, from the viewpoint of kneading properties during production. preferable. The melting point or softening point of the second epoxy resin is preferably 50° C. to 150° C., and more preferably 60° C. to 130° C. from the viewpoint of moldability of the sealing composition and kneading property during production. It is preferably 70° C. to 120° C., further preferably.
また、第2のエポキシ樹脂における硬化後ガラス転移温度は、特に限定されるものではなく、40℃より高いことが好ましく、成形性と室温弾性率低減の両立の観点から、80℃~200℃であることがより好ましく、120℃~180℃であることがさらに好ましい。 The epoxy group equivalent in the second epoxy resin is not particularly limited and is preferably less than 300 g/eq, and is 120 g/eq to 270 g/eq from the viewpoint of both moldability and reduction of high temperature elastic modulus. More preferably, it is more preferably 150 g/eq to 240 g/eq.
Further, the glass transition temperature after curing in the second epoxy resin is not particularly limited and is preferably higher than 40° C., and from the viewpoint of achieving both moldability and reduction of room temperature elastic modulus, it is from 80° C. to 200° C. More preferably, it is more preferably 120°C to 180°C.
なお、上記エポキシ基は、グリシジル基、グリシジルオキシ基、グリシジルオキシカルボニル基、及びエポキシシクロアルキル基(エポキシシクロペンチル基、エポキシシクロヘキシル基、エポキシシクロオクチル基等)からなる群より選択される少なくとも一種の一部として、第1のエポキシ樹脂の分子中に含まれていてもよい。 The second epoxy resin has at least two epoxy groups in the molecule. The number of epoxy groups contained in one molecule of the second epoxy resin is not particularly limited and may be 2-8, preferably 2-6, more preferably 2-3, and particularly preferably 2.
The epoxy group is at least one selected from the group consisting of glycidyl group, glycidyloxy group, glycidyloxycarbonyl group, and epoxycycloalkyl group (epoxycyclopentyl group, epoxycyclohexyl group, epoxycyclooctyl group, etc.). As a part, it may be contained in the molecule of the first epoxy resin.
なお、下記一般式(2)中、*は結合部を示し、R1~R8は、それぞれ独立に、水素原子、炭素数1~12のアルキル基、又は炭素数4~18の芳香族基を示す。 The second epoxy resin preferably has a divalent linking group represented by the following general formula (2) in the molecule, in addition to two or more epoxy groups.
In the general formula (2) below, * represents a bond, and R 1 to R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aromatic group having 4 to 18 carbon atoms. Indicates.
また、前記一般式(2)中、R5~R8は、それぞれ独立に、水素原子又は炭素数1~3のアルキル基が好ましく、水素原子又はメチル基がより好ましく、水素原子がさらに好ましい。 In the general formula (2), R 1 to R 4 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, and further preferably a methyl group.
In the general formula (2), R 5 to R 8 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.
また、封止組成物全体に対する第2のエポキシ樹脂の含有率は、1質量%~5質量%であることが好ましく、1.5質量%~4質量%であることがより好ましく、1.7質量%~3質量%であることがさらに好ましい。 The content of the second epoxy resin with respect to the total amount of all epoxy resins contained in the encapsulating composition is 50% by mass to 90% by mass from the viewpoint of achieving both room temperature elastic modulus and high temperature elastic modulus reduction and moldability. It is preferably in the range of 55% by mass to 80% by mass, and more preferably in the range of 60% by mass to 75% by mass.
Further, the content ratio of the second epoxy resin to the entire sealing composition is preferably 1% by mass to 5% by mass, more preferably 1.5% by mass to 4% by mass, and 1.7. More preferably, it is from 3% by mass to 3% by mass.
無機充填材を除く封止組成物に占める全エポキシ樹脂の含有率は、40質量%~70質量%であることが好ましく、45質量%~64質量%であることがより好ましく、48質量%~55質量%であることがさらに好ましい。 The total epoxy resin content in the encapsulating composition is preferably 2.0% by mass to 6% by mass, more preferably 3.0% by mass to 5.5% by mass, and 3.0 It is more preferable that the content is from 5.0% by mass to 5.0% by mass.
The content of the total epoxy resin in the sealing composition excluding the inorganic filler is preferably 40% by mass to 70% by mass, more preferably 45% by mass to 64% by mass, and 48% by mass to It is more preferably 55% by mass.
封止組成物は、硬化剤を含有する。硬化剤の種類は特に限定されず、公知の硬化剤を使用することができる。
硬化剤としては、フェノール硬化剤、アミン硬化剤、酸無水物硬化剤、ポリメルカプタン硬化剤、ポリアミノアミド硬化剤、イソシアネート硬化剤、ブロックイソシアネート硬化剤等が挙げられる。硬化剤は、流動性を維持しつつ耐リフロー性に優れる封止組成物を得る観点から、フェノール硬化剤、アミン硬化剤、及び酸無水物硬化剤が好ましく、フェノール硬化剤がより好ましい。硬化剤は1種類を単独で使用しても、2種類以上を併用してもよい。 -Curing agent-
The sealing composition contains a curing agent. The type of curing agent is not particularly limited, and known curing agents can be used.
Examples of the curing agent include a phenol curing agent, an amine curing agent, an acid anhydride curing agent, a polymercaptan curing agent, a polyaminoamide curing agent, an isocyanate curing agent, and a blocked isocyanate curing agent. The curing agent is preferably a phenol curing agent, an amine curing agent, and an acid anhydride curing agent, and more preferably a phenol curing agent, from the viewpoint of obtaining a sealing composition having excellent reflow resistance while maintaining fluidity. The curing agent may be used alone or in combination of two or more.
一般式(3)中のb1~b5は、0~1の整数であることが好ましく、0であることがより好ましい
一般式(3)中のnは、1~7であることが好ましく、2~5であることがより好ましい。 The monovalent organic group having 1 to 18 carbon atoms represented by R 11 to R 15 in the general formula (3) includes a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted Examples thereof include an aryl group and a substituted or unsubstituted aralkyl group.
B1 to b5 in the general formula (3) are preferably integers of 0 to 1, more preferably 0, and n in the general formula (3) is preferably 1 to 7. More preferably, it is -5.
硬化剤の融点又は軟化点は、エポキシ樹脂の融点又は軟化点と同様にして測定される値とする。 When the curing agent is solid, its softening point or melting point is not particularly limited. The softening point or melting point of the curing agent is preferably 40° C. to 180° C. from the viewpoint of moldability and reflow resistance, and the softening point or melting point from the viewpoint of handleability during production of the sealing composition. Is more preferably 50° C. to 130° C., further preferably 55° C. to 100° C.
The melting point or softening point of the curing agent is a value measured in the same manner as the melting point or softening point of the epoxy resin.
無機充填材は、1種類を単独で使用しても、2種類以上を併用してもよい。
無機充填材を2種類以上併用する場合としては、成分、平均粒子径、形状等が異なる無機充填材を2種類以上用いる場合が挙げられる。
無機充填材の形状は特に制限されず、粉状、球状、繊維状等が挙げられる。封止組成物の成形時の流動性及び金型摩耗性の点からは、無機充填材の形状は球状であることが好ましい。 -Inorganic filler-
The inorganic filler may be used alone or in combination of two or more.
Examples of the case where two or more kinds of inorganic fillers are used in combination include a case where two or more kinds of inorganic fillers having different components, average particle diameters, shapes, etc. are used.
The shape of the inorganic filler is not particularly limited, and examples thereof include powder, sphere, and fiber. The shape of the inorganic filler is preferably spherical from the viewpoints of fluidity during molding of the encapsulating composition and mold wear resistance.
アルミナと併用可能なその他の無機充填材としては、球状シリカ、結晶シリカ等のシリカ、ジルコン、酸化マグネシウム、珪酸カルシウム、炭酸カルシウム、チタン酸カリウム、炭化珪素、窒化珪素、窒化ホウ素、ベリリア、ジルコニアなどが挙げられる。さらに、難燃効果のある無機充填材としては水酸化アルミニウム、硼酸亜鉛等が挙げられる。 The inorganic filler preferably contains alumina from the viewpoint of high thermal conductivity. All the inorganic fillers may be alumina, or alumina and other inorganic fillers may be used in combination.
Other inorganic fillers that can be used in combination with alumina include spherical silica, silica such as crystalline silica, zircon, magnesium oxide, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, boron nitride, beryllia and zirconia. Are listed. Furthermore, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide and zinc borate.
無機充填材としてアルミナとシリカとが併用される場合、無機充填材に占めるアルミナの含有率は、50質量%以上であることが好ましく、70質量%以上であることがより好ましく、85質量%以上であることがさらに好ましく、95質量%以上であることが特に好ましい。また、無機充填材に占めるアルミナの含有率は、99.6質量%以下であってもよい。 When alumina and other inorganic fillers are used together as the inorganic filler, silica is preferably used as the other inorganic filler from the viewpoint of fluidity.
When alumina and silica are used together as the inorganic filler, the content of alumina in the inorganic filler is preferably 50% by mass or more, more preferably 70% by mass or more, and 85% by mass or more. Is more preferable, and 95% by mass or more is particularly preferable. Further, the content rate of alumina in the inorganic filler may be 99.6% by mass or less.
また、無機充填材の含有率は、高熱伝導性の観点から、封止組成物の全体に対して78体積%以上であることが好ましく、80体積%以上であることがより好ましい。無機充填材の含有率は、封止組成物の成形性及び流動性の観点から、封止組成物の全体に対して95体積%以下であることが好ましく、90体積%以下であることがより好ましく、85体積%以下であることがさらに好ましい。無機充填材の含有率は、高熱伝導性と封止組成物の成形性及び流動性とを両立する観点から、78体積%~90体積%が好ましく、78体積%~85体積%がより好ましく、80体積%~85体積%がさらに好ましい。 From the viewpoint of hygroscopicity, reduction of linear expansion coefficient, strength improvement, and solder heat resistance, the content of the inorganic filler is preferably 60% by volume or more, and 70% by volume with respect to the entire sealing composition. More preferably, it is more preferably 75% by volume or more.
From the viewpoint of high thermal conductivity, the content of the inorganic filler is preferably 78% by volume or more, more preferably 80% by volume or more, based on the whole sealing composition. From the viewpoint of moldability and fluidity of the sealing composition, the content of the inorganic filler is preferably 95% by volume or less, and more preferably 90% by volume or less with respect to the entire sealing composition. It is preferably 85% by volume or less, and more preferably 85% by volume or less. The content of the inorganic filler is preferably 78% by volume to 90% by volume, more preferably 78% by volume to 85% by volume, from the viewpoint of achieving both high thermal conductivity and moldability and fluidity of the sealing composition. 80% by volume to 85% by volume is more preferable.
封止組成物の硬化物の熱伝導率は、無機充填材の平均粒子径が大きくなる程、高くなる傾向にある。
無機充填材の平均粒子径は、以下の方法により測定することができる。 The average particle size of the inorganic filler is preferably 4 μm to 100 μm, more preferably 7 μm to 70 μm, and further preferably 7 μm to 40 μm. In the present disclosure, the average particle diameter of the inorganic filler is the average particle diameter of alumina when alumina is used alone as the inorganic filler, and alumina and other inorganic fillers are used as the inorganic filler in combination. In this case, the average particle size of the whole inorganic filler is referred to.
The thermal conductivity of the cured product of the sealing composition tends to increase as the average particle size of the inorganic filler increases.
The average particle size of the inorganic filler can be measured by the following method.
封止組成物の流動性は、無機充填材の比表面積が小さくなる程、高くなる傾向にある。
本開示において、無機充填材の比表面積は、無機充填材として例えばアルミナが単独で用いられている場合にはアルミナの比表面積を、無機充填材としてアルミナとその他の無機充填材とが併用されている場合には無機充填材の混合物の比表面積をいう。
無機充填材の比表面積(BET比表面積)は、JIS Z 8830:2013に準じて窒素吸着能から測定することができる。評価装置としては、QUANTACHROME社:AUTOSORB-1(商品名)を用いることができる。BET比表面積の測定を行う際には、試料表面及び構造中に吸着している水分がガス吸着能に影響を及ぼすと考えられることから、まず、加熱による水分除去の前処理を行うことが好ましい。
前処理では、0.05gの測定試料を投入した測定用セルを、真空ポンプで10Pa以下に減圧した後、110℃で加熱し、3時間以上保持した後、減圧した状態を保ったまま常温(25℃)まで自然冷却する。この前処理を行った後、評価温度を77Kとし、評価圧力範囲を相対圧(飽和蒸気圧に対する平衡圧力)にて1未満として測定する。 The specific surface area of the inorganic filler, from the viewpoint of fluidity and moldability, is preferably from 0.7m 2 /g~4.0m 2 / g, with 0.9m 2 /g~3.0m 2 / g more preferably in, still more preferably 1.0m 2 /g~2.5m 2 / g.
The fluidity of the sealing composition tends to increase as the specific surface area of the inorganic filler decreases.
In the present disclosure, the specific surface area of the inorganic filler is the specific surface area of alumina when, for example, alumina is used alone as the inorganic filler, and alumina and other inorganic fillers are used in combination as the inorganic filler. If so, it refers to the specific surface area of the mixture of inorganic fillers.
The specific surface area (BET specific surface area) of the inorganic filler can be measured from the nitrogen adsorption capacity according to JIS Z 8830:2013. As an evaluation device, QUANTACHROME company: AUTOSORB-1 (trade name) can be used. When the BET specific surface area is measured, it is considered that the water adsorbed on the sample surface and structure influences the gas adsorption ability. Therefore, it is preferable to first perform a pretreatment for removing water by heating. ..
In the pretreatment, the measurement cell charged with 0.05 g of the measurement sample was depressurized to 10 Pa or less by a vacuum pump, heated at 110° C., held for 3 hours or more, and then kept at room temperature (vacuum) while maintaining the depressurized state. Cool naturally to 25°C). After performing this pretreatment, the evaluation temperature is set to 77K, and the evaluation pressure range is measured as relative pressure (equilibrium pressure to saturated vapor pressure) of less than 1.
(硬化促進剤)
封止組成物は、硬化促進剤をさらに含有してもよい。硬化促進剤の種類は特に制限されず、公知の硬化促進剤を使用することができる。
硬化促進剤としては、具体的には、1,8-ジアザ-ビシクロ[5.4.0]ウンデセン-7、1,5-ジアザ-ビシクロ[4.3.0]ノネン、5,6-ジブチルアミノ-1,8-ジアザ-ビシクロ[5.4.0]ウンデセン-7等のシクロアミジン化合物;シクロアミジン化合物に無水マレイン酸、1,4-ベンゾキノン、2,5-トルキノン、1,4-ナフトキノン、2,3-ジメチルベンゾキノン、2,6-ジメチルベンゾキノン、2,3-ジメトキシ-5-メチル-1,4-ベンゾキノン、2,3-ジメトキシ-1,4-ベンゾキノン、フェニル-1,4-ベンゾキノン等のキノン化合物、ジアゾフェニルメタン、フェノール樹脂などのπ結合をもつ化合物を付加してなる分子内分極を有する化合物;ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス(ジメチルアミノメチル)フェノール等の3級アミン化合物;3級アミン化合物の誘導体;2-メチルイミダゾール、2-フェニルイミダゾール、2-フェニル-4-メチルイミダゾール等のイミダゾール化合物;イミダゾール化合物の誘導体;トリブチルホスフィン、メチルジフェニルホスフィン、トリフェニルホスフィン、トリス(4-メチルフェニル)ホスフィン、ジフェニルホスフィン、フェニルホスフィン等の有機ホスフィン化合物;有機ホスフィン化合物に無水マレイン酸、上記キノン化合物、ジアゾフェニルメタン、フェノール樹脂等のπ結合をもつ化合物を付加してなる分子内分極を有するリン化合物;テトラフェニルホスホニウムテトラフェニルボレート、トリフェニルホスフィンテトラフェニルボレート、2-エチル-4-メチルイミダゾールテトラフェニルボレート、N-メチルモルホリンテトラフェニルボレート等のテトラフェニルボロン塩;テトラフェニルボロン塩の誘導体;トリフェニルホスホニウム-トリフェニルボラン、N-メチルモルホリンテトラフェニルホスホニウム-テトラフェニルボレート等のホスフィン化合物とテトラフェニルボロン塩との付加物;などが挙げられる。硬化促進剤は、1種類を単独で使用しても、2種類以上を併用してもよい。 -Other ingredients-
(Curing accelerator)
The sealing composition may further contain a curing accelerator. The type of curing accelerator is not particularly limited, and known curing accelerators can be used.
Specific examples of the curing accelerator include 1,8-diaza-bicyclo[5.4.0]undecene-7, 1,5-diaza-bicyclo[4.3.0]nonene and 5,6-dibutyl. Cycloamidine compounds such as amino-1,8-diaza-bicyclo[5.4.0]undecene-7; cycloamidine compounds with maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone Compounds having an intramolecular polarization formed by adding a compound having a π bond such as a quinone compound such as diazophenylmethane or phenol resin; benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, etc. Tertiary amine compounds; derivatives of tertiary amine compounds; imidazole compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole; derivatives of imidazole compounds; tributylphosphine, methyldiphenylphosphine, triphenyl Organic phosphine compounds such as phosphine, tris(4-methylphenyl)phosphine, diphenylphosphine and phenylphosphine; Maleic anhydride, the above quinone compound, diazophenylmethane, compounds having a π bond such as phenol resin are added to the organic phosphine compound. A phosphorus compound having an intramolecular polarization: tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, tetraphenylboron salt such as N-methylmorpholine tetraphenylborate; Derivatives of tetraphenylboron salts; adducts of phosphine compounds such as triphenylphosphonium-triphenylborane, N-methylmorpholine tetraphenylphosphonium-tetraphenylborate and tetraphenylboron salts; and the like. The curing accelerator may be used alone or in combination of two or more.
封止組成物は、イオントラップ剤をさらに含有してもよい。
本開示において使用可能なイオントラップ剤は、半導体装置の製造用途に用いられる封止材において、一般的に使用されているイオントラップ剤であれば特に制限されるものではない。イオントラップ剤としては、下記一般式(4)又は下記一般式(5)で表される化合物等が挙げられる。 (Ion trap agent)
The sealing composition may further contain an ion trap agent.
The ion trap agent that can be used in the present disclosure is not particularly limited as long as it is an ion trap agent that is generally used in the encapsulating material used for manufacturing semiconductor devices. Examples of the ion trapping agent include compounds represented by the following general formula (4) or the following general formula (5).
(一般式(4)中、aは0<a≦0.5であり、uは正数である。)
BiOb(OH)c(NO3)d (5)
(一般式(5)中、bは0.9≦b≦1.1、cは0.6≦c≦0.8、dは0.2≦d≦0.4である。) Mg 1-a Al a (OH) 2 (CO 3 ) a/2 ·uH 2 O (4)
(In the general formula (4), a is 0<a≦0.5, and u is a positive number.)
BiO b (OH) c (NO 3 ) d (5)
(In the general formula (5), b is 0.9≦b≦1.1, c is 0.6≦c≦0.8, and d is 0.2≦d≦0.4.)
イオントラップ剤は、1種類を単独で使用しても、2種類以上を併用してもよい。 Examples of ion trapping agents other than those mentioned above include hydrous oxides of elements selected from the group consisting of magnesium, aluminum, titanium, zirconium, antimony and the like.
The ion trap agents may be used alone or in combination of two or more.
封止組成物は、カップリング剤をさらに含有してもよい。カップリング剤の種類は、特に制限されず、公知のカップリング剤を使用することができる。カップリング剤としては、シランカップリング剤、チタンカップリング剤等が挙げられる。カップリング剤は、1種類を単独で使用しても、2種類以上を併用してもよい。 (Coupling agent)
The sealing composition may further contain a coupling agent. The type of coupling agent is not particularly limited, and known coupling agents can be used. Examples of the coupling agent include silane coupling agents and titanium coupling agents. As the coupling agent, one type may be used alone, or two or more types may be used in combination.
なお、封止組成物は、上記カップリング剤として、炭素数6以上の鎖状炭化水素基がケイ素原子に結合した構造を有するシラン化合物(以下「特定シラン化合物」ともいう)を含有してもよい。
上記鎖状炭化水素基は、分岐していてもよく、置換基を有していてもよい。なお、本開示において、鎖状炭化水素基の炭素数とは、分岐又は置換基の炭素を含まない炭素数を意味する。鎖状炭化水素基は、不飽和結合を含んでいても含んでいなくてもよく、不飽和結合を含まないことが好ましい。 -Specific silane compound-
The sealing composition may contain, as the coupling agent, a silane compound having a structure in which a chain hydrocarbon group having 6 or more carbon atoms is bonded to a silicon atom (hereinafter also referred to as “specific silane compound”). Good.
The chain hydrocarbon group may be branched or may have a substituent. In addition, in this indication, carbon number of a chain hydrocarbon group means carbon number which does not contain carbon of a branch or a substituent. The chain hydrocarbon group may or may not contain an unsaturated bond, and preferably does not contain an unsaturated bond.
また、カップリング剤の含有率は、無機充填材100質量部に対して、0.01質量部以上であってもよく、0.02質量部以上であってもよい。カップリング剤の含有量は無機充填材100質量部に対して5質量部以下であることが好ましく、2.5質量部以下であることがより好ましい。カップリング剤の含有量は、流動性とパッケージの成形性とを両立する観点から、無機充填材100質量部に対して0.05質量部~2.0質量部が好ましく、0.1質量部~1.5質量部がより好ましく、0.2質量部~1.0質量部がさらに好ましい。 When the sealing composition contains a coupling agent, the content of the coupling agent is preferably 3% by mass or less, more preferably 2% by mass or less, and more preferably 1% by mass, based on the entire sealing composition. % Or less is more preferable, and from the viewpoint of exerting the effect, it is preferably 0.1% by mass or more, more preferably 0.15% by mass or more, and further preferably 0.2% by mass or more.
The content of the coupling agent may be 0.01 parts by mass or more, and may be 0.02 parts by mass or more, based on 100 parts by mass of the inorganic filler. The content of the coupling agent is preferably 5 parts by mass or less, and more preferably 2.5 parts by mass or less with respect to 100 parts by mass of the inorganic filler. The content of the coupling agent is preferably 0.05 parts by mass to 2.0 parts by mass, and 0.1 parts by mass with respect to 100 parts by mass of the inorganic filler, from the viewpoint of achieving both fluidity and moldability of the package. It is more preferably to 1.5 parts by mass, still more preferably 0.2 parts to 1.0 parts by mass.
封止組成物は、離型剤をさらに含有してもよい。離型剤の種類は特に制限されず、公知の離型剤を使用することができる。具体的には、離型剤としては、高級脂肪酸、カルナバワックス、モンタンワックス、ポリエチレン系ワックス等が挙げられる。離型剤は、1種類を単独で使用しても、2種類以上を併用してもよい。
封止組成物が離型剤を含有する場合、離型剤の含有率は、エポキシ樹脂と硬化剤の合計量に対して、10質量%以下であることが好ましく、その効果を発揮させる観点からは、0.5質量%以上であることが好ましい。 (Release agent)
The sealing composition may further contain a release agent. The type of release agent is not particularly limited, and known release agents can be used. Specifically, examples of the release agent include higher fatty acids, carnauba wax, montan wax, polyethylene wax and the like. The release agent may be used alone or in combination of two or more.
When the sealing composition contains a release agent, the content of the release agent is preferably 10% by mass or less based on the total amount of the epoxy resin and the curing agent, and from the viewpoint of exerting the effect. Is preferably 0.5% by mass or more.
封止組成物は、着色剤(カーボンブラック等)を含有してもよい。また、封止組成物は、改質剤(シリコーン、シリコーンゴム等)を含有してもよい。着色剤及び改質剤は、それぞれ、1種類を単独で使用しても、2種類以上を併用してもよい。 (Colorants and modifiers)
The sealing composition may contain a colorant (carbon black or the like). Further, the sealing composition may contain a modifier (silicone, silicone rubber, etc.). Each of the colorant and the modifier may be used alone or in combination of two or more.
封止組成物が導電性粒子を含有する場合、導電性粒子の含有率は、エポキシ樹脂と硬化剤の合計量に対して3質量%以下であることが好ましい。 When conductive particles such as carbon black are used as the colorant, the conductive particles preferably have a content of particles having a particle diameter of 10 μm or more of 1% by mass or less.
When the sealing composition contains conductive particles, the content of the conductive particles is preferably 3% by mass or less based on the total amount of the epoxy resin and the curing agent.
封止組成物は、必要に応じて、さらにその他添加剤を含んでもよい。
その他添加剤としては、難燃剤、陰イオン交換体、可塑剤等が挙げられる。また、組成物には、必要に応じて当技術分野で周知の各種添加剤を添加してもよい。 (Other additives)
The sealing composition may further contain other additives, if necessary.
Other additives include flame retardants, anion exchangers, plasticizers and the like. Further, various additives well known in the art may be added to the composition, if necessary.
封止組成物の作製方法は特に制限されず、公知の方法により行うことができる。例えば、所定の配合量の原材料の混合物をミキサー等によって充分混合した後、熱ロール、押出機等によって混練し、冷却、粉砕等の処理を経ることによって封止組成物を作製することができる。封止組成物の状態は特に制限されず、粉末状、固体状、液体状等であってよい。 <Method for producing sealing composition>
The method for producing the sealing composition is not particularly limited, and a known method can be used. For example, a sealing composition can be prepared by thoroughly mixing a mixture of raw materials in a predetermined amount with a mixer or the like, kneading the mixture with a heat roll, an extruder, or the like, and then cooling, pulverizing, or the like. The state of the sealing composition is not particularly limited and may be powdery, solid, liquid or the like.
本開示の半導体装置は、半導体素子と、前記半導体素子を封止してなる本開示の封止組成物の硬化物と、を含む。 <Semiconductor device>
A semiconductor device of the present disclosure includes a semiconductor element and a cured product of the sealing composition of the present disclosure obtained by sealing the semiconductor element.
下記に示す成分を表1に示す配合割合(質量部)で予備混合(ドライブレンド)した後、二軸ニーダーで混練し、冷却粉砕して粉末状の封止組成物を製造した。
なお、表1に示す成分の詳細は以下の通りである。 <Examples 1 to 5 and Comparative Example 1>
The components shown below were premixed (dry blended) at the blending ratio (parts by mass) shown in Table 1, kneaded with a biaxial kneader, and cooled and pulverized to produce a powdery sealing composition.
The details of the components shown in Table 1 are as follows.
エポキシ樹脂A1-1:第1のエポキシ樹脂、三菱ケミカル株式会社、エポキシ基当量「440g/eq」、硬化後ガラス転移温度「-57℃」、分子内に2つのエポキシ基、ゴム弾性骨格、及び前記構造式(1)で表される2価の連結基を有するエポキシ樹脂
エポキシ樹脂A1-2:第1のエポキシ樹脂、三菱ケミカル株式会社、エポキシ基当量「489g/eq」、硬化後ガラス転移温度「31℃」、分子内に2つのエポキシ基、柔軟骨格、芳香環を含む骨格、及び前記構造式(1)で表される2価の連結基を有するエポキシ樹脂
エポキシ樹脂A1-3:第1のエポキシ樹脂、三菱ケミカル株式会社、エポキシ基当量「501g/eq」、硬化後ガラス転移温度「19℃」、分子内に2つのエポキシ基を有するエポキシ樹脂
エポキシ樹脂A2:第2のエポキシ樹脂、三菱ケミカル株式会社、品名「YX4000H」、エポキシ基当量「192g/eq」、硬化後ガラス転移温度「150℃」、軟化点「107℃」、ビフェニル型エポキシ樹脂 (A) Epoxy resin Epoxy resin A1-1: First epoxy resin, Mitsubishi Chemical Corporation, epoxy group equivalent “440 g/eq”, glass transition temperature after curing “−57° C.”, two epoxy groups in the molecule, Epoxy Resin Having Rubber Elastic Skeleton and Divalent Linking Group Represented by Structural Formula (1) Epoxy Resin A1-2: First Epoxy Resin, Mitsubishi Chemical Co., Epoxy Group Equivalent “489 g/eq”, Epoxy resin having a glass transition temperature after curing “31° C.”, two epoxy groups in the molecule, a flexible skeleton, a skeleton containing an aromatic ring, and a divalent linking group represented by the structural formula (1). Epoxy resin A1 -3: First epoxy resin, Mitsubishi Chemical Corporation, epoxy group equivalent "501 g/eq", glass transition temperature after curing "19°C", epoxy resin having two epoxy groups in the molecule Epoxy resin A2: second Epoxy resin, Mitsubishi Chemical Corporation, product name "YX4000H", epoxy group equivalent "192 g/eq", glass transition temperature after curing "150°C", softening point "107°C", biphenyl type epoxy resin
なお、測定用硬化物の作製において、多官能フェノール樹脂硬化剤は、測定対象であるエポキシ樹脂のエポキシ基の数(すなわち総数)とフェノール樹脂の水酸基の数(すなわち総数)とが同程度になるように添加し、リン系硬化促進剤は、エポキシ樹脂と多官能フェノール樹脂硬化剤との合計100質量部に対しリン系硬化促進剤の含有量が3質量部~6質量部になるように添加した。
また、ガラス転移温度の測定は、得られた測定用硬化物を切断して、10mgをはかり取り、示差走査熱量計(ティー・エイ・インスツルメント・ジャパン社、品名「DSC Q100」)を用いて昇温速度10℃/分の条件にて測定を行い、得られたチャートの変曲点前後における接線の交点をガラス転移温度とした。 Here, the value of the glass transition temperature after curing in the epoxy resin is the epoxy resin to be measured, "HE910-09" (Air Water Co., Ltd.) which is a polyfunctional phenol resin curing agent, and phosphorus-based curing acceleration. It is the value of the glass transition temperature in the cured product for measurement, which was obtained by heating the mixture obtained by mixing the agent "addition product of tributylphosphine and benzoquinone" at 175°C for 6 hours.
In the preparation of the cured product for measurement, the number of epoxy groups (that is, the total number) of the epoxy resin that is the measurement target of the polyfunctional phenol resin curing agent and the number of the hydroxyl groups (that is, the total number) of the phenol resin are approximately the same. The phosphorus-based curing accelerator is added so that the content of the phosphorus-based curing accelerator is 3 to 6 parts by mass with respect to 100 parts by mass of the epoxy resin and the polyfunctional phenol resin curing agent in total. did.
Further, the glass transition temperature is measured by cutting the obtained cured product for measurement, weighing 10 mg, and using a differential scanning calorimeter (TA Instruments Japan Co., product name "DSC Q100"). The temperature was raised at a rate of 10° C./min, and the glass transition temperature was defined as the intersection of tangents before and after the inflection point of the obtained chart.
硬化剤B1:トリフェニルメタン型フェノール樹脂、エア・ウォーター株式会社、品名「HE910-09」、水酸基当量「92~104g/eq」、軟化点「75~85℃」 (B) Hardener Hardener B1: Triphenylmethane type phenol resin, Air Water Co., Ltd., product name "HE910-09", hydroxyl group equivalent "92 to 104 g/eq", softening point "75 to 85°C"
硬化促進剤C1:リン系硬化促進剤(トリブチルホスフィンとベンゾキノンの付加物)
(D)カップリング剤
カップリング剤D1:8-メタクリロキシオクチルトリメトキシシラン、信越化学工業株式会社、品名「KBM-5803」
(E)離型剤
離型剤E1:モンタンワックス、クラリアント社、品名「HW-E」
(F)着色剤
顔料F1:カーボンブラック、三菱ケミカル株式会社、商品名「MA600」
(G)添加剤
添加剤G1:トリフェニルホスフィンオキシド
(H)改質剤
改質剤H1:シリコーン、東レ・ダウコーニング株式会社、品名「BY16-876」 (C) Curing accelerator Curing accelerator C1: Phosphorus curing accelerator (addition product of tributylphosphine and benzoquinone)
(D) Coupling agent Coupling agent D1:8-methacryloxyoctyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd., product name "KBM-5803"
(E) Release Agent Release Agent E1: Montan Wax, Clariant Company, Product Name “HW-E”
(F) Colorant Pigment F1: Carbon black, Mitsubishi Chemical Corporation, trade name "MA600"
(G) Additive Additive G1: Triphenylphosphine oxide (H) Modifier Modifier H1: Silicone, Toray Dow Corning Co., Ltd., product name "BY16-876"
フィラI1:シリカ粒子、球状、比表面積「190m2/g~230m2/g」
フィラI2:アルミナ粒子、球状、平均粒子径「0.7μm」
フィラI3:アルミナ粒子、球状、平均粒子径「10μm」 (I) Inorganic filler filler I1: silica particles, spherical, specific surface area "190 m 2 /g to 230 m 2 /g"
Filler I2: Alumina particles, spherical, average particle size “0.7 μm”
Filler I3: Alumina particles, spherical, average particle size “10 μm”
実施例及び比較例で作製した封止組成物の特性を、次の特性試験により評価した。評価結果を下記表1に示す。 -Evaluation-
The characteristics of the sealing compositions produced in the examples and comparative examples were evaluated by the following characteristic tests. The evaluation results are shown in Table 1 below.
上記で得られた封止組成物を用いて、トランスファ成形機により、金型温度175℃、成形圧力6.9MPa、硬化時間90秒で成形し、直径50mm×厚み3mmの円板形状である試験片を作製した。成形後直ちにショアD型硬度計(高分子計器株式会社、アスカー、タイプDデュロメータ)を用いて硬化物の熱時硬度を測定した。 (Hardness when heated)
Using the sealing composition obtained above, a transfer molding machine was used to perform molding at a mold temperature of 175° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds, and a disk-shaped test with a diameter of 50 mm and a thickness of 3 mm was performed. Pieces were made. Immediately after molding, the hot hardness of the cured product was measured using a Shore D hardness meter (Kobunshi Keiki Co., Ltd., Asker, type D durometer).
上記で得られた封止組成物を用いて、トランスファ成形機により、金型温度175℃、成形圧力6.9MPa、硬化時間90秒の条件で、127mm×12.7mm×4mmの形状の試験片を作製した。その後、後硬化を175℃で6時間の条件で行った。評価装置として、テンシロン(A&D社)を用い、JIS-K-7171(2016)に準拠した3点支持型曲げ試験を、25℃及び260℃においてそれぞれ行い、試験片の曲げ弾性率を求めた。
なお、曲げ弾性率Eは下記式にて定義され、25℃における測定によって得られた曲げ弾性率を「室温弾性率」、260℃における測定によって得られた曲げ弾性率を「高温弾性率」とする。
下記式中、Eは曲げ弾性率(MPa)、Pはロードセルの値(N)、yは変位量(mm)、lはスパン=64mm、wは試験片幅=12.7mm、hは試験片厚さ=4mmである。 (Room temperature elastic modulus and high temperature elastic modulus)
Using the sealing composition obtained above, a test piece having a shape of 127 mm×12.7 mm×4 mm was formed by a transfer molding machine under the conditions of a mold temperature of 175° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Was produced. Then, post-curing was performed at 175° C. for 6 hours. Using Tensilon (A&D Co.) as an evaluation device, a three-point support type bending test based on JIS-K-7171 (2016) was carried out at 25° C. and 260° C., and the bending elastic modulus of the test piece was obtained.
The flexural modulus E is defined by the following formula, and the flexural modulus obtained by measurement at 25° C. is referred to as “room temperature modulus” and the flexural modulus obtained at 260° C. is referred to as “high temperature modulus”. To do.
In the following formula, E is a bending elastic modulus (MPa), P is a load cell value (N), y is a displacement amount (mm), l is a span=64 mm, w is a test piece width=12.7 mm, and h is a test piece. Thickness=4 mm.
上記で得られた封止組成物を用いてトランスファ成形機により、金型温度175℃~180℃、成形圧力7MPa、硬化時間300秒の条件で熱伝導率評価用の試験片を作製した。次いで、成形した試験片について、厚さ方向の熱拡散率を測定した。熱拡散率の測定はレーザーフラッシュ法(装置:LFA467 nanoflash、NETZSCH社)にて行った。パルス光照射は、パルス幅0.31(ms)、印加電圧247Vの条件で行った。測定は雰囲気温度25℃±1℃で行った。また上記試験片の密度は電子比重計(AUX220、株式会社島津製作所)を用いて測定した。比熱は、各材料の比熱の文献値と配合比率より算出した封止組成物の理論比熱を用いた。
次いで、式(6)を用いて比熱及び密度を熱拡散率に乗算することによって,熱伝導率の値を得た。
λ=α×Cp×ρ・・・式(6)
(式(6)中、λは熱伝導率(W/(m・K))、αは熱拡散率(m2/s)、Cpは比熱(J/(kg・K))、ρは密度(kg/m3)をそれぞれ示す。)
結果を表1に示す。 (Thermal conductivity)
Using the above-obtained sealing composition, a transfer molding machine was used to prepare a test piece for thermal conductivity evaluation under the conditions of a mold temperature of 175° C. to 180° C., a molding pressure of 7 MPa, and a curing time of 300 seconds. Next, the thermal diffusivity of the molded test piece in the thickness direction was measured. The thermal diffusivity was measured by the laser flash method (apparatus: LFA467 nanoflash, NETZSCH). The pulsed light irradiation was performed under the conditions of a pulse width of 0.31 (ms) and an applied voltage of 247V. The measurement was performed at an ambient temperature of 25°C ± 1°C. The density of the test piece was measured using an electronic hydrometer (AUX220, Shimadzu Corporation). As the specific heat, the theoretical specific heat of the sealing composition calculated from the literature value of the specific heat of each material and the compounding ratio was used.
The thermal diffusivity was then obtained by multiplying the thermal diffusivity by the specific heat and density using equation (6).
λ=α×Cp×ρ... Formula (6)
(In Formula (6), λ is thermal conductivity (W/(m·K)), α is thermal diffusivity (m 2 /s), Cp is specific heat (J/(kg·K)), and ρ is density. (Indicates kg/m 3 respectively.)
The results are shown in Table 1.
表1の評価結果から明らかなように、第1のエポキシ樹脂を含有する実施例1~5の封止組成物は、第1のエポキシ樹脂を含有しない比較例1の封止組成物に比較して、室温弾性率及び高温弾性率の低い硬化物が得られている。また、実施例1~5の封止組成物の硬化物の熱伝導率は、比較例1の封止組成物の硬化物の熱伝導率と同等又はそれよりも高い値となっている。また、実施例1~5の封止組成物は、比較例1の封止組成物に比較して、室温弾性率及び高温弾性率を低減しつつ、熱時硬度が維持されている。 In Table 1, "average particle size of filler" means the volume-based average particle size of the whole inorganic filler used, and "filler content" is the content of the whole inorganic filler used with respect to the entire sealing composition. Means
As is clear from the evaluation results of Table 1, the sealing compositions of Examples 1 to 5 containing the first epoxy resin were compared with the sealing composition of Comparative Example 1 containing no first epoxy resin. As a result, a cured product having a low room temperature elastic modulus and a high temperature elastic modulus is obtained. Further, the thermal conductivity of the cured products of the sealing compositions of Examples 1 to 5 is equal to or higher than the thermal conductivity of the cured products of the sealing composition of Comparative Example 1. Further, the sealing compositions of Examples 1 to 5 have lower room temperature elastic modulus and high temperature elastic modulus as compared with the sealing composition of Comparative Example 1, while maintaining the hot hardness.
本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に取り込まれる。 The disclosure of Japanese Patent Application No. 2018-239253 filed on Dec. 21, 2018 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards mentioned herein are to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference, Incorporated herein.
Claims (8)
- エポキシ基当量が300g/eq以上であり、多官能フェノール樹脂硬化剤及びリン系硬化促進剤を用いて硬化させたときのガラス転移温度が40℃以下である第1のエポキシ樹脂と、
硬化剤と、
無機充填材と、
を含有する封止組成物。 A first epoxy resin having an epoxy group equivalent of 300 g/eq or more and having a glass transition temperature of 40° C. or less when cured using a polyfunctional phenol resin curing agent and a phosphorus-based curing accelerator;
A curing agent,
An inorganic filler,
A sealing composition containing: - 前記無機充填材の含有率は、封止組成物全体に対して78体積%以上である請求項1に記載の封止組成物。 The encapsulating composition according to claim 1, wherein the content of the inorganic filler is 78% by volume or more based on the entire encapsulating composition.
- 融点又は軟化点が50℃以上である第2のエポキシ樹脂をさらに含有する請求項1又は請求項2に記載の封止組成物。 The encapsulating composition according to claim 1 or 2, further comprising a second epoxy resin having a melting point or a softening point of 50°C or higher.
- 前記第1のエポキシ樹脂の含有率は、封止組成物に含有されるエポキシ樹脂の総量に対して20質量%以上である請求項1~請求項3のいずれか1項に記載の封止組成物。 The encapsulating composition according to any one of claims 1 to 3, wherein the content of the first epoxy resin is 20% by mass or more based on the total amount of the epoxy resins contained in the encapsulating composition. Stuff.
- 前記第1のエポキシ樹脂の含有率は、封止組成物に含有されるエポキシ樹脂の総量に対して50質量%以下である請求項1~請求項4のいずれか1項に記載の封止組成物。 The encapsulating composition according to any one of claims 1 to 4, wherein the content of the first epoxy resin is 50% by mass or less based on the total amount of the epoxy resins contained in the encapsulating composition. Stuff.
- 前記第1のエポキシ樹脂は、分子内に2つのエポキシ基を有する請求項1~請求項5のいずれか1項に記載の封止組成物。 The encapsulating composition according to any one of claims 1 to 5, wherein the first epoxy resin has two epoxy groups in the molecule.
- 前記第1のエポキシ樹脂は、分子内に下記構造式(1)で表される2価の連結基を有する請求項1~請求項6のいずれか1項に記載の封止組成物。
(上記構造式(1)中、*は結合部を示す。) The sealing composition according to any one of claims 1 to 6, wherein the first epoxy resin has a divalent linking group represented by the following structural formula (1) in the molecule.
(In the structural formula (1), * represents a bonding portion.) - 半導体素子と、前記半導体素子を封止してなる請求項1~請求項7のいずれか1項に記載の封止組成物の硬化物と、を含む半導体装置。 A semiconductor device comprising a semiconductor element and a cured product of the encapsulating composition according to any one of claims 1 to 7 obtained by encapsulating the semiconductor element.
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JP2013071950A (en) * | 2011-09-27 | 2013-04-22 | Nippon Kayaku Co Ltd | Curable resin composition and cured product thereof |
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JP2019001841A (en) * | 2017-06-12 | 2019-01-10 | 信越化学工業株式会社 | Epoxy resin composition and semiconductor device having cured product of composition |
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JP2007194405A (en) * | 2006-01-19 | 2007-08-02 | Nitto Shinko Kk | Epoxy resin composition for heat conduction |
WO2012091000A1 (en) * | 2010-12-27 | 2012-07-05 | 東レ・ダウコーニング株式会社 | Curable epoxy resin composition |
JP2013071950A (en) * | 2011-09-27 | 2013-04-22 | Nippon Kayaku Co Ltd | Curable resin composition and cured product thereof |
JP2016219619A (en) * | 2015-05-21 | 2016-12-22 | 日東電工株式会社 | Adhesive sheet, dicing tape-integrated adhesive sheet, film, manufacturing method of semiconductor device, and semiconductor device |
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US11282194B2 (en) | 2015-12-23 | 2022-03-22 | Gauss Surgical, Inc. | Method for estimating blood component quantities in surgical textiles |
US11790637B2 (en) | 2015-12-23 | 2023-10-17 | Gauss Surgical Inc. | Method for estimating blood component quantities in surgical textiles |
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