WO2019208604A1 - 樹脂組成物、積層体、樹脂組成物層付き半導体ウェハ、樹脂組成物層付き半導体搭載用基板、及び半導体装置 - Google Patents
樹脂組成物、積層体、樹脂組成物層付き半導体ウェハ、樹脂組成物層付き半導体搭載用基板、及び半導体装置 Download PDFInfo
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- WO2019208604A1 WO2019208604A1 PCT/JP2019/017329 JP2019017329W WO2019208604A1 WO 2019208604 A1 WO2019208604 A1 WO 2019208604A1 JP 2019017329 W JP2019017329 W JP 2019017329W WO 2019208604 A1 WO2019208604 A1 WO 2019208604A1
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- QGYKUYUCDSXCRH-UHFFFAOYSA-N C(c(cccc1)c1OC1)N1c(cc1)ccc1Oc(cc1)ccc1N1COc2ccccc2C1 Chemical compound C(c(cccc1)c1OC1)N1c(cc1)ccc1Oc(cc1)ccc1N1COc2ccccc2C1 QGYKUYUCDSXCRH-UHFFFAOYSA-N 0.000 description 2
- NAEJIUKUFIHRKT-UHFFFAOYSA-N CC(C)(c(cc1)cc(C2)c1OCN2c1ccccc1)c(cc1)cc(C2)c1OCN2c1ccccc1 Chemical compound CC(C)(c(cc1)cc(C2)c1OCN2c1ccccc1)c(cc1)cc(C2)c1OCN2c1ccccc1 NAEJIUKUFIHRKT-UHFFFAOYSA-N 0.000 description 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/106—Esters of polycondensation macromers
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- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- 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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- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
- C08K5/357—Six-membered rings
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- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
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- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
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- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/295—Organic, e.g. plastic containing a filler
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- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0233—Polyamines derived from (poly)oxazolines, (poly)oxazines or having pendant acyl groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
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- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
- H01L2224/29001—Core members of the layer connector
- H01L2224/29099—Material
- H01L2224/2919—Material with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
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- H01L2224/29099—Material
- H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
- H01L2224/29199—Material of the matrix
- H01L2224/2929—Material of the matrix with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
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- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/06—Polymers
- H01L2924/0635—Acrylic polymer
Definitions
- the present invention relates to a resin composition, a laminate using the resin composition, a semiconductor wafer with a resin composition layer, a semiconductor mounting substrate with a resin composition layer, and a semiconductor device. Specifically, the present invention relates to a resin composition useful as an underfill material.
- semiconductor chips (hereinafter sometimes abbreviated as “chips”) are mounted on semiconductor mounting substrates (hereinafter sometimes abbreviated as “substrates”) as semiconductor devices become smaller and have higher performance.
- flip chip mounting has attracted attention.
- flip-chip mounting a method of bonding a chip and a substrate, filling an underfill material in a gap between the chip and the substrate, and curing is generally used.
- the pitches of electrodes arranged on a chip and the gaps between electrodes have progressed.
- the occurrence of filling defects such as filling is a problem.
- the construction method which joins a chip
- the underfill material is a member that is in direct contact with the chip and the substrate, one of the important characteristics required for the underfill material is a chip that can withstand long-term use in an environment where the semiconductor device is used. And adhesion to the substrate (hereinafter sometimes abbreviated as “chip adhesion”).
- Patent Document 1 describes a pre-applied underfill material using a radical polymerizable monomer as a main resin. This Patent Document 1 describes the blending of a silane coupling agent for the purpose of improving the adhesiveness with a chip.
- Patent Document 2 describes an underfill material containing an epoxy resin, an imidazole compound, and a maleimide compound.
- Patent Document 3 describes a pre-applied underfill material using an epoxy compound and a carboxyl group-containing flux component, and mentions adhesion.
- Patent Document 4 describes a resin composition containing a maleimide compound, an epoxy resin, and an epoxy resin curing agent as essential components, and describes that high adhesiveness was obtained in the resin composition after heat curing.
- Patent Document 5 discloses a thermosetting resin composition used for forming an insulating layer in a printed wiring board, which includes a maleimide compound having a specific structure, a benzoxazine compound, and an inorganic filler (C). There is description about the resin composition for printed wiring boards containing this.
- Patent Document 6 describes an adhesive for electronic parts containing an aliphatic epoxy compound and a benzoxazine compound as a curing main agent and a phenol-based curing agent.
- Patent Document 7 contains a thermosetting compound, a polymer having a functional group capable of reacting with the thermosetting compound, and a thermosetting agent, and has a melt viscosity at a bonding temperature of 10 Pa ⁇ s to 15000 Pa ⁇ s.
- an adhesive composition in which the gel time at the bonding temperature is 10 seconds or longer and the gel time at 240 ° C. is 1 second or longer and 10 seconds or shorter.
- Patent Document 8 describes a method for manufacturing a semiconductor device using a sheet-like thermosetting resin composition.
- the object when joining the chip and the substrate via a metal that is easily oxidized, for example, solder or copper, the object is to remove the metal oxide film that hinders the joining from the joint and obtain a good metal joint.
- a flux component derived from carboxylic acid or the like is added to the pre-applied underfill material.
- radically polymerizable monomers cure quickly, and the main resin that has been polymerized before the silane coupling agent contained in the adhesive site has sufficient mobility to form a sufficient number of bonds with the silanol groups on the chip surface. Will be rate-limited.
- the pre-applied underfill material described in Patent Document 1 cannot provide sufficient adhesion to a substrate such as a chip and a printed wiring board.
- the radically polymerizable monomer is cured quickly, it cures before the resin composition is buried in the irregularities present on the chip surface. Therefore, the pre-applied underfill material described in Patent Document 1 is useful for improving adhesiveness. There is a problem that the anchor effect is not sufficiently obtained.
- Patent Document 2 has a problem that its application range is narrow because it only acts on the polyimide passivation film.
- Patent Document 5 there is no description about the flux activity, and there is no description about the flux component. Therefore, the resin composition described in Patent Document 5 has a problem that good metal bonding cannot be obtained.
- Patent Document 6 although the adhesiveness of the epoxy compound is high, the epoxy compound also reacts with the flux component, and there is a problem that sufficient flux activity cannot be obtained in order to obtain good metal bonding.
- the adhesive composition of Patent Document 7 includes a thermosetting agent having flux properties, but in the examples, an epoxy compound and a polymer containing an epoxy group are used, and both react at a temperature lower than the bonding temperature. Therefore, it is difficult to obtain sufficient flux activity.
- the present invention has been made in view of such problems, and has a resin composition suitable for an underfill material, a laminate, and a resin having excellent adhesion to a chip and a substrate and excellent flux activity.
- the object is to provide a semiconductor wafer with a composition layer, a semiconductor mounting substrate with a resin composition layer, and a semiconductor device.
- a resin composition, a laminate, and a resin composition suitable for an underfill material having excellent adhesion to a chip and excellent adhesion to a substrate such as a printed wiring board and having excellent flux activity
- the object is to provide a semiconductor wafer with a physical layer, a semiconductor mounting substrate with a resin composition layer, and a semiconductor device.
- the present inventors have determined from a benzoxazine compound (A), an organic compound (B) having a flux function, a phenol resin, and a thermosetting resin having radical polymerizability.
- the present inventors have found that a resin composition suitable for a material can solve the above problems, and have reached the present invention.
- the present invention includes the following contents.
- thermosetting resin having radical polymerizability is a resin or compound having at least one functional group selected from the group consisting of an alkenyl group, a maleimide group, and a (meth) acryloyl group, and the benzoxazine A resin composition having a mass ratio ((A) / (C)) of the compound (A) and the thermosetting component (C) of 20/80 to 90/10.
- the benzoxazine compound (A) contains at least one selected from the group consisting of compounds represented by the following formula (1), the following formula (2), the following formula (3), and the following formula (4).
- each R 1 independently represents an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group
- each R 2 independently represents a hydrogen atom, an aryl group, or an aralkyl group.
- each R 3 independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group
- each R 4 independently represents an aryl group or an aralkyl group.
- each R 5 independently represents an alkyl group, a cycloalkyl group, or a phenyl group which may have a substituent).
- each R 6 independently represents an alkyl group, a cycloalkyl group, or an optionally substituted phenyl group).
- each R a independently represents an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group
- each R b independently represents a hydrogen atom, an aryl group, A group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group.
- each R 7 independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group
- each R 8 independently represents a hydrogen atom or an aryl group.
- X 1 represents an alkylene group, a group represented by the following formula (7), a group represented by the formula “—SO 2 —”, “— A group represented by “CO—”, an oxygen atom, or a single bond.
- each R 9 independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group or a cycloalkyl group
- each R 10 independently represents a hydrogen atom or an aryl group.
- X 2 represents an alkylene group, a group represented by the following formula (7), a group represented by the formula “—SO 2 —”, “— A group represented by “CO—”, an oxygen atom, or a single bond.
- Y is a hydrocarbon group having 6 to 30 carbon atoms having an alkylene group or an aromatic ring, n 3 represents an integer of 0 to 5.
- the benzoxazine compound (A) is a compound represented by the following formula (5-1), a compound represented by the following formula (5-2), a compound represented by the following formula (5-3), Containing at least one selected from the group consisting of a compound represented by (6-1), a compound represented by the following formula (6-2), and a compound represented by the following formula (6-3) , [1] to [4].
- R each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms).
- the organic compound (B) having the flux function is abietic acid, neoabietic acid, dehydroabietic acid, pimaric acid, isopimaric acid, parastrinic acid, diphenolic acid, dihydroabietic acid, tetrahydroabietic acid, rosin acid modified resin, N , N′-bis (salicylidene) -1,2-propanediamine, N, N′-bis (salicylidene) -1,3-propanediamine, and at least one selected from the group consisting of phenolphthalene , [1] to [7].
- thermosetting component (C) is a maleimide compound.
- thermosetting component (C) is 2,2-bis ⁇ 4- (4-maleimidophenoxy) phenyl ⁇ propane, a maleimide compound represented by the following formula (8), a maleimide represented by the following formula (9) A compound, a maleimide compound represented by the following formula (10), a maleimide compound represented by the following formula (11), a compound represented by the following formula (12), and a compound represented by the following formula (13).
- the resin composition according to any one of [1] to [9], containing at least one selected from the group.
- each R 11 independently represents a hydrogen atom or a methyl group, and n 4 represents an integer of 1 or more and 10 or less).
- n 5 represents an integer of 1 or more and 30 or less).
- each R 12 independently represents a hydrogen atom, a methyl group, or an ethyl group
- each R 13 independently represents a hydrogen atom or a methyl group
- each R 14 independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n 6 represents an integer of 1 to 10.
- R 15 and R 17 each independently represents a hydrocarbon group in which 8 or more atoms are linearly linked, and R 16 each independently represents a substituted or unsubstituted ring.
- a cyclic hydrocarbon group which may contain a hetero atom having 4 to 10 atoms, and n 7 represents a number of 1 to 10.
- each R 18 independently represents an alkylene group
- each R 19 independently represents an alkylene group, a group represented by the following formula (7), a formula “—SO 2 —” And a group represented by “—CO—”, a group represented by the following formula (14), an oxygen atom, or a single bond
- n 8 represents a number of 1 or more and 10 or less.
- Y is a hydrocarbon group having 6 to 30 carbon atoms having an alkylene group or an aromatic ring, n 3 represents an integer of 0 to 5.
- the content of the organic compound (B) having the flux function is 1 part by mass or more with respect to a total of 100 parts by mass of the benzoxazine compound (A) and the thermosetting component (C).
- the radical polymerization initiator (D) is dicumyl peroxide, di (2-tert-butylperoxyisopropyl) benzene, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethyl-2,
- the content of the radical polymerization initiator (D) in the resin composition is 0.05 parts by mass or more with respect to 100 parts by mass in total of the benzoxazine compound (A) and the thermosetting component (C).
- the inorganic filler (E) contains at least one selected from the group consisting of silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, magnesium oxide, and magnesium hydroxide, [18] or [19] The resin composition according to [19].
- Content of the said inorganic filler (E) in the said resin composition is 500 mass parts or less with respect to a total of 100 mass parts of the said benzoxazine compound (A) and the said thermosetting component (C).
- the flexibility imparting component (F) contains a thermoplastic polymer compound, and the polymer compound has a mass average molecular weight of 1,000 or more and 1,000,000 or less. Resin composition.
- thermosetting component (C) in the resin composition is 100 parts by mass of the benzoxazine compound (A), the thermosetting component (C), and the flexibility-imparting component (F).
- [27] Content of the organic compound (B) having the flux function in the resin composition is a total of the benzoxazine compound (A), the thermosetting component (C), and the flexibility imparting component (F).
- [28] Content of the said inorganic filler (E) in the said resin composition is 100 mass parts in total of the said benzoxazine compound (A), the said thermosetting component (C), and a flexibility provision component (F).
- a laminate comprising a supporting substrate and a layer containing the resin composition according to any one of [1] to [29] laminated on the supporting substrate.
- a semiconductor wafer with a resin composition layer comprising: a semiconductor wafer; and the laminate according to [30] laminated on the semiconductor wafer, wherein the layer containing the resin composition is laminated on the semiconductor wafer.
- a resin composition comprising: a semiconductor mounting substrate; and the laminate according to [30] stacked on the semiconductor mounting substrate, wherein the layer containing the resin composition is stacked on the semiconductor mounting substrate.
- a semiconductor device comprising the semiconductor wafer with a resin composition layer according to [31] and / or the semiconductor mounting substrate with a resin composition layer according to [32].
- tip and a printed wiring board, and the outstanding flux activity, a laminated body, with a resin composition layer A semiconductor wafer, a semiconductor mounting substrate with a resin composition layer, and a semiconductor device can be obtained.
- the present embodiment a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described.
- the following embodiment is an exemplification for explaining the present invention, and the present invention is not limited to the present embodiment.
- the resin composition is selected from a benzoxazine compound (A), an organic compound (B) having a flux function, a phenol resin, and a thermosetting resin having radical polymerizability. And at least one selected from the group consisting of an alkenyl group, a maleimide group, and a (meth) acryloyl group.
- a resin or compound having the above functional group, wherein the mass ratio ((A) / (C)) of the benzoxazine compound (A) to the thermosetting component (C) is 20/80 to 90/10. is there.
- the resin composition is preferably used for an underfill material, and more preferably used for a pre-applied underfill material, from the viewpoint of more effectively and reliably achieving the effects of the present invention.
- Another aspect of this embodiment is a resin composition containing a radical polymerization initiator (D) in addition to the resin composition components.
- Another aspect of the present embodiment is a resin composition containing an inorganic filler (E) in addition to the resin composition components.
- Another aspect of the present embodiment is a resin composition containing a flexibility imparting component (F) in addition to the resin composition component.
- a laminate obtained using the resin composition according to the present embodiment, a resin composition layer produced using the laminate.
- a semiconductor wafer with a semiconductor substrate a semiconductor mounting substrate with a resin composition layer produced using a laminate, and a semiconductor device produced using the resin composition of the present invention.
- (meth) acryloyl means both “acryloyl” and the corresponding “methacryloyl”
- (meth) acryl means “acryl” and the corresponding “methacryl”.
- (Meth) acrylate” means both “acrylate” and the corresponding “methacrylate”
- (meth) allyl” means both “allyl” and the corresponding “methallyl”. means.
- the resin composition of the present embodiment is preferably a resin composition used as an underfill material used for flip chip mounting of a chip, which is a benzoxazine compound (A) and an organic compound having a flux function (B And at least one thermosetting component (C) selected from phenolic resins and thermosetting resins having radical polymerizability.
- thermosetting resin having radical polymerizability is a thermosetting resin having a functional group that is polymerized by radicals, and at least one selected from the group consisting of alkenyl groups, maleimide groups, and (meth) acryloyl groups. It is a resin or compound having a functional group.
- the mass ratio ((A) / (C)) between the benzoxazine compound (A) and the thermosetting component (C) is excellent with respect to substrates such as chips and printed wiring boards. From the viewpoint of obtaining a resin composition suitable for an underfill material having adhesiveness and excellent flux activity, it is 20/80 to 90/10, preferably 25/75 to 85/15, preferably 25/75 to 80/20 is more preferable, and 25/75 to 75/25 is still more preferable.
- the content ratio of the benzoxazine compound (A) is smaller than the lower limit of the above range, sufficient adhesion with the substrate cannot be obtained.
- it is larger than the upper limit the reaction between the benzoxazine compound and the flux component becomes obvious, and the flux activity cannot be sufficiently obtained.
- the resin composition of the present embodiment may contain at least one of a radical polymerization initiator (D), an inorganic filler (E), and a flexibility imparting component (F).
- D radical polymerization initiator
- E inorganic filler
- F flexibility imparting component
- the reason why a resin composition suitable for use in an underfill material having excellent adhesion to a substrate such as a chip and a printed wiring board and having excellent flux activity is not clear.
- the benzoxazine compound generates a phenolic hydroxyl group and a tertiary amino group as polar groups that contribute to adhesion after ring-opening polymerization.
- strong adhesiveness can be obtained because a polar group present on the surface of the adherend and a chemical interaction such as hydrogen bonding are effectively expressed.
- the benzoxazine compound is less likely to react with the flux component during storage or heat treatment than the epoxy compound, and the flux is not deactivated.
- the benzoxazine compound (A) in the resin composition of the present embodiment is not particularly limited as long as it has an oxazine ring as a basic skeleton.
- the benzoxazine compound (A) includes a compound having a polycyclic oxazine skeleton such as a naphthoxazine compound.
- the benzoxazine compound (A) does not generate a volatile by-product upon heating, and the benzoxazine ring is suitably cured by ring-opening polymerization.
- the cured product is excellent in heat resistance, water resistance, and flame retardancy.
- the phenolic hydroxyl group and tertiary amino group which are polar groups are produced
- substrate adhesiveness can be anticipated.
- the benzoxazine compound (A) may be used in combination with a thermosetting component (C) other than the following benzoxazine compound (A) as long as the adhesiveness of the benzoxazine compound (A) is not impaired.
- a thermosetting component (C) a compound which shows reactivity with the benzoxazine compound (A) and does not show reactivity with the flux component is preferable.
- the molecular weight of the benzoxazine compound (A) is not particularly limited as long as the effects of the present embodiment are exhibited. Is preferably 400 or more. On the other hand, from the viewpoint of obtaining more sufficient flux activity, the molecular weight of the benzoxazine compound (A) is preferably 500 or less.
- the benzoxazine compound (A) contains at least one selected from the group consisting of compounds represented by the following formula (1), the following formula (2), the following formula (3), and the following formula (4). It is preferable to do.
- the benzoxazine compound (A) may contain an oligomer produced by polymerization of monomers.
- each R 1 independently represents an aryl group, an aralkyl group, an alkenyl group, an alkyl group or a cycloalkyl group.
- R 2 each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, a cycloalkyl group or a monovalent to tetravalent organic group represented by the general formulas (a) to (t).
- n 1 represents an integer of 1 to 4.
- the aryl group is preferably an aryl group having 6 to 18 carbon atoms.
- aryl groups include phenyl, naphthyl, indenyl, biphenyl, and anthryl groups. Can be mentioned. Of these, a phenyl group is more preferable.
- These aryl groups may have one or more, preferably 1 to 3, lower alkyl groups having 1 to 4 carbon atoms. Examples of such an aryl group having a lower alkyl group include a tolyl group, a xylyl group, and a methylnaphthyl group.
- the aralkyl group is preferably a benzyl group or a phenethyl group, which has one or more lower alkyl groups having 1 to 4 carbon atoms on the phenyl group, preferably 1 to You may have in 3 ranges.
- examples of the alkenyl group include a vinyl group, a (meth) allyl group, a propenyl group, a butenyl group, and a hexenyl group.
- a vinyl group, an allyl group, and a propenyl group are preferable, and an allyl group is more preferable.
- the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms.
- the alkyl group having 3 or more carbon atoms may be linear or branched.
- methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group examples thereof include n-heptyl group, n-octyl group, n-ethylhexyl group, n-nonyl group, and n-decyl group.
- examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. Preferably, it is a cyclohexyl group.
- each R 3 independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group.
- R 4 each independently represents an aryl group, an aralkyl group, an alkenyl group, an alkyl group, a cycloalkyl group, or a monovalent to tetravalent organic group represented by the following general formulas (a) to (o).
- n 2 represents an integer of 1 to 4.
- R 3 and R 4 the aryl group, aralkyl group, alkenyl group, alkyl group, and cycloalkyl group are as described above.
- each R 5 independently represents an alkyl group, a cycloalkyl group, or a phenyl group which may have a substituent.
- the alkyl group and cycloalkyl group in R 5 are as described above.
- phenyl group which may have a substituent examples include, for example, an unsubstituted phenyl group; a monosubstituted phenyl group of 4-methylphenyl group, 3-methoxyphenyl group, 4-cyclohexylphenyl group, and 4-methoxyphenyl group A disubstituted phenyl group of 3,5-dimethylphenyl group, 3,4-dimethylphenyl group and 3,5-dimethoxyphenyl group; a trisubstituted phenyl group of 3,4,5-trimethylphenyl group; a 2-naphthyl group; , 3-methyl-2-naphthyl group, and 2-naphthyl group which may have a substituent of 4-methyl-2-naphthyl group.
- each R 6 independently represents an alkyl group, a cycloalkyl group, or an optionally substituted phenyl group.
- the alkyl group, cycloalkyl group, or phenyl group which may have a substituent in R 6 is as described above.
- each R a independently represents an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group.
- Each R b independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group.
- R a and R b the aryl group, aralkyl group, alkenyl group, alkyl group, and cycloalkyl group are as described above.
- the benzoxazine compound (A) preferably contains at least one selected from the group consisting of compounds represented by the following formula (5) and the following formula (6) from the viewpoint of solvent solubility.
- each R 7 independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group.
- R 8 each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group.
- X 1 represents an alkylene group, a group represented by the following formula (7), a group represented by the formula “—SO 2 —”, a group represented by “—CO—”, an oxygen atom, or a single bond.
- R 7 and R 8 the aryl group, aralkyl group, alkenyl group, alkyl group, and cycloalkyl group are as described above.
- alkylene group a linear or branched alkylene group is preferable.
- linear alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decanylene, trimethylene, tetramethylene, pentamethylene. Groups and hexamethylene groups.
- branched alkylene group include —C (CH 3 ) 2 —, —CH (CH 3 ) —, —CH (CH 2 CH 3 ) —, —C (CH 3 ) (CH 2 CH 3 ).
- each R 9 independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group.
- R 10 each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group.
- X 2 represents an alkylene group, a group represented by the following formula (7), a group represented by the formula “—SO 2 —”, a group represented by “—CO—”, an oxygen atom, or a single bond.
- R 9 and R 10 the aryl group, aralkyl group, alkenyl group, alkyl group, and cycloalkyl group are as described above.
- the alkylene group for X 2 is as described above.
- Y is a hydrocarbon group having 6 to 30 carbon atoms and having an alkylene group or an aromatic ring.
- n 3 represents an integer of 0 or more and 5 or less.
- n 3 is preferably an integer of 1 or more and 3 or less, and more preferably 1 or 2.
- the alkylene group for Y is as described above.
- hydrocarbon group having 6 to 30 carbon atoms having an aromatic ring examples include aromatic compounds such as benzene, biphenyl, naphthalene, anthracene, fluorene, phenanthrene, indacene, terphenyl, acenaphthylene, and phenalene. And a divalent group obtained by removing two hydrogen atoms from the nucleus.
- benzoxazine compound (A) a compound represented by the following formula (5-1), a compound represented by the following formula (5-2), a compound represented by the following formula (5-3), Containing at least one selected from the group consisting of a compound represented by (6-1), a compound represented by the following formula (6-2), and a compound represented by the following formula (6-3) It is preferable from the viewpoint that excellent solvent solubility is obtained and high chip adhesion and substrate adhesion are obtained.
- R each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms).
- the production method of the benzoxazine compound (A) is not particularly limited and can be produced by a known method.
- As the production method for example, a first step of preparing a reaction solution in which a primary amine, aldehyde, and phenol are reacted in a solvent to dissolve or partially suspend a product benzoxazine compound. And a second step of adding an alcohol solvent to the reaction solution to precipitate a benzoxazine compound.
- a reaction liquid containing a benzoxazine compound monomer as a main product is obtained.
- This benzoxazine compound monomer is obtained by dehydration condensation of primary amines, aldehydes, and phenols. Generate by.
- benzoxazine compound (A) commercially available products may be used. Examples thereof include Pd type benzoxazine (manufactured by Shikoku Kasei Kogyo Co., Ltd.) and Fa type benzoxazine (manufactured by Shikoku Kasei Kogyo Co., Ltd.). It is done.
- the resin composition of this embodiment contains an organic compound (B) having a flux function in order to develop flux activity during flip chip mounting.
- the organic compound (B) having a flux function is not particularly limited as long as it is an organic compound having one or more acidic sites in the molecule.
- As the acidic site for example, a phosphoric acid group, a phenolic hydroxyl group, a carboxyl group, and a sulfonic acid group are preferable.
- a semiconductor device using the resin composition of this embodiment as an underfill material preferably a pre-applied underfill material. From the viewpoint of more effectively preventing migration and corrosion of metals such as solder and copper constituting the joint, a phenolic hydroxyl group or a carboxyl group is more preferable.
- the organic compound (B) having a flux function preferably has an acid dissociation constant pKa of 3.8 or more and 15.0 or less in order to sufficiently remove the oxide film at the junction. From the viewpoint of achieving both storage stability and flux activity, it is more preferably 4.0 or more and 14.0 or less.
- the organic compound (B) having a flux function in the resin composition of the present embodiment is volatilized before the flux activity is expressed during flip chip mounting, that is, before removing the oxide film at the junction.
- the molecular weight is preferably 200 or more, and more preferably 250 or more.
- the molecular weight is preferably 8000 or less, more preferably 1000 or less, and even more preferably 500 or less.
- Examples of the organic compound (B) having a flux function include abietic acid, neoabietic acid, dehydroabietic acid, pimaric acid, isopimaric acid, parastrinic acid, diphenolic acid, dihydroabietic acid, tetrahydroabietic acid, rosin acid-modified resin, N , N′-bis (salicylidene) -1,2-propanediamine, N, N′-bis (salicylidene) -1,3-propanediamine, and at least one selected from the group consisting of phenolphthalene Is preferable from the viewpoints of solvent solubility and storage stability.
- dehydroabietic acid diphenolic acid, dihydroabietic acid, tetrahydroabietic acid, and rosin acid modified More preferred are resins, N, N′-bis (salicylidene) -1,2-propanediamine, and N, N′-bis (salicylidene) -1,3-propanediamine.
- the content of the organic compound (B) having a flux function in the resin composition of the present embodiment is not particularly limited. However, the flux activity of the resin composition and an important characteristic when forming and using a laminate are used. From the viewpoint of achieving both flexibility, the total amount of the benzoxazine compound (A), the following thermosetting component (C), and the following flexibility-imparting component (F) is 100 parts by mass. It is preferably no less than 50 parts by mass and more preferably no less than 5 parts by mass and no greater than 40 parts by mass, and even more preferably no less than 10 parts by mass and no greater than 30 parts by mass. However, when the flexibility imparting component (F) is not included in the resin composition of the present embodiment, the content of the organic compound (B) is the benzoxazine compound (A) and the thermosetting resin (C). ) To 100 parts by mass in total.
- thermosetting component (C) The resin composition of this embodiment contains thermosetting components other than the benzoxazine compound (A).
- examples of the thermosetting component (C) include compounds that are reactive with the benzoxazine compound (A) and that are not reactive with the flux component, and are thermosetting having phenol resin and / or radical polymerizability. Is preferred.
- phenol resin examples include bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, and aralkyl novolac.
- Type phenol resin biphenyl aralkyl type phenol resin, cresol novolac type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolac resin, polyfunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolak type phenol resin, phenol aralkyl type phenol Resin, naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, Phenyl type phenol resins, alicyclic phenol resins, polyol-type phenolic resin, a phosphorus-containing phenol resins, and hydroxyl-containing silicone resins and the like. These phenol resins can be used alone or in combination of two or more.
- phenol resin examples include 9,9-Bis- (4-hydroxy-3-methylphenyl) fluorene, bisphenolfluorene, 2,4,6-tris (3 ′, 5′-di-tert-butyl-4 ′).
- thermosetting resin having radical polymerizability is not particularly limited as long as it is a thermosetting resin having a functional group that is polymerized by radicals.
- a thermosetting resin is not particularly limited, but is preferably a resin or compound having at least one functional group selected from the group consisting of an alkenyl group, a maleimide group, and a (meth) acryloyl group. .
- These thermosetting resins having radical polymerizability can be used alone or in combination of two or more.
- thermosetting resin having an alkenyl group is not particularly limited as long as it is a resin or a compound having one or more carbon-carbon double bonds in the molecule.
- a thermosetting resin having a vinyl group examples thereof include a thermosetting resin having a (meth) allyl group and a thermosetting resin having a propenyl group.
- thermosetting resin having a vinyl group examples include divinylbenzene, divinylnaphthalene, styrene, and a styrene compound.
- thermosetting resin having a (meth) allyl group is not particularly limited as long as it is a resin or compound having one or more (meth) allyl groups in the molecule.
- a resin or compound having one or more (meth) allyl groups in the molecule for example, tri (meth) allyl cyanurate, tri (Meth) allyl isocyanurate, tri (meth) allyl trimellitate, tetra (meth) allyl pyromellitate, and pentaerythritol tri (meth) allyl ether.
- thermosetting resin having a propenyl group is not particularly limited as long as it is a resin or compound having one or more propenyl groups in the molecule, and examples thereof include propenylphenoxybenzophenone.
- thermosetting resin having radical polymerizability a maleimide compound is preferable from the viewpoint of reactivity with the benzoxazine compound (A).
- the resin composition obtained by the addition reaction between the benzoxazine compound (A) and the maleimide compound can impart the heat resistance of the maleimide compound, but is a disadvantage of the resin composition obtained by single curing of the maleimide compound. It is estimated that low adhesion can be improved by the benzoxazine compound (A).
- As a mechanism for improving adhesion in addition to the introduction of polar groups such as phenolic hydroxyl groups and tertiary amino groups generated in the process of ring-opening polymerization of the oxazine ring, high crosslink density by polymerization of maleimide groups can be increased. It is presumed that moderate followability is exhibited with respect to the adherend by relaxing by the addition reaction.
- thermosetting resin having a maleimide group is not particularly limited as long as it is a resin or compound having one or more maleimide groups in the molecule.
- each R 11 independently represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of more effectively and reliably achieving the effects of the present embodiment.
- n 4 represents an integer of 1 to 10. The upper limit of n 4 is preferably 7 from the viewpoint of solubility in organic solvents.
- n 5 is in the range of 1 to 30. From the viewpoint of more effectively and surely achieving the operational effects of the present embodiment, n 5 is preferably 7 or more and 30 or less, and more preferably 7 or more and 18 or less, as an average value.
- R ⁇ 12 > shows a hydrogen atom, a methyl group, or an ethyl group each independently.
- R ⁇ 13 > shows a hydrogen atom or a methyl group each independently.
- each R 14 independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n 6 represents an integer of 1 to 10.
- alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, And neopentyl groups.
- R 15 and R 17 each independently represents a hydrocarbon group in which 8 or more atoms are linked in a straight chain.
- R 16 each independently represents a substituted or unsubstituted cyclic hydrocarbon group which may contain a hetero atom having 4 to 10 atoms constituting the ring.
- n 7 represents a number of 1 or more and 10 or less.
- examples of the hydrocarbon group in which 8 or more atoms are linked in a straight chain include, for example, a substituted or unsubstituted divalent hydrocarbon group having 8 or more carbon atoms.
- a substituted or unsubstituted bivalent hydrocarbon group For example, a substituted or unsubstituted linear aliphatic hydrocarbon group, a substituted or unsubstituted branched aliphatic hydrocarbon group, and substituted Or an unsubstituted cycloaliphatic hydrocarbon group is mentioned. Examples include octylene group, nonamethylene group, decamethylene group, dodecamethylene group, hexadecamethylene group, and octadecamethylene group.
- the cyclic hydrocarbon group which may contain a substituted or unsubstituted heteroatom having 4 to 10 atoms constituting the ring includes, for example, a substituted or unsubstituted atom constituting the ring.
- the heterocyclic group which is the following is mentioned.
- the number of atoms constituting the ring is the number of atoms linked in a ring, and does not include the number of atoms such as side chain substituents.
- Examples of the alicyclic moiety in the substituted or unsubstituted alicyclic group include a divalent or divalent or higher valent cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, and cyclodecyl group.
- the substituent is an alkyl group
- the alkyl group is not particularly limited, but an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 3 to 10 carbon atoms is more preferable.
- alkyl group having 1 to 10 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, A neopentyl group, n-hexyl group, texyl group, n-heptyl group, n-octyl group, n-ethylhexyl group, n-nonyl group, and n-decyl group can be mentioned. There may be one alkyl group-substituted alkyl group, or two or more.
- R 18 each independently represents an alkylene group.
- R 19 each independently represents an alkylene group, a group represented by the following formula (7), a group represented by the formula “—SO 2 —”, a group represented by “—CO—”, the following formula (14 ), An oxygen atom, or a single bond.
- n 8 represents a number of 1 or more and 10 or less.
- the alkylene group is as described above.
- Y is a hydrocarbon group having 6 to 30 carbon atoms and having an alkylene group or an aromatic ring.
- n 3 represents an integer of 0 or more and 5 or less.
- n 3 is preferably an integer of 1 or more and 3 or less, and more preferably 1 or 2.
- the hydrocarbon group having 6 to 30 carbon atoms and having an alkylene group and an aromatic ring is as described above.
- the maleimide compound represented by the said Formula (9) is preferable from a soluble viewpoint to an organic solvent, and a flexible viewpoint, and also 2 with the maleimide compound represented by the said Formula (9).
- 2-bis ⁇ 4- (4-maleimidophenoxy) phenyl ⁇ propane at least one selected from the group consisting of the maleimide compound represented by the formula (8) and the maleimide compound represented by the formula (10) More preferably, it contains a maleimide compound.
- a maleimide compound when used, it is not particularly limited. From the viewpoint of obtaining good solubility in an organic solvent and good flexibility, a benzoxazine compound (A), a heat
- the maleimide compound represented by the formula (9) is preferably contained in an amount of 5 to 40 parts by mass with respect to a total of 100 parts by mass of the curable component (C) and the flexibility-imparting component (F). More preferably, the content is 35 parts by mass.
- the flexibility imparting component (F) is not included in the resin composition of the present embodiment, the content of the maleimide compound is 100 in total of the benzoxazine compound (A) and the thermosetting component (C). It is said amount with respect to a mass part.
- the maleimide compound can also be contained in the resin composition in the form of a prepolymer obtained by polymerizing the maleimide compound and a prepolymer obtained by polymerizing the maleimide compound with another compound such as an amine compound.
- maleimide compound commercially available products may be used.
- BMI-2300 manufactured by Daiwa Kasei Kogyo Co., Ltd.
- BMI-70, BMI-80, BMI-1000P manufactured by KAI Kasei Co., Ltd., Designer Molecules Inc.
- BMI-1500, BMI-1700, BMI-3000, and BMI-5000 examples thereof include BMI-1500, BMI-1700, BMI-3000, and BMI-5000.
- thermosetting resin having a (meth) acryloyl group is not particularly limited as long as it is a resin or compound having one or more (meth) acryloyl groups in the molecule.
- examples of the thermosetting resin having a (meth) acryloyl group include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol ( (Meth) acrylate monomethyl ether, phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (Meth) acrylate, n
- thermosetting components (C) can be used alone or in combination of two or more.
- thermosetting component (C) in the resin composition of this embodiment is not specifically limited, Since it is the range which does not impair the adhesiveness which the said benzoxazine compound (A) has, it is a benzoxazine compound (A ) And the thermosetting component (C) are preferably contained in an amount of 10 to 80 parts by mass, and more preferably 15 to 75 parts by mass.
- the content of the thermosetting component (C) in the resin composition of this embodiment is not particularly limited. Since it is a range which does not impair the adhesiveness which an oxazine compound (A) has, with respect to a total of 100 mass parts of a benzoxazine compound (A), a thermosetting component (C), and a flexibility provision component (F),
- the content is preferably 10 parts by mass or more and 70 parts by mass or less, and more preferably 15 parts by mass or more and 68 parts by mass or less.
- the resin composition of the present embodiment preferably contains a radical polymerization initiator (D) as a known initiator generally used for radical polymerization.
- the 10-hour half-life temperature of the radical polymerization initiator (D) is not particularly limited, but is 100 ° C. or higher, and more preferably 110 ° C. or higher from the viewpoint of manufacturability.
- the radical polymerization initiator (D) preferably satisfies the 10-hour half-life temperature in the above range.
- radical polymerization initiator examples include dicumyl peroxide, di (2-tert-butylperoxyisopropyl) benzene, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethyl-2,5.
- organic peroxides are preferable, and peroxyesters, peroxyketals, dialkyl peroxides, and organic peroxides having a hydroperoxide skeleton are more preferable.
- Dicumyl peroxide, di (2-tert) -Butylperoxyisopropyl) benzene, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexyne-3, and tert-butyl hydroperoxide Is more preferable from the viewpoint of manufacturability.
- radical polymerization initiators (D) can be used alone or in combination of two or more, and a known curing accelerator may be used in combination.
- the content of the radical polymerization initiator (D) is not particularly limited, but with respect to a total of 100 parts by mass of the benzoxazine compound (A) and the thermosetting component (C), It is preferable that they are 0.05 mass part or more and 10 mass parts or less.
- the resin composition of the present embodiment can contain an inorganic filler (E) for improved flame resistance, improved thermal conductivity, and reduced thermal expansion coefficient.
- an inorganic filler By using an inorganic filler, the flame resistance and thermal conductivity of the resin composition and the like can be improved, and the thermal expansion coefficient can be reduced.
- the average particle diameter of the inorganic filler (E) is not limited, but when the resin composition of the present embodiment is used as an underfill material, preferably as a pre-applied underfill material, the pitch of electrodes arranged on a chip is narrowed. And from the viewpoint of reducing the gap between the electrodes, it is preferably 3 ⁇ m or less, more preferably 1 ⁇ m or less. Although the lower limit of the average particle diameter is not particularly limited, it is, for example, 10 nm. In the present specification, the “average particle diameter” of the inorganic filler (E) means the median diameter of the inorganic filler (E).
- the median diameter refers to the volume of particles on the larger particle size side and the volume of particles on the smaller particle size side when the particle size distribution of the powder is divided into two based on a certain particle size. Means a particle size that occupies 50% of the total powder.
- the average particle diameter (median diameter) of the inorganic filler (E) is measured by a wet laser diffraction / scattering method.
- silica such as natural silica, fused silica, amorphous silica, and hollow silica
- Aluminum compounds such as boehmite, aluminum hydroxide, an alumina, and aluminum nitride
- Magnesium compounds such as magnesium oxide and magnesium hydroxide
- calcium compounds such as calcium carbonate and calcium sulfate
- molybdenum compounds such as molybdenum oxide and zinc molybdate
- boron nitride barium sulfate
- talc such as natural talc and calcined talc Mica
- glass such as short fiber glass, spherical glass, and fine powder glass (for example, E glass, T glass, D glass).
- conductivity or anisotropic conductivity for example, gold, silver, nickel, copper, tin alloy, and palladium metal particles are used as the inorganic filler
- silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, magnesium oxide, And magnesium hydroxide are preferable, silica, alumina, and boron nitride are more preferable, and among them, fused silica is more preferable.
- fused silica examples include SFP-120MC and SFP-130MC manufactured by Denka Co., Ltd., 0.3 ⁇ m SX-CM1, 0.3 ⁇ m SX-EM1, 0.3 ⁇ m SV-EM1, SC1050-MLQ manufactured by Admatechs Co., Ltd. SC2050-MNU, SC2050-MTX, 2.2 ⁇ m SC6103-SQ, SE2053-SQ, YA050C-MJF, and YA050C-MJA.
- These inorganic fillers (E) can be used singly or in appropriate combination of two or more.
- a surface treated with a silane coupling agent may be used.
- the silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for surface treatment of inorganic substances.
- vinyltrisilane silane coupling agents such as vinyltrimethoxysilane and ⁇ -methacryloxypropyltrimethoxysilane
- phenylaminosilane silane coupling agents such as N-phenyl-3-aminopropyltrimethoxysilane
- trimethoxyphenyl examples thereof include phenylsilane-based silane coupling agents such as silane; imidazolesilane-based silane coupling agents.
- These silane coupling agents can be used individually by 1 type or in mixture of 2 or more types as appropriate.
- the content in the resin composition is that of the underfill material, preferably a pre-applied underfill, while improving the flame resistance of the resin composition and reducing the coefficient of thermal expansion.
- the content is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and further preferably 50 parts by mass or more.
- the content of the inorganic filler (E) is the benzoxazine compound (A) and the thermosetting resin ( It is said amount with respect to a total of 100 parts by mass of C).
- these total amount fills the range of the said content.
- Flexibility imparting component (F) In the resin composition of this embodiment, it is preferable to contain a flexibility provision component (F).
- the flexibility-imparting component (F) is not particularly limited as long as it can impart flexibility to the layer containing the resin composition.
- SBR isoprene rubber
- BR butadiene rubber
- NBR acrylonitrile butadiene rubber
- polyurethane polypropylene
- acrylic oligomer polypropylene
- silicone resin etc.
- thermoplastic high molecular compound is mentioned.
- (meth) acrylic Oligomers or (meth) acrylic polymers are preferred.
- the (meth) acrylic oligomer or (meth) acrylic polymer include “ARUFON (registered trademark)” series from Toagosei Co., Ltd., “Act Flow (registered trademark)” series from Soken Chemical Co., Ltd., Negami Kogyo ( "PARACRON (registered trademark)” series, and Kuraray's "KURRARITY (registered trademark)” series.
- the molecular weight of the flexibility-imparting component (F) is not particularly limited, but from the viewpoint of imparting flexibility to the resin composition, the mass average molecular weight is preferably 1,000 or more, and 2,000 or more. It is more preferable that Further, when the resin composition is used as an underfill material, preferably as a pre-applied underfill material, there is no biting of the resin composition in the metal joint portion, and in order to obtain a good and stable joint, It is necessary to control the melt viscosity of the resin composition to be low and to ensure the fluidity of the resin composition during bonding.
- the mass average molecular weight of the flexibility-imparting component (E) is preferably 1,000,000 or less, more preferably 800,000 or less, still more preferably 100,000 or less, and 10,000.
- the flexibility-imparting component (E) having a mass average molecular weight within the above range the flexibility of the resin composition and bonding when used as an underfill material, preferably as a pre-applied underfill material
- the properties can be balanced with a better balance.
- the “mass average molecular weight” of the flexibility-imparting component (E) means a mass average molecular weight in terms of polystyrene standard by gel permeation chromatography (GPC) method.
- the content in the resin composition is selected from the viewpoint of controllability of the melt viscosity, the benzoxazine compound (A), the thermosetting component (C), and the flexibility. It is preferably 87.5 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 30 parts by mass or less with respect to 100 parts by mass of the total amount of the imparting component (F). Further, the content of the flexibility imparting component (F) in the resin composition is preferably 1 part by mass or more, and more preferably 5 parts by mass or more. In addition, when using together 2 or more types of flexibility provision components (F), it is preferable that these total amount satisfy
- the resin composition of the present embodiment comprises a benzoxazine compound (A), an organic compound (B) having a flux function, a thermosetting component (C), a radical polymerizable initiator (D), an inorganic filler (E), In addition to the flexibility-imparting component (F), one or more other components may be included.
- the resin composition of the present embodiment may contain a coupling agent for the purpose of improving the adhesion at the interface between the resin and the filler and improving the moisture absorption heat resistance.
- a coupling agent for the purpose of improving the adhesion at the interface between the resin and the filler and improving the moisture absorption heat resistance.
- vinyltrisilane silane coupling agents such as vinyltrimethoxysilane and ⁇ -methacryloxypropyltrimethoxysilane
- phenylaminosilane silane coupling agents such as N-phenyl-3-aminopropyltrimethoxysilane
- trimethoxyphenyl examples thereof include phenylsilane-based silane coupling agents such as silane; imidazolesilane-based silane coupling agents.
- These silane coupling agents can be used individually by 1 type or in mixture of 2 or more types as appropriate.
- the benzoxazine compound (A), thermosetting is preferably 0.05 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass in total of the sex component (C) and the flexibility-imparting component (F). More preferably, it is 1 part by mass or more and 15 parts by mass or less.
- the content of the coupling agent is that of the benzoxazine compound (A) and the thermosetting resin (C). The amount is 100 parts by mass in total.
- silane coupling agents it is preferable that these total amount exists in the range of the said content.
- the resin composition of the present embodiment may contain a wetting and dispersing agent for the purpose of improving the productivity of the laminate and the dispersibility of the filler.
- the wetting and dispersing agent is not particularly limited as long as it is a wetting and dispersing agent generally used in paints and the like. Examples include Disperbyk (registered trademark) -110, -111, -180, -161, BYK-W996, -W9010, and -W903 manufactured by Big Chemie Japan Co., Ltd. These wetting and dispersing agents can be used singly or in appropriate combination of two or more.
- the wetting and dispersing agent When the wetting and dispersing agent is used, its content in the resin composition is not particularly limited, but from the viewpoint of improving the productivity of the laminate, it is 0.1 parts by mass with respect to 100 parts by mass of the inorganic filler (E).
- the amount is preferably 5 parts by mass or less, and more preferably 0.5 parts by mass or more and 3 parts by mass or less.
- these total amount satisfy
- the resin composition of the present embodiment may contain a curing accelerator for the purpose of adjusting the curing speed.
- the curing accelerator is not particularly limited as long as it is known as a curing accelerator for thermosetting resins and is generally used.
- the curing accelerator include imidazoles such as 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, and 2,4,5-triphenylimidazole, and Derivatives thereof; tertiary amines such as triethylamine and tributylamine are listed.
- These hardening accelerators can be used individually by 1 type or in mixture of 2 or more types as appropriate.
- the content of the curing accelerator is preferably 0.01 parts by mass or more and 10 parts by mass or less, and more preferably 0.05 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass in total of (F). More preferably, it is 0.1 to 1 part by mass.
- the content of the curing accelerator is that of the benzoxazine compound (A) and the thermosetting resin (C).
- the amount is 100 parts by mass in total.
- the resin composition of the present embodiment may contain various additives for various purposes within a range where the intended characteristics are not impaired.
- additives include ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, antifoaming agents, leveling agents, brighteners, A flame retardant and an ion trap agent are mentioned. These additives can be used individually by 1 type or in mixture of 2 or more types as appropriate.
- the content of other additives is not particularly limited, but is usually the benzoxazine compound (A), the thermosetting component (C), and the flexibility-imparting component (F).
- each amount is 0.01 to 10 parts by mass with respect to 100 parts by mass in total.
- the content of other additives is benzoxazine compound (A) and thermosetting resin (C). It is set as the said quantity with respect to the said quantity with respect to a total of 100 mass parts.
- the resin composition of the present embodiment comprises a benzoxazine compound (A), an organic compound (B) having a flux function, a thermosetting component (C), a radical polymerizable initiator (D), an inorganic filler (E), It is prepared by appropriately mixing the flexibility-imparting component (F) and other components. As needed, it is good also as a form of the varnish which melt
- the varnish of the resin composition of this embodiment can be used suitably as a varnish at the time of producing the laminated body of this embodiment as follows.
- the organic solvent is not particularly limited as long as it can suitably dissolve or disperse the above components and does not impair the desired effect of the resin composition of the present embodiment.
- organic solvent examples include alcohols such as methanol, ethanol, and propanol; ketones such as acetone, methyl ethyl ketone (hereinafter sometimes abbreviated as “MEK”), and methyl isobutyl ketone; dimethylacetamide, and dimethylformamide.
- Amides such as: aromatic hydrocarbons such as toluene and xylene.
- the resin composition of this embodiment is excellent in adhesiveness with a chip, adhesiveness with a substrate, and flux activity. Moreover, the laminated body which has a resin layer excellent in adhesiveness with a chip
- the resin composition of this embodiment is used as a pre-applied underfill material used in the form of a laminate, it has excellent chip adhesion, adhesion to a substrate, and flux activity, and in addition, bondability and insulation reliability. Other suitable effects such as excellent properties can also be exhibited.
- the resin composition of the present embodiment has various excellent characteristics, and in particular, can satisfy the adhesiveness with the chip, the adhesiveness with the substrate, and the flux activity at a high level. It is useful as a fill material and more useful as a pre-applied underfill material.
- the laminated body, the semiconductor wafer with a resin composition layer, the substrate with a resin composition layer such as a semiconductor mounting substrate with a resin composition layer, and the semiconductor device all use the above-described resin composition of the present invention. Formed.
- the laminated body of this embodiment is equipped with a support base material and the layer containing the resin composition of this embodiment laminated
- the above-described resin composition of the present embodiment is attached to a support substrate.
- the support substrate is not particularly limited, but a polymer film can be used.
- polyesters such as polyvinyl chloride, polyvinylidene chloride, polybutene, polybutadiene, polyurethane, ethylene-vinyl oxide copolymer, polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate, polyethylene, polypropylene
- polyester, polyimide, and polyamide are preferable, and among them, polyethylene terephthalate, which is a kind of polyester, is more preferable.
- the thickness of the support substrate of the present embodiment is not limited, but is 10 to 100 ⁇ m from the viewpoint of the productivity of the laminate, for example, the stability of the coating thickness when the resin composition is applied to the support substrate. Is preferred. Also, from the viewpoint of transportability of the laminate, the thickness is preferably 10 to 100 ⁇ m. Further, the lower limit of the thickness is more preferably 12 ⁇ m or more, further preferably 25 ⁇ m or more, and even more preferably 30 ⁇ m or more, from the viewpoint of securing the yield when producing a laminate. In addition, the upper limit of the thickness is 80 ⁇ m or less from the viewpoint of the manufacturing cost of the laminated body because the supporting base material does not finally exist as a component of the semiconductor device and is peeled off during the process. More preferably, it is 50 ⁇ m or less.
- a method for producing a layered product of the present embodiment by forming a layer containing the resin composition of the present embodiment (hereinafter also simply referred to as “resin composition layer”) on the support substrate.
- resin composition layer a layer containing the resin composition of the present embodiment (hereinafter also simply referred to as “resin composition layer”) on the support substrate.
- a varnish in which the resin composition of the present embodiment is dissolved or dispersed in an organic solvent is applied to the surface of the support substrate, and heated and / or dried under reduced pressure.
- a method of forming the resin composition layer by removing the solvent and solidifying the resin composition of this embodiment can be mentioned.
- the drying conditions are not particularly limited, but the content ratio of the organic solvent to the resin composition layer is usually 10 parts by mass or less, preferably 5 parts by mass or less, with respect to the total amount (100 parts by mass) of the resin composition layer.
- Conditions for achieving such drying also vary depending on the type and blending amount of the organic solvent in the varnish.
- drying is usually about 3 to 10 minutes under a heating condition of 90 to 160 ° C. under 1 atm.
- the thickness of the resin composition layer in the laminate of the present embodiment is not particularly limited, but the viewpoint of better removing light volatiles when the resin composition layer is dried, and the function as a laminate are more effective and reliable.
- the range of 5 to 500 ⁇ m is preferable, and the range of 10 to 100 ⁇ m is more preferable.
- the semiconductor wafer with a resin composition layer according to the present embodiment includes a semiconductor wafer and the resin composition layer in the stacked body that is stacked on the semiconductor wafer. From the stacked body and the semiconductor wafer according to the present embodiment described above. It is formed. Moreover, the board
- the method for producing the semiconductor wafer with a resin composition layer of the present embodiment is not particularly limited.
- the lamination of the present embodiment is performed on the surface of the semiconductor wafer on which the electrodes are formed, that is, the surface to be bonded to the substrate. It is obtained by pasting together so that the resin composition layers of the body face each other.
- the method for producing the substrate with the resin composition layer of the present embodiment is not particularly limited.
- the substrate is attached so that the resin composition layer of the laminate of the present embodiment faces the surface on the chip mounting side of the substrate. Obtained by combining.
- the method for bonding the laminate of this embodiment to a semiconductor wafer or substrate is not particularly limited, but a vacuum / pressure laminator can be suitably used.
- a method in which the laminate of the present embodiment is pressed through an elastic body such as rubber and bonded is preferable.
- Lamination conditions are not particularly limited as long as they are generally used in the industry. For example, a temperature of 50 to 140 ° C., a contact pressure in the range of 1 to 11 kgf / cm 2 , and an atmospheric pressure reduction of 20 hPa or less. Done under.
- the laminated body may be smoothed by hot pressing with a metal plate.
- the laminating step and the smoothing step can be continuously performed by a commercially available vacuum pressurizing laminator. In any case, the laminate attached to the semiconductor wafer or the substrate is removed before the flip chip mounting of the chip.
- the semiconductor device of the present embodiment includes the semiconductor wafer with the resin composition layer of the present embodiment and / or the substrate with the resin composition layer of the present embodiment. From the resin composition layer, the chip, the substrate, and the like of the present embodiment. Composed.
- the method for manufacturing the semiconductor device of the present embodiment is not particularly limited.For example, the semiconductor wafer with the resin composition layer of the present embodiment is thinned by means such as grinding, and separated into pieces by a dicing saw or the like, There is a technique in which a chip with a resin composition layer is formed and mounted on a substrate. Moreover, you may mount a chip
- a flip chip bonder compatible with the thermocompression bonding method can be suitably used.
- the case where the chip is flip-chip mounted on the substrate is described for convenience, but the target to which the resin composition of the present embodiment is applied is other than the substrate while the chip is flip-chip mounted.
- the resin composition of the present embodiment is a chip laminate that performs chip-to-chip connection via a junction between a semiconductor wafer and a chip when mounting the chip on a semiconductor wafer, or through a TSV (Through Silicon Via). It is also possible to use it at the junction between the chips, and in any case, the advantages of the present invention can be obtained.
- Example 1 As the benzoxazine compound (A), 160 parts by mass of a MEK solution (non-volatile content 50% by mass) of a benzoxazine compound of the above general formula (5-1) (Pd-type benzoxazine manufactured by Shikoku Kasei Kogyo Co., Ltd.) Dehydroabietic acid (molecular weight: 300.44, pKa: 4 to 5, functional group equivalent at acidic site: 300 g / eq., Sum) as organic compound (B) having a flux function and 80 parts by mass in terms of nonvolatile content 40 parts by mass (20 parts by mass in terms of nonvolatile content) of MEK solution (manufactured by Kojun Pharmaceutical Co., Ltd.) (non-volatile content 50% by mass) and thermosetting component (C), R 11 in the above formula (8) is all hydrogen atom, a maleimide compound n 4 is 1 ⁇ 3 MEK solution (nonvola
- the varnish was applied to a 38 ⁇ m thick polyethylene terephthalate film (TR1-38, manufactured by Unitika Co., Ltd.) with a release agent coated on the surface, dried by heating at 100 ° C. for 5 minutes, and the resin composition of this embodiment A resin laminate having a physical layer thickness of 30 ⁇ m was obtained.
- Example 2 As the benzoxazine compound (A), 80 parts by mass of the benzoxazine compound of the general formula (5-1) is converted to 20 parts by mass in terms of nonvolatile content, and the maleimide compound of the formula (8) is used as the thermosetting component (C). 5 parts by mass is converted to 45 parts by mass in terms of non-volatile content, 15 parts by mass of the maleimide compound of formula (9) is changed to 25 parts by mass in terms of non-volatile content, and an acrylic polymer (mass by mass) is added as the flexibility-imparting component (F).
- a varnish was prepared in the same manner as in Example 1 except that 10 parts by mass of an average molecular weight: 2900 and ARUFON (registered trademark) US-6170 manufactured by Toagosei Co., Ltd. were obtained, and a resin laminate was obtained.
- thermosetting component (C) As a thermosetting component (C), instead of the maleimide compound of the formula (8) and the maleimide compound of the formula (9), 20 parts by mass of dipentaerythritol hexaacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.) In addition, instead of dicumyl peroxide as a radical polymerization initiator, tert-butyl hydroperoxide (Lupelox TBH manufactured by Arkema Yoshitomi Corp., 10 hour half-life temperature: 165 ° C.) was changed to 0.5 parts by mass. Except for the above, a varnish was prepared in the same manner as in Example 1 to obtain a resin laminate.
- DPHA manufactured by Nippon Kayaku Co., Ltd. dipentaerythritol hexaacrylate
- dicumyl peroxide as a radical polymerization initiator
- tert-butyl hydroperoxide Liupelox TBH manufactured by Arkema Yoshito
- Example 4 Without adding 5 parts by mass of the maleimide compound of the formula (8) as the thermosetting component (C), 15 parts by mass of the maleimide compound of the formula (9) is changed to 10 parts by mass in terms of nonvolatile content.
- a varnish was prepared in the same manner as in Example 1 except that 10 parts by mass of an acrylic polymer (ARUFON (registered trademark) US-6170 manufactured by Toagosei Co., Ltd.) was mixed as a flexibility imparting component (F). A laminate was obtained.
- ARUFON registered trademark
- US-6170 manufactured by Toagosei Co., Ltd.
- Example 5 As a benzoxazine compound (A), 50 parts by mass of a MEK solution (non-volatile content 50% by mass) of a benzoxazine compound of the above general formula (5-1) (Pd-type benzoxazine manufactured by Shikoku Kasei Kogyo Co., Ltd.) A maleimide compound (BMI-2300, Yamato) in which R 11 in formula (8) is all a hydrogen atom and n 4 is 1 to 3 as a thermosetting component (C) and 25 parts by mass in terms of nonvolatile content 16 parts by mass (8 parts by mass in terms of nonvolatile content) of MEK solution (made by Kasei Kogyo Co., Ltd.) (non-volatile content: 50% by mass), bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-) 70, manufactured by Kay Kasei Chemical Co., Ltd.) MEK solution (non-volatile content 50% by mass
- MEK solution non-volatile content 50% by mass
- 32 parts by mass 16 parts by mass in terms of non-volatile content
- maleimide compound represented by the above formula (9) (above n 5 in the formula (9) is 14 (average value)
- BMI-1000P MEK solution (nonvolatile content 50%) 50 parts by weight of KI Kasei Co., Ltd.) (in terms of a non-volatile component 25 Part by weight)
- an organic compound (B) having a flux function 40 parts by mass of MEK solution (non-volatile content 50% by mass) of dehydroabietic acid (molecular weight: 300.44, functional group equivalent of acidic site: 300 g / eq., Manufactured by Wako Pure Chemical Industries, Ltd.) (20 in terms of
- Example 6 Example 5 except that the organic compound (B) having a flux function was changed to rosin-modified maleic resin (Marquide (registered trademark) No. 32 manufactured by Arakawa Chemical Industries, Ltd.) instead of dehydroabietic acid. A varnish was prepared in the same manner as described above to obtain a resin laminate.
- rosin-modified maleic resin Marquide (registered trademark) No. 32 manufactured by Arakawa Chemical Industries, Ltd.
- Example 7 As an organic compound (B) having a flux function, N, N′-bis (salicylidene) -1,2-propanediamine (pKa: 12 to 13, manufactured by Tokyo Chemical Industry Co., Ltd.) instead of dehydroabietic acid A varnish was prepared in the same manner as in Example 5 except that the resin laminate was obtained.
- N, N′-bis (salicylidene) -1,2-propanediamine pKa: 12 to 13, manufactured by Tokyo Chemical Industry Co., Ltd.
- Example 8 As an organic compound (B) having a flux function, N, N′-bis (salicylidene) -1,3-propanediamine (pKa: 12 to 13, manufactured by Tokyo Chemical Industry Co., Ltd.) instead of dehydroabietic acid A varnish was prepared in the same manner as in Example 5 except that the resin laminate was obtained.
- N, N′-bis (salicylidene) -1,3-propanediamine pKa: 12 to 13, manufactured by Tokyo Chemical Industry Co., Ltd.
- Example 9 As an inorganic filler (E), instead of slurry silica (SC1050-MLQ manufactured by Admatechs), slurry silica (0.3 ⁇ m SV-EM1 manufactured by Admatechs, average particle size 0.3 ⁇ m, low ⁇ -ray grade, vinyl silane treatment), phenylaminosilane (KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.) is not blended as a silane coupling agent, and DISPERBYK (registered trademark) -111 (wet dispersant) is used as a wetting dispersant.
- a varnish was prepared in the same manner as in Example 6 except that 1 part by mass of Big Chemie Japan Co., Ltd.) was mixed to obtain a resin laminate.
- Example 10 As an inorganic filler (E), instead of slurry silica (0.3 ⁇ m SV-EM1, manufactured by Admatechs Co., Ltd., average particle size 0.3 ⁇ m, low ⁇ -ray grade, vinyl silane treatment), slurry silica (Co., Ltd.) A varnish was prepared in the same manner as in Example 9 except for changing to 0.3 ⁇ m SX-EM1, manufactured by Mattex, average particle size 0.3 ⁇ m, low ⁇ ray grade, and phenylaminosilane treatment, to obtain a resin laminate.
- SX-EM1 manufactured by Mattex
- thermosetting component (C) 25 parts by mass of the benzoxazine compound of the general formula (5-1) is converted to 40 parts by mass in terms of nonvolatile content, and the maleimide compound of the formula (8) is used as the thermosetting component (C).
- Example 12 As the benzoxazine compound (A), instead of the benzoxazine compound of the general formula (5-1), a benzoxazine compound of the general formula (6-1) (Fa-type benzox manufactured by Shikoku Kasei Kogyo Co., Ltd.) As an organic compound (B) having a flux function, dehydroabietic acid (molecular weight: molecular weight: instead of rosin-modified maleic acid resin (Marquide (registered trademark) No.
- dehydroabietic acid molecular weight: molecular weight: instead of rosin-modified maleic acid resin (Marquide (registered trademark) No.
- Example 13 25 parts by mass of the benzoxazine compound of the general formula (6-1) is converted into 50 parts by mass in terms of non-volatile content, and 8 parts by mass of the maleimide compound of the formula (8) in terms of non-volatile content as the thermosetting component (C).
- thermosetting component As a thermosetting component, a MEK solution (nonvolatile content) of a maleimide compound (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.) in which R 11 in the formula (8) is all hydrogen atoms and n 4 is 1 to 3 50 mass%) 26 mass parts (13 mass parts in terms of non-volatile content), MEK of bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-70, manufactured by KAI Kasei Co., Ltd.) 52 parts by mass of solution (non-volatile content: 50% by mass) (26 parts by mass in terms of non-volatile content), 2,2-bis ⁇ 4- (4-maleimidophenoxy) phenyl ⁇ propane (BMI-80, Kay Kasei Co., Ltd.) 52 parts by mass of MEK solution (non-volatile content: 50% by mass) (26 mass parts in terms of non-volatile content), male
- Comparative Example 2 Furthermore, 5 parts by mass of phenylaminosilane (KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, and 0.05 parts by mass of a silicone surface conditioner (BYK-310 manufactured by BYK Chemie) as a leveling agent A varnish was prepared in the same manner as in Comparative Example 1 except that a resin laminate was obtained.
- phenylaminosilane KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.
- a silicone surface conditioner BYK-310 manufactured by BYK Chemie
- Comparative Example 4 Comparative Example 3 was used except that the organic compound having a flux function was changed to rosin-modified maleic resin (Marquide (registered trademark) No. 32 manufactured by Arakawa Chemical Industries, Ltd.) instead of dehydroabietic acid. A varnish was prepared to obtain a resin laminate.
- rosin-modified maleic resin Marquide (registered trademark) No. 32 manufactured by Arakawa Chemical Industries, Ltd.
- thermosetting component As a thermosetting component, a MEK solution (nonvolatile content) of a maleimide compound (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.) in which R 11 in the formula (8) is all hydrogen atoms and n 4 is 1 to 3 50 mass%) 24 mass parts (12 mass parts in terms of non-volatile content), MEK of bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-70, manufactured by KAI Kasei Co., Ltd.) 48 parts by mass of solution (non-volatile content 50% by mass) (24 parts by mass in terms of non-volatile content), 2,2-bis ⁇ 4- (4-maleimidophenoxy) phenyl ⁇ propane (BMI-80, K.I.
- the varnish was applied to a 38 ⁇ m thick polyethylene terephthalate film (TR1-38, manufactured by Unitika Co., Ltd.) with a release agent coated on the surface, dried by heating at 100 ° C. for 5 minutes, and the resin composition of this embodiment A resin laminate having a physical layer thickness of 30 ⁇ m was obtained.
- thermosetting component (C) 40 parts by mass (20 parts by mass in terms of non-volatiles) of MEK solution (manufactured by Kojun Pharmaceutical Co., Ltd.) (non-volatile content 50% by mass) and the thermosetting component (C) are represented by the above formula (9).
- the varnish was applied to a 38 ⁇ m thick polyethylene terephthalate film (TR1-38, manufactured by Unitika Co., Ltd.) with a release agent coated on the surface, dried by heating at 100 ° C. for 5 minutes, and the resin composition of this embodiment A resin laminate having a physical layer thickness of 30 ⁇ m was obtained.
- the varnish was applied to a 38 ⁇ m thick polyethylene terephthalate film (TR1-38, manufactured by Unitika Co., Ltd.) with a release agent coated on the surface, dried by heating at 100 ° C. for 5 minutes, and the resin composition of this embodiment A resin laminate having a physical layer thickness of 30 ⁇ m was obtained.
- thermosetting components 124 parts by mass (62 parts by mass in terms of non-volatile content) of a MEK solution (non-volatile content 50% by mass) of a bisphenol A type epoxy compound (EXA-850CRP manufactured by DIC Corporation), and a novolac type phenol compound 76 parts by mass (38 parts by mass in terms of nonvolatile content) of MEK solution (Phenolite (registered trademark) KA-1163 manufactured by DIC Corporation) (nonvolatile content: 50% by mass), and an organic compound having a flux function, 40 parts by mass of MEK solution (non-volatile content 50% by mass) of abietic acid (molecular weight: 300.44, functional group equivalent of acidic site: 300 g / eq., Manufactured by Wako Pure Chemical Industries, Ltd.) (20 mass in terms of non-volatile content) Part) was mixed and stirred for 30 minutes using a high-speed stirrer to obtain a varnish.
- the varnish was applied to a 38 ⁇ m thick polyethylene terephthalate film (TR1-38, manufactured by Unitika Co., Ltd.) with a release agent coated on the surface, dried by heating at 100 ° C. for 5 minutes, and the resin composition of this embodiment A resin laminate having a physical layer thickness of 30 ⁇ m was obtained.
- thermosetting component 45 parts by mass of a cresol novolak type epoxy compound (EOCN-1020-70 manufactured by Nippon Kayaku Co., Ltd.) (non-volatile content: 50% by mass) (22.5 mass parts in terms of non-volatile content) And 20 parts by mass (10 parts by mass in terms of non-volatile content) of a MEK solution (non-volatile content 50% by mass) of a novolac type phenolic compound (PS-4271 manufactured by Gunei Chemical Industry Co., Ltd.), and an organic compound having a flux function As a MEK solution (non-volatile content 50% by mass) of phenol phthaline (molecular weight: 320.34, functional group equivalent of acidic site: 320.34 g / eq., Manufactured by Wako Pure Chemical Industries, Ltd.) 20 parts by mass (non-volatile) 10 parts by mass) and acrylic polymer (Mw: 850,000, non-vola cresol novolak type epoxy compound (EO
- the varnish was applied to a 38 ⁇ m thick polyethylene terephthalate film (TR1-38, manufactured by Unitika Co., Ltd.) with a release agent coated on the surface, dried by heating at 100 ° C. for 5 minutes, and the resin composition of this embodiment A resin laminate having a physical layer thickness of 30 ⁇ m was obtained.
- Chip adhesion Chip adhesion is JIS Evaluation was performed according to K5600-5-6.
- the resin laminate obtained in Examples 1 to 13 and Comparative Examples 1 to 7 was attached to a chip separated into 4 cm ⁇ 4 cm by a vacuum pressure laminator to obtain a chip with a resin composition layer.
- the chip with the resin composition layer was heated at 200 ° C. for 3 hours using an oven. After returning to room temperature, six cuts were made in the resin composition layer chip at 1 mm intervals in the vertical and horizontal directions so as to be orthogonal to each other, thereby producing a 25 square lattice pattern.
- a chip with a notched resin composition layer is subjected to pressure moisture absorption treatment for up to 96 hours with a pressure cooker (temperature: 121 ° C., humidity: 100% RH, pressure: 2 atm), and then transparently attached at room temperature
- a tape peel test was performed. As a result of the peeling test, A indicates that no peeling has been confirmed, B indicates that peeling has been confirmed only in a very small part, and C indicates that peeling has been largely confirmed. The results are shown in Tables 1 and 2.
- test sample after the pretreatment was measured for continuous humidity insulation resistance under conditions of a temperature of 130 ° C., a humidity of 85% and an applied voltage of 5.0V.
- a resistance value of 10 7 ⁇ or less was short-circuited, and the time until short-circuiting was described as A for 300 hours or more and C as 100 hours or less.
- the results are shown in Tables 1 and 2.
- the resin composition of the present embodiment exhibits various effects such as excellent chip adhesion, adhesion to the substrate, and flux activity. Therefore, it is useful as an underfill material, preferably as a pre-applied underfill material. is there.
- the resin composition of the present embodiment is excellent in flux activity and excellent in adhesion between the chip and the substrate, the bonding between the chip and the substrate, the bonding between the chip and the semiconductor wafer, and further the bonding between the chip and the chip.
- the obtained laminate can be imparted with high reliability that can withstand long-term use in an environment where it is used, and is extremely useful.
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Abstract
Description
ベンゾオキサジン化合物(A)と、フラックス機能を有する有機化合物(B)と、フェノール樹脂及びラジカル重合性を有する熱硬化性樹脂より選択される少なくとも1種の熱硬化性成分(C)と、を含有し、前記ラジカル重合性を有する熱硬化性樹脂が、アルケニル基、マレイミド基、及び(メタ)アクリロイル基からなる群より選択される少なくとも1以上の官能基を有する樹脂又は化合物であり、前記ベンゾオキサジン化合物(A)と熱硬化性成分(C)との質量比((A)/(C))が、20/80~90/10である、樹脂組成物。
前記ベンゾオキサジン化合物(A)が、400以上の分子量を有する、[1]に記載の樹脂組成物。
前記ベンゾオキサジン化合物(A)が、下記式(1)、下記式(2)、下記式(3)、及び下記式(4)で表される化合物からなる群より選択される少なくとも1種を含有する、[1]又は[2]に記載の樹脂組成物。
前記ベンゾオキサジン化合物(A)が、下記式(5)及び下記式(6)で表される化合物からなる群より選択される少なくとも1種を含有する、[1]~[3]のいずれかに記載の樹脂組成物。
前記ベンゾオキサジン化合物(A)が、下記式(5-1)で表される化合物、下記式(5-2)で表される化合物、下記式(5-3)で表される化合物、下記式(6-1)で表される化合物、下記式(6-2)で表される化合物、及び下記式(6-3)で表される化合物からなる群より選択される少なくとも1種を含有する、[1]~[4]のいずれかに記載の樹脂組成物。
前記フラックス機能を有する有機化合物(B)の酸解離定数pKaが、3.8以上15.0以下である、[1]~[5]のいずれかに記載の樹脂組成物。
前記フラックス機能を有する有機化合物(B)が、200以上8,000以下の分子量を有する、[1]~[6]のいずれかに記載の樹脂組成物。
前記フラックス機能を有する有機化合物(B)が、アビエチン酸、ネオアビエチン酸、デヒドロアビエチン酸、ピマール酸、イソピマール酸、パラストリン酸、ジフェノール酸、ジヒドロアビエチン酸、テトラヒドロアビエチン酸、ロジン酸変性樹脂、N,N’-ビス(サリチリデン)-1,2-プロパンジアミン、N,N’-ビス(サリチリデン)-1,3-プロパンジアミン、及びフェノールフタリンからなる群より選択される少なくとも1種を含有する、[1]~[7]のいずれかに記載の樹脂組成物。
前記熱硬化性成分(C)が、マレイミド化合物である、[1]~[8]のいずれかに記載の樹脂組成物。
前記熱硬化性成分(C)が、2,2-ビス{4-(4-マレイミドフェノキシ)フェニル}プロパン、下記式(8)で表されるマレイミド化合物、下記式(9)で表されるマレイミド化合物、下記式(10)で表されるマレイミド化合物、下記式(11)で表されるマレイミド化合物、下記式(12)で表される化合物、及び下記式(13)で表される化合物からなる群より選択される少なくとも1種を含有する、[1]~[9]のいずれかに記載の樹脂組成物。
前記樹脂組成物において、前記フラックス機能を有する有機化合物(B)の含有量が、前記ベンゾオキサジン化合物(A)及び前記熱硬化性成分(C)の合計100質量部に対して、1質量部以上50質量部以下である、[1]~[10]のいずれかに記載の樹脂組成物。
ラジカル重合開始剤(D)を更に含有する、[1]~[11]のいずれかに記載の樹脂組成物。
前記ラジカル重合開始剤(D)の10時間半減期温度が、100℃以上である、[12]に記載の樹脂組成物。
前記ラジカル重合開始剤(D)が、有機過酸化物である、[12]又は[13]に記載の樹脂組成物。
前記ラジカル重合開始剤(D)が、パーオキシエステル、パーオキシケタール、ジアルキルパーオキサイド、又はハイドロパーオキサイド骨格を有する、[12]~[14]のいずれかに記載の樹脂組成物。
前記ラジカル重合開始剤(D)が、ジクミルパーオキサイド、ジ(2-tert-ブチルペルオキシイソプロピル)ベンゼン、1,1,3,3-テトラメチルブチルハイドロパーオキサイド、2,5-ジメチル-2,5-ビス(tert-ブチルペルオキシ)ヘキシン-3、及びtert―ブチルハイドロパーオキサイドからなる群より選択される少なくとも1種を含有する、[12]~[15]のいずれかに記載の樹脂組成物。
前記樹脂組成物中における前記ラジカル重合開始剤(D)の含有量が、前記ベンゾオキサジン化合物(A)及び前記熱硬化性成分(C)の合計100質量部に対して、0.05質量部以上10質量部以下である、[12]~[16]のいずれかに記載の樹脂組成物。
無機充填材(E)を更に含有する、[1]~[17]のいずれかに記載の樹脂組成物。
前記無機充填材(E)の平均粒子径が、3μm以下である、[18]に記載の樹脂組成物。
前記無機充填材(E)が、シリカ、水酸化アルミニウム、アルミナ、ベーマイト、窒化ホウ素、窒化アルミニウム、酸化マグネシウム、及び水酸化マグネシウムからなる群より選択される少なくとも1種を含有する、[18]又は[19]に記載の樹脂組成物。
前記無機充填材(E)が、シリカである、[18]~[20]のいずれかに記載の樹脂組成物。
前記樹脂組成物中における前記無機充填材(E)の含有量が、前記ベンゾオキサジン化合物(A)及び前記熱硬化性成分(C)の合計100質量部に対して、500質量部以下である、[18]~[21]のいずれかに記載の樹脂組成物。
可撓性付与成分(F)を更に含有する、[1]~[22]のいずれかに記載の樹脂組成物。
前記可撓性付与成分(F)が、熱可塑性の高分子化合物を含有し、前記高分子化合物の質量平均分子量が、1,000以上1,000,000以下である、[23]に記載の樹脂組成物。
前記可撓性付与成分(F)が、(メタ)アクリルオリゴマー及び/又は(メタ)アクリルポリマーである、[23]又は[24]に記載の樹脂組成物。
前記樹脂組成物中における前記熱硬化性成分(C)の含有量が、前記ベンゾオキサジン化合物(A)、前記熱硬化性成分(C)、及び可撓性付与成分(F)の合計100質量部に対して、10質量部以上70質量部以下である、[23]~[25]のいずれかに記載の樹脂組成物。
前記樹脂組成物中にける前記フラックス機能を有する有機化合物(B)の含有量が、前記ベンゾオキサジン化合物(A)、前記熱硬化性成分(C)、及び可撓性付与成分(F)の合計100質量部に対し、1質量部以上50質量部以下である、[23]~[26]のいずれかに記載の樹脂組成物。
前記樹脂組成物中における前記無機充填材(E)の含有量が、前記ベンゾオキサジン化合物(A)、前記熱硬化性成分(C)、及び可撓性付与成分(F)の合計100質量部に対して、500質量部以下である、[23]~[27]のいずれかに記載の樹脂組成物。
プリアプライドアンダーフィル材用である、[1]~[28]のいずれかに記載の樹脂組成物。
支持基材と、前記支持基材上に積層された[1]~[29]のいずれかに記載の樹脂組成物を含有する層と、を備える積層体。
半導体ウェハと、前記半導体ウェハに積層された[30]に記載の積層体と、を備え、前記樹脂組成物を含有する層が、前記半導体ウェハに積層された、樹脂組成物層付き半導体ウェハ。
半導体搭載用基板と、前記半導体搭載用基板に積層された[30]に記載の積層体と、を備え、前記樹脂組成物を含有する層が、前記半導体搭載用基板に積層された、樹脂組成物層付き半導体搭載用基板。
[31]に記載の樹脂組成物層付き半導体ウェハ、及び/又は、[32]に記載の樹脂組成物層付き半導体搭載用基板を備える、半導体装置。
本実施形態の樹脂組成物は、好適にはチップのフリップチップ実装に使用されるアンダーフィル材として用いられる樹脂組成物であって、ベンゾオキサジン化合物(A)と、フラックス機能を有する有機化合物(B)と、フェノール樹脂及びラジカル重合性を有する熱硬化性樹脂より選択される少なくとも1種の熱硬化性成分(C)と、を含有する。
本実施形態の樹脂組成物におけるベンゾオキサジン化合物(A)は、基本骨格としてオキサジン環を有していれば、特に限定されない。本実施形態において、ベンゾオキサジン化合物(A)には、ナフトオキサジン化合物などの多環オキサジン骨格を有する化合物も含まれる。
本実施形態の樹脂組成物は、フリップチップ実装中においてフラックス活性を発現させるため、フラックス機能を有する有機化合物(B)を含有する。フラックス機能を有する有機化合物(B)は、分子中に1個以上の酸性部位を有する有機化合物であれば、特に限定されない。酸性部位としては、例えば、リン酸基、フェノール性水酸基、カルボキシル基、及びスルホン酸基が好ましく、本実施形態の樹脂組成物をアンダーフィル材、好ましくはプリアプライドアンダーフィル材として用いた半導体装置において、接合部を構成するはんだや銅等の金属のマイグレーション、及び腐食をより有効に防止する観点から、フェノール性水酸基又はカルボキシル基がより好ましい。
本実施形態の樹脂組成物は、ベンゾオキサジン化合物(A)以外の熱硬化性成分を含有する。熱硬化性成分(C)としては、ベンゾオキサジン化合物(A)と反応性を示し、かつ、フラックス成分とは反応性を示さない化合物が挙げられ、フェノール樹脂及び/又はラジカル重合性を有する熱硬化性樹脂が好ましい。
これらのフェノール樹脂は、1種もしくは2種以上を適宜混合して使用することが可能である。
これらのラジカル重合性を有する熱硬化性樹脂は、1種もしくは2種以上を適宜混合して使用することが可能である。
例えば、N-フェニルマレイミド、N-ヒドロキシフェニルマレイミド、ビス(4-マレイミドフェニル)メタン、4,4-ジフェニルメタンビスマレイミド、ビス(3,5-ジメチル-4-マレイミドフェニル)メタン、ビス(3-エチル-5-メチル-4-マレイミドフェニル)メタン、ビス(3,5-ジエチル-4-マレイミドフェニル)メタン、フェニルメタンマレイミド、o-フェニレンビスマレイミド、m-フェニレンビスマレイミド、p-フェニレンビスマレイミド、o-フェニレンビスシトラコンイミド、m-フェニレンビスシトラコンイミド、p-フェニレンビスシトラコンイミド、2,2-ビス(4-(4-マレイミドフェノキシ)-フェニル)プロパン、3,3-ジメチル-5,5-ジエチル-4,4-ジフェニルメタンビスマレイミド、4-メチル-1,3-フェニレンビスマレイミド、1,6-ビスマレイミド-(2,2,4-トリメチル)ヘキサン、4,4-ジフェニルエーテルビスマレイミド、4,4-ジフェニルスルフォンビスマレイミド、1,3-ビス(3-マレイミドフェノキシ)ベンゼン、1,3-ビス(4-マレイミドフェノキシ)ベンゼン、4,4-ジフェニルメタンビスシトラコンイミド、2,2-ビス[4-(4-シトラコンイミドフェノキシ)フェニル]プロパン、ビス(3,5-ジメチル-4-シトラコンイミドフェニル)メタン、ビス(3-エチル-5-メチル-4-シトラコンイミドフェニル)メタン、ビス(3,5-ジエチル-4-シトラコンイミドフェニル)メタン、ポリフェニルメタンマレイミド、ノボラック型マレイミド化合物、ビフェニルアラルキル型マレイミド化合物、2,2-ビス{4-(4-マレイミドフェノキシ)フェニル}プロパン、1,2-ビス(マレイミド)エタン、1,4-ビス(マレイミド)ブタン、1,6-ビス(マレイミド)ヘキサン、N,N’-1,3-フェニレンジマレイミド、N,N’-1,4-フェニレンジマレイミド、N-フェニルマレイミド、下記式(8)で表されるマレイミド化合物、下記式(9)で表されるマレイミド化合物、下記式(10)で表されるマレイミド化合物、下記式(11)で表されるマレイミド化合物、下記式(12)で表されるマレイミド化合物、及び下記式(13)で表されるマレイミド化合物などが挙げられる。
式(10)中、R13は、各々独立に、水素原子又はメチル基を示す。
炭素数1~5のアルキル基としては、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、t-ブチル基、n-ペンチル基、及びネオペンチル基が挙げられる。
R15及びR17共に、8以上の原子が直鎖状に連結した炭化水素基としては、例えば、8以上の炭素原子を有する、置換又は非置換の2価の炭化水素基が挙げられる。置換又は非置換の2価の炭化水素基としては、特に限定されないが、例えば、置換又は非置換の直鎖状脂肪族炭化水素基、置換又は非置換の分岐状脂肪族炭化水素基、及び置換又は非置換の環状脂肪族炭化水素基が挙げられる。例えば、オクチレン基、ノナメチレン基、デカメチレン基、ドデカメチレン基、ヘキサデカメチレン基、及びオクタデカメチレン基が挙げられる。
R16において、置換又は非置換の、環を構成する原子数が4以上10以下のヘテロ原子を含んでもよい環状炭化水素基としては、例えば、置換又は非置換の、環を構成する原子数が4以上10以下である脂環基、置換又は非置換の、環を構成する原子数が4以上10以下である芳香族基、及び置換又は非置換の、環を構成する原子数が4以上10以下である複素環基が挙げられる。なお、環を構成する原子数とは、環状に連結している原子の数であって、側鎖の置換基等の原子数は含まれない。置換又は非置換の脂環基における脂環部分の基としては、例えば、2価又は2価以上の、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロオクチル基、及びシクロデシル基が挙げられる。また、置換基がアルキル基である場合、アルキル基としては、特に限定されないが、炭素数1~10のアルキル基が好ましく、炭素数3~10のアルキル基がより好ましい。炭素数1~10のアルキル基としては、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、t-ブチル基、n-ペンチル基、ネオペンチル基、n-ヘキシル基、テキシル基、n-へプチル基、n-オクチル基、n-エチルヘキシル基、n-ノニル基、及びn-デシル基が挙げられる。アルキル基置換のアルキル基は、1つでもよく、2以上であってもよい。
R18及びR19共に、アルキレン基は前記のとおりである。
Yにおいて、アルキレン基及び芳香族環を有する炭素数6以上30以下の炭化水素基については、前記のとおりである。
本実施形態の樹脂組成物は、一般にラジカル重合に用いられる公知の開始剤として、ラジカル重合開始剤(D)含有することが好ましい。
2,2’-アゾビスブチロニトリル、2,2’-アゾビス(2,4-ジメチルバレロニトリル)、及び2,2’-アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)等のアゾ化合物;アルキルフェノン系光重合開始剤;アシルホスフィンオキシド系光重合開始剤;チタノセン系光重合開始剤などが挙げられる。本実施形態においては、有機過酸化物が好ましく、パーオキシエステル、パーオキシケタール、ジアルキルパーオキサイド、及びハイドロパーオキサイド骨格を有する有機過酸化物がより好ましく、ジクミルパーオキサイド、ジ(2-tert-ブチルペルオキシイソプロピル)ベンゼン、1,1,3,3-テトラメチルブチルハイドロパーオキサイド、2,5-ジメチル-2,5-ビス(tert-ブチルペルオキシ)ヘキシン-3、及びtert―ブチルハイドロパーオキサイドが、製造性の観点から、更に好ましい。
本実施形態の樹脂組成物は、耐燃性の向上、熱伝導率の向上、及び熱膨張率の低減のため、無機充填材(E)を含有することができる。無機充填材を使用することにより、樹脂組成物等の耐燃性、及び熱伝導率を向上させ、熱膨張率を低減することができる。
シランカップリング剤としては、一般に無機物の表面処理に使用されているシランカップリング剤であれば、特に限定されない。例えば、ビニルトリメトキシシラン、及びγ-メタアクリロキシプロピルトリメトキシシラン等のビニルシラン系シランカップリング剤;N-フェニル-3-アミノプロピルトリメトキシシラン等のフェニルアミノシラン系シランカップリング剤;トリメトキシフェニルシラン等のフェニルシラン系シランカップリング剤;イミダゾールシラン系シランカップリング剤が挙げられる。これらのシランカップリング剤は、1種を単独で又は2種以上を適宜混合して使用することができる。
本実施形態の樹脂組成物では、可撓性付与成分(F)を含有することが好ましい。可撓性付与成分(F)は、樹脂組成物を含有する層に対して可撓性を付与できるような成分であれば、特に限定されないが、例えば、ポリイミド、ポリアミドイミド、ポリスチレン、ポリオレフィン、スチレン-ブタジエンゴム(SBR)、イソプレンゴム(IR)、ブタジエンゴム(BR)、(メタ)アクリロニトリルブタジエンゴム(NBR)、ポリウレタン、ポリプロピレン、(メタ)アクリルオリゴマー、(メタ)アクリルポリマー、及びシリコーン樹脂等の熱可塑性の高分子化合物が挙げられる。
これらの可撓性付与成分(F)は、1種を単独で又は2種以上を適宜混合して使用することができる。
本実施形態の樹脂組成物は、ベンゾオキサジン化合物(A)、フラックス機能を有する有機化合物(B)、熱硬化性成分(C)、ラジカル重合性開始剤(D)、無機充填材(E)、及び可撓性付与成分(F)の他に、その他の成分を1種又は2種以上含んでいてもよい。
なお、2種以上の湿潤分散剤を併用する場合には、これらの合計量が前記比率を満たすことが好ましい。
本実施形態の樹脂組成物において、その他の添加剤の含有量は、特に限定されないが、通常、ベンゾオキサジン化合物(A)、熱硬化性成分(C)、及び可撓性付与成分(F)の合計100質量部に対して、それぞれ0.01~10質量部である。ただし、本実施形態の樹脂組成物に可撓性付与成分(F)が含まれない場合には、その他の添加剤の含有量は、ベンゾオキサジン化合物(A)、及び熱硬化性樹脂(C)の合計100質量部に対する前記量に対する前記量とする。
本実施形態の積層体、樹脂組成物層付き半導体ウェハ、樹脂組成物層付き半導体搭載用基板などの樹脂組成物層付き基板、及び半導体装置は、いずれも前記した本発明の樹脂組成物を用いて形成される。
本実施形態の積層体は、支持基材と、支持基材上に積層された本実施形態の樹脂組成物を含有する層と、を備える。このような積層体は、前記した本実施形態の樹脂組成物が、支持基材に添着される。支持基材としては、特に限定されないが、高分子フィルムを使用することができる。高分子フィルムの材質としては、例えば、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリブテン、ポリブタジエン、ポリウレタン、エチレン-酸化ビニル共重合体、ポリエチレンテレフタレート、ポリエチレンナフタレート、及びポリブチレンテレフタレート等のポリエステル、ポリエチレン、ポリプロピレン、エチレン-プロピレン共重合体、ポリメチルペンテン、ポリイミド、及びポリアミドからなる群より選ばれる少なくとも1種以上の樹脂を含有するフィルム、並びにこれらのフィルムの表面に離型剤を塗布した離型フィルムが挙げられる。これらの中でも、ポリエステル、ポリイミド、及びポリアミドが好ましく、その中でもポリエステルの一種である、ポリエチレンテレフタレートがより好ましい。
本実施形態の樹脂組成物層付き半導体ウェハは、半導体ウェハと、その半導体ウェハに積層された前記の積層体における樹脂組成物層とを備え、前記した本実施形態の積層体と半導体ウェハとから形成される。また、本実施形態の樹脂組成物層付き基板は、基板と、その基板に積層された前記の積層体における樹脂組成物層とを備え、前記した本実施形態の積層体と基板から形成される。
本実施形態の半導体装置は、本実施形態の樹脂組成物層付き半導体ウェハ、及び/又は本実施形態の樹脂組成物層付き基板を備え、本実施形態の樹脂組成物層、チップ及び基板等から構成される。本実施形態の半導体装置を製造する方法は、特に限定されないが、例えば、本実施形態の樹脂組成物層付き半導体ウェハを研削等の手段で薄化、及びダイシングソー等による個片化を行い、樹脂組成物層付きチップとし、これを基板に搭載する手法が挙げられる。また、本実施形態の樹脂組成物層付き基板に、チップを搭載してもよい。樹脂組成物層付きチップを基板に搭載する方法、及び半導体チップを樹脂組成物層付き基板に搭載する方法では、熱圧着工法に対応したフリップチップボンダを好適に使用することができる。また、本実施形態ではチップを基板にフリップチップ実装する場合を便宜的に説明しているが、チップをフリップチップ実装しつつ、本実施形態の樹脂組成物を適用する対象は基板以外とすることも可能である。例えば、本実施形態の樹脂組成物は、半導体ウェハ上へチップを搭載する際の半導体ウェハとチップとの接合部や、TSV(Through Silicon Via)等を経由してチップ間接続を行うチップ積層体の、各チップ間の接合部に使用することも可能であり、いずれの場合も本発明による優位性を得ることができる。
(実施例1)
ベンゾオキサジン化合物(A)として、前記一般式(5-1)のベンゾオキサジン化合物(四国化成工業(株)社製P-d型ベンゾオキサジン)のMEK溶液(不揮発分50質量%)160質量部(不揮発分換算で80質量部)と、フラックス機能を有する有機化合物(B)として、デヒドロアビエチン酸(分子量:300.44、pKa:4~5、酸性部位の官能基当量:300g/eq.、和光純薬工業(株)製)のMEK溶液(不揮発分50質量%)40質量部(不揮発分換算で20質量部)と、熱硬化性成分(C)として、前記式(8)におけるR11がすべて水素原子であり、n4が1~3であるマレイミド化合物(BMI-2300、大和化成工業(株)製)のMEK溶液(不揮発分50質量%)10質量部(不揮発分換算で5質量部)、及び前記式(9)で表されるマレイミド化合物(前記式(9)中のn5は、14(平均値)である、BMI-1000P、ケイ・アイ化成(株)製)のMEK溶液(不揮発分50質量%)30質量部(不揮発分換算で15質量部)と、無機充填材(E)として、スラリーシリカ(平均粒子径:0.3μm、不揮発分65質量%(株)アドマテックス社製0.3μmSX-CM1、フェニルアミノシラン処理)153.8質量部(不揮発分換算で100質量部)、ラジカル重合開始剤として、ジクミルパーオキサイド(10時間半減期温度:116.4℃、キシダ化学(株)社製)0.5質量部を混合し、高速攪拌装置を用いて30分間撹拌して、ワニスを得た。このワニスを、表面に離型剤をコートした厚さ38μmのポリエチレンテレフタレートフィルム(TR1-38、ユニチカ(株)製)に塗布し、100℃で5分間加熱乾燥して、本実施形態の樹脂組成物層の厚さが30μmである樹脂積層体を得た。
ベンゾオキサジン化合物(A)として、前記一般式(5-1)のベンゾオキサジン化合物80質量部を不揮発分換算で20質量部に、熱硬化性成分(C)として、前記式(8)のマレイミド化合物5質量部を不揮発分換算で45質量部に、前記式(9)のマレイミド化合物15質量部を不揮発分換算で25質量部に変更し、可撓性付与成分(F)として、アクリルポリマー(質量平均分子量:2900、東亞合成(株)社製ARUFON(登録商標)US-6170)10質量部を混合した以外は、実施例1と同様にしてワニスを調製し、樹脂積層体を得た。
熱硬化性成分(C)として、前記式(8)のマレイミド化合物、及び前記式(9)のマレイミド化合物の代わりに、ジペンタエリスリトールヘキサアクリレート(日本化薬(株)社製DPHA)20質量部に、ラジカル重合開始剤として、ジクミルパーオキサイドの代わりに、tert―ブチルハイドロパーオキサイド(アルケマ吉富(株)社製ルペロックスTBH、10時間半減期温度:165℃)0.5質量部に変更した以外は、実施例1と同様にしてワニスを調製し、樹脂積層体を得た。
熱硬化性成分(C)として、前記式(8)のマレイミド化合物5質量部を配合せずに、前記式(9)のマレイミド化合物15質量部を不揮発分換算で10質量部に変更し、可撓性付与成分(F)として、アクリルポリマー(東亞合成(株)社製ARUFON(登録商標)US-6170)10質量部を混合した以外は、実施例1と同様にしてワニスを調製し、樹脂積層体を得た。
ベンゾオキサジン化合物(A)として、前記一般式(5-1)のベンゾオキサジン化合物(四国化成工業(株)社製P-d型ベンゾオキサジン)のMEK溶液(不揮発分50質量%)50質量部(不揮発分換算で25質量部)と、熱硬化性成分(C)として、前記式(8)におけるR11がすべて水素原子であり、n4が1~3であるマレイミド化合物(BMI-2300、大和化成工業(株)製)のMEK溶液(不揮発分50質量%)16質量部(不揮発分換算で8質量部)、ビス-(3-エチル-5-メチル-4-マレイミドフェニル)メタン(BMI-70、ケイ・アイ化成(株)製)のMEK溶液(不揮発分50質量%)32質量部(不揮発分換算で16質量部)、2,2-ビス{4-(4-マレイミドフェノキシ)フェニル}プロパン(BMI-80、ケイ・アイ化成(株)製)のMEK溶液(不揮発分50質量%)32質量部(不揮発分換算で16質量部)、前記式(9)で表されるマレイミド化合物(前記式(9)中のn5は、14(平均値)である、BMI-1000P、ケイ・アイ化成(株)製)のMEK溶液(不揮発分50質量%)50質量部(不揮発分換算で25質量部)と、可撓性付与成分(F)として、アクリルポリマー(東亞合成(株)社製ARUFON(登録商標)US-6170)10質量部と、フラックス機能を有する有機化合物(B)として、デヒドロアビエチン酸(分子量:300.44、酸性部位の官能基当量:300g/eq.、和光純薬工業(株)製)のMEK溶液(不揮発分50質量%)40質量部(不揮発分換算で20質量部)と、無機充填材(E)として、スラリーシリカ(平均粒子径:0.3μm、不揮発分65質量%(株)アドマテックス社製SC1050-MLQ、ビニルシラン処理)153.8質量部(不揮発分換算で100質量部)と、シランカップリング剤として、フェニルアミノシラン(信越化学工業(株)社製KBM-573)2質量部と、ラジカル重合開始剤として、ジクミルパーオキサイド(10時間半減期温度:116.4℃、キシダ化学(株)社製)0.5質量部を混合し、高速攪拌装置を用いて30分間撹拌して、ワニスを得た。このワニスを、表面に離型剤をコートした厚さ38μmのポリエチレンテレフタレートフィルム(TR1-38、ユニチカ(株)製)に塗布し、100℃で5分間加熱乾燥して、本実施形態の樹脂組成物層の厚さが30μmである樹脂積層体を得た。
フラックス機能を有する有機化合物(B)として、デヒドロアビエチン酸の代わりに、ロジン変性マレイン酸樹脂(荒川化学工業(株)社製マルキード(登録商標)No.32)に変更した以外は、実施例5と同様にしてワニスを調製し、樹脂積層体を得た。
フラックス機能を有する有機化合物(B)として、デヒドロアビエチン酸の代わりに、N,N'-ビス(サリチリデン)-1,2-プロパンジアミン(pKa:12~13、東京化成工業(株)社製)に変更した以外は、実施例5と同様にしてワニスを調製し、樹脂積層体を得た。
フラックス機能を有する有機化合物(B)として、デヒドロアビエチン酸の代わりに、N,N'-ビス(サリチリデン)-1,3-プロパンジアミン(pKa:12~13、東京化成工業(株)社製)に変更した以外は、実施例5と同様にしてワニスを調製し、樹脂積層体を得た。
無機充填材(E)として、スラリーシリカ((株)アドマテックス社製SC1050-MLQ)の代わりに、スラリーシリカ((株)アドマテックス社製0.3μmSV-EM1、平均粒子径0.3μm、低α線グレード、ビニルシラン処理)に変更し、シランカップリング剤として、フェニルアミノシラン(信越化学工業(株)社製KBM-573)を配合せず、湿潤分散剤として、DISPERBYK(登録商標)-111(ビッグケミー・ジャパン(株)製)1質量部を混合した以外は、実施例6と同様にしてワニスを調製し、樹脂積層体を得た。
無機充填材(E)として、スラリーシリカ((株)アドマテックス社製0.3μmSV-EM1、平均粒子径0.3μm、低α線グレード、ビニルシラン処理)の代わりに、スラリーシリカ((株)アドマテックス社製0.3μmSX-EM1、平均粒子径0.3μm、低α線グレード、フェニルアミノシラン処理)に変更した以外は、実施例9と同様にしてワニスを調製し、樹脂積層体を得た。
ベンゾオキサジン化合物(A)として、前記一般式(5-1)のベンゾオキサジン化合物25質量部を不揮発分換算で40質量部に、熱硬化性成分(C)として、前記式(8)のマレイミド化合物8質量部を不揮発分換算で5質量部に、ビス-(3-エチル-5-メチル-4-マレイミドフェニル)メタン(BMI-70、ケイ・アイ化成(株)製)16質量部を不揮発分換算で10質量部に、2,2-ビス{4-(4-マレイミドフェノキシ)フェニル}プロパン(BMI-80、ケイ・アイ化成(株)製)16質量部を不揮発分換算で10質量部に変更した以外は、実施例10と同様にしてワニスを調製し、樹脂積層体を得た。
ベンゾオキサジン化合物(A)として、前記一般式(5-1)のベンゾオキサジン化合物の代わりに、前記一般式(6-1)のベンゾオキサジン化合物(四国化成工業(株)社製F-a型ベンゾオキサジン)に変更し、フラックス機能を有する有機化合物(B)として、ロジン変性マレイン酸樹脂(荒川化学工業(株)社製マルキード(登録商標)No.32)の代わりに、デヒドロアビエチン酸(分子量:300.44、pKa:4~5、酸性部位の官能基当量:300g/eq.、和光純薬工業(株)製)に変更し、無機充填材(E)として、スラリーシリカ(平均粒子径:0.3μm、不揮発分65質量%、(株)アドマテックス社製SC1050-MLQ、ビニルシラン処理)の代わりに、スラリーシリカ(平均粒子径:0.3μm、不揮発分65質量%、(株)アドマテックス社製0.3μmSX-CM1、フェニルアミノシラン処理)に変更し、シランカップリング剤として、フェニルアミノシラン(信越化学工業(株)社製KBM-573)2質量部を配合しなかった以外は、実施例6と同様にしてワニスを調製し、樹脂積層体を得た。
前記一般式(6-1)のベンゾオキサジン化合物25質量部を不揮発分換算で50質量部に、熱硬化性成分(C)として、前記式(8)のマレイミド化合物8質量部を不揮発分換算で3質量部に、ビス-(3-エチル-5-メチル-4-マレイミドフェニル)メタン(BMI-70、ケイ・アイ化成(株)製)16質量部を不揮発分換算で6質量部に、2,2-ビス{4-(4-マレイミドフェノキシ)フェニル}プロパン(BMI-80、ケイ・アイ化成(株)製)16質量部を不揮発分換算で6質量部に変更した以外は、実施例12と同様にしてワニスを調製し、樹脂積層体を得た。
熱硬化性成分として、前記式(8)におけるR11がすべて水素原子であり、n4が1~3であるマレイミド化合物(BMI-2300、大和化成工業(株)製)のMEK溶液(不揮発分50質量%)26質量部(不揮発分換算で13質量部)、ビス-(3-エチル-5-メチル-4-マレイミドフェニル)メタン(BMI-70、ケイ・アイ化成(株)製)のMEK溶液(不揮発分50質量%)52質量部(不揮発分換算で26質量部)、2,2-ビス{4-(4-マレイミドフェノキシ)フェニル}プロパン(BMI-80、ケイ・アイ化成(株)製)のMEK溶液(不揮発分50質量%)52質量部(不揮発分換算で26質量部)、前記式(9)で表されるマレイミド化合物(前記式(9)中のn5は、14(平均値)である、BMI-1000P、ケイ・アイ化成(株)製)のMEK溶液(不揮発分50質量%)50質量部(不揮発分換算で25質量部)と、可撓性付与成分として、アクリルポリマー(東亞合成(株)社製ARUFON(登録商標)US-6170)10質量部と、フラックス機能を有する有機化合物として、デヒドロアビエチン酸(分子量:300.44、酸性部位の官能基当量:300g/eq.、和光純薬工業(株)製)のMEK溶液(不揮発分50質量%)40質量部(不揮発分換算で20質量部)と、無機充填材(E)として、スラリーシリカ(平均粒子径:0.3μm、不揮発分65質量%、(株)アドマテックス社製SC1050-MLQ、ビニルシラン処理)153.8質量部(不揮発分換算で100質量部)と、硬化促進剤として、2-エチル-4-メチルイミダゾール(2E4MZ、四国化成工業(株)製)のMEK溶液(不揮発分10質量%)1質量部(不揮発分換算で0.1質量部)を混合し、高速攪拌装置を用いて30分間撹拌して、ワニスを得た。このワニスを、表面に離型剤をコートした厚さ38μmのポリエチレンテレフタレートフィルム(TR1-38、ユニチカ(株)製)に塗布し、100℃で5分間加熱乾燥して、本実施形態の樹脂組成物層の厚さが30μmである樹脂積層体を得た。
さらに、シランカップリング剤として、フェニルアミノシラン(信越化学工業(株)社製KBM-573)5質量部と、レベリング剤として、シリコーン系表面調整剤(ビックケミー社製BYK-310)0.05質量部を混合した以外は、比較例1と同様にしてワニスを調製し、樹脂積層体を得た。
さらに、シランカップリング剤として、フェニルアミノシラン(信越化学工業(株)社製KBM-573)3質量部と、ラジカル重合開始剤として、ジクミルパーオキサイド(10時間半減期温度:116.4℃、キシダ化学(株)社製)0.5質量部を混合し、硬化促進剤である2-エチル-4-メチルイミダゾール0.1質量部を配合しなかった以外は、比較例1と同様にしてワニスを調製し、樹脂積層体を得た。
フラックス機能を有する有機化合物として、デヒドロアビエチン酸の代わりに、ロジン変性マレイン酸樹脂(荒川化学工業(株)社製マルキード(登録商標)No.32)に変更した以外は、比較例3と同様にしてワニスを調製し、樹脂積層体を得た。
熱硬化性成分として、前記式(8)におけるR11がすべて水素原子であり、n4が1~3であるマレイミド化合物(BMI-2300、大和化成工業(株)製)のMEK溶液(不揮発分50質量%)24質量部(不揮発分換算で12質量部)、ビス-(3-エチル-5-メチル-4-マレイミドフェニル)メタン(BMI-70、ケイ・アイ化成(株)製)のMEK溶液(不揮発分50質量%)48質量部(不揮発分換算で24質量部)、2,2-ビス{4-(4-マレイミドフェノキシ)フェニル}プロパン(BMI-80、ケイ・アイ化成(株)製)のMEK溶液(不揮発分50質量%)48質量部(不揮発分換算で24質量部)と、可撓性付与成分として、アクリルポリマー(Mw:700,000、不揮発分20質量%、ナガセケムテックス(株)社製テイサンレジン(登録商標)SG-708-6)150質量部(不揮発分換算で30質量部)、及びアクリルポリマー(東亞合成(株)社製ARUFON(登録商標)US-6170)10質量部と、フラックス機能を有する有機化合物として、2-(p-トルオイル)安息香酸(東京化成工業(株)社製)のMEK溶液(不揮発分50質量%)40質量部(不揮発分換算で20質量部)と、無機充填材(E)として、スラリーシリカ(平均粒子径:0.3μm、不揮発分65質量%(株)アドマテックス社製SC1050-MLQ、ビニルシラン処理)153.8質量部(不揮発分換算で100質量部)と、シランカップリング剤として、フェニルアミノシラン(信越化学工業(株)社製KBM-573)3質量部と、ラジカル重合開始剤として、ジクミルパーオキサイド(10時間半減期温度:116.4℃、キシダ化学(株)社製)0.5質量部を混合し、高速攪拌装置を用いて30分間撹拌して、ワニスを得た。このワニスを、表面に離型剤をコートした厚さ38μmのポリエチレンテレフタレートフィルム(TR1-38、ユニチカ(株)製)に塗布し、100℃で5分間加熱乾燥して、本実施形態の樹脂組成物層の厚さが30μmである樹脂積層体を得た。
ベンゾオキサジン化合物(A)として、前記一般式(5-1)のベンゾオキサジン化合物(四国化成工業(株)社製P-d型ベンゾオキサジン)のMEK溶液(不揮発分50質量%)180質量部(不揮発分換算で90質量部)と、フラックス機能を有する有機化合物(B)として、デヒドロアビエチン酸(分子量:300.44、pKa:4~5、酸性部位の官能基当量:300g/eq.、和光純薬工業(株)製)のMEK溶液(不揮発分50質量%)40質量部(不揮発分換算で20質量部)と、熱硬化性成分(C)として、前記式(9)で表されるマレイミド化合物(前記式(9)中のn5は、14(平均値)である、BMI-1000P、ケイ・アイ化成(株)製)のMEK溶液(不揮発分50質量%)10質量部(不揮発分換算で5質量部)と、無機充填材(E)として、スラリーシリカ((株)アドマテックス社製0.3μmSX-EM1、平均粒子径0.3μm、低α線グレード、フェニルアミノシラン処理)153.8質量部(不揮発分換算で100質量部)、可撓性付与成分(F)として、アクリルポリマー(東亞合成(株)社製ARUFON(登録商標)US-6170)5質量部、ラジカル重合開始剤として、ジクミルパーオキサイド(10時間半減期温度:116.4℃、キシダ化学(株)社製)0.5質量部、湿潤分散剤として、DISPERBYK(登録商標)-111(ビッグケミー・ジャパン(株)製)1質量部を混合し、高速攪拌装置を用いて30分間撹拌して、ワニスを得た。このワニスを、表面に離型剤をコートした厚さ38μmのポリエチレンテレフタレートフィルム(TR1-38、ユニチカ(株)製)に塗布し、100℃で5分間加熱乾燥して、本実施形態の樹脂組成物層の厚さが30μmである樹脂積層体を得た。
ベンゾオキサジン化合物(A)として、前記一般式(5-1)のベンゾオキサジン化合物(四国化成工業(株)社製P-d型ベンゾオキサジン)のMEK溶液(不揮発分50質量%)30質量部(不揮発分換算で15質量部)と、フラックス機能を有する有機化合物(B)として、デヒドロアビエチン酸(分子量:300.44、pKa:4~5、酸性部位の官能基当量:300g/eq.、和光純薬工業(株)製)のMEK溶液(不揮発分50質量%)40質量部(不揮発分換算で20質量部)と、熱硬化性成分(C)として、前記式(8)におけるR11がすべて水素原子であり、n4が1~3であるマレイミド化合物(BMI-2300、大和化成工業(株)製)のMEK溶液(不揮発分50質量%)60質量部(不揮発分換算で30質量部)と、前記式(9)で表されるマレイミド化合物(前記式(9)中のn5は、14(平均値)である、BMI-1000P、ケイ・アイ化成(株)製)のMEK溶液(不揮発分50質量%)90質量部(不揮発分換算で45質量部)と、無機充填材(E)として、スラリーシリカ((株)アドマテックス社製0.3μmSX-EM1、平均粒子径0.3μm、低α線グレード、フェニルアミノシラン処理)153.8質量部(不揮発分換算で100質量部)、可撓性付与成分(F)として、アクリルポリマー(東亞合成(株)社製ARUFON(登録商標)US-6170)10質量部、ラジカル重合開始剤として、ジクミルパーオキサイド(10時間半減期温度:116.4℃、キシダ化学(株)社製)0.5質量部、湿潤分散剤として、DISPERBYK(登録商標)-111(ビッグケミー・ジャパン(株)製)1質量部を混合し、高速攪拌装置を用いて30分間撹拌して、ワニスを得た。このワニスを、表面に離型剤をコートした厚さ38μmのポリエチレンテレフタレートフィルム(TR1-38、ユニチカ(株)製)に塗布し、100℃で5分間加熱乾燥して、本実施形態の樹脂組成物層の厚さが30μmである樹脂積層体を得た。
熱硬化性成分として、ビスフェノールA型エポキシ化合物(DIC(株)社製EXA-850CRP)のMEK溶液(不揮発分50質量%)124質量部(不揮発分換算で62質量部)と、ノボラック型フェノール化合物(DIC(株)社製フェノライト(登録商標)KA-1163)のMEK溶液(不揮発分50質量%)76質量部(不揮発分換算で38質量部)と、フラックス機能を有する有機化合物として、デヒドロアビエチン酸(分子量:300.44、酸性部位の官能基当量:300g/eq.、和光純薬工業(株)製)のMEK溶液(不揮発分50質量%)40質量部(不揮発分換算で20質量部)を混合し、高速攪拌装置を用いて30分間撹拌して、ワニスを得た。このワニスを、表面に離型剤をコートした厚さ38μmのポリエチレンテレフタレートフィルム(TR1-38、ユニチカ(株)製)に塗布し、100℃で5分間加熱乾燥して、本実施形態の樹脂組成物層の厚さが30μmである樹脂積層体を得た。
熱硬化性成分として、クレゾールノボラック型エポキシ化合物(日本化薬(株)社製EOCN-1020-70)のMEK溶液(不揮発分50質量%)45質量部(不揮発分換算で22.5質量部)と、ノボラック型フェノール化合物(群栄化学工業(株)社製PS-4271)のMEK溶液(不揮発分50質量%)20質量部(不揮発分換算で10質量部)と、フラックス機能を有する有機化合物として、フェノールフタリン(分子量:320.34、酸性部位の官能基当量:320.34g/eq.、和光純薬工業(株)製)のMEK溶液(不揮発分50質量%)20質量部(不揮発分換算で10質量部)と、可撓性付与成分(F)として、アクリルポリマー(Mw:850,000、不揮発分15質量%、ナガセケムテックス(株)社製テイサンレジン(登録商標)SG-P3)のMEK溶液450質量部(不揮発分換算で67.5質量部)と、シリカ(平均粒子径:2.2μm(株)アドマテックス社製SC6103-SQ、SQ処理)137.5質量部と、シランカップリング剤として、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン(信越化学工業(株)社製KBM-303)1.25質量部と、硬化促進剤として、2-フェニル-4-メチルイミダゾール(2P4MZ、四国化成工業(株)製)のMEK溶液(不揮発分10質量%)12.5質量部(不揮発分換算で1.25質量部)を混合し、高速攪拌装置を用いて30分間撹拌して、ワニスを得た。このワニスを、表面に離型剤をコートした厚さ38μmのポリエチレンテレフタレートフィルム(TR1-38、ユニチカ(株)製)に塗布し、100℃で5分間加熱乾燥して、本実施形態の樹脂組成物層の厚さが30μmである樹脂積層体を得た。
(1)フラックス活性
実施例1~13、及び比較例1~9で得られた樹脂積層体を8mm×8mmにカットし、半導体搭用載基板(株)ウォルツ製WALTS-KIT
MB50-0102JYのパッド部分(15μmCu)を覆うように貼り付け、樹脂積層体付き半導体搭載用基板を得た。次に、フリップチップボンダ―を用いて、半導体チップ(株)ウォルツ製WALTS-TEG
MB50-0101JYのバンプ部分(30μmCuピラー+15μmSnAgはんだ)と樹脂積層体付き半導体搭載用基板のパッド部分が正確に重なるように位置合わせした後、はんだ溶融接合させ半導体装置を得た。得られた半導体装置を200℃のオーブンで2時間熱処理した後、接合部分の断面研磨観察を実施し、はんだ接合状態を確認した。断面観察の結果、十分なはんだ濡れ性が確認できたものをA、はんだ濡れ性が確認できなかったものをCとして記載した。結果を表1及び2に示す。
チップ接着性をJIS
K5600-5-6に準じて評価を実施した。例えば、実施例1~13、及び比較例1~7で得られた樹脂積層体を4cm×4cmに個片化したチップに真空加圧式ラミネータにより貼り付けることで樹脂組成物層付きチップを得た。その樹脂組成物層付きチップを、オーブンを使用し、200℃で3時間加熱した。室温に戻した後、樹脂組成物層チップに縦、横それぞれに1mm間隔で各6本の切り込みを互いに直交するように入れ、25マスの直角格子パターンを作製した。切り込み入り樹脂組成物層付きチップに対して、プレッシャークッカー(温度:121℃、湿度:100%RH、圧力:2atm)により96時間まで加圧吸湿処理を施した後に、室温環境下にて透明付着テープによる剥離試験を行った。
剥離試験の結果、全く剥離が確認されなかったものをA、極一部のみに剥離が確認されたものをB、大きく剥離が確認されたものをCとして記載した。結果を表1及び2に示す。
プリント配線基板のL/S=40/40μmの微細回路パターン上に、実施例1~13、及び比較例1~7で得られた樹脂積層体を真空ラミネータにより貼り付け、微細配線間を埋め込んだ。オーブンを使用し、前記で作製した樹脂積層体付き微細回路パターン基板を200℃で3時間加熱し、試験サンプルを作製した。得られた試験サンプルを前処理として、温度85℃、湿度60%の条件下で168時間加湿熱処理し、処理後のサンプルを最高温度260℃に設定したリフロー工程に3回流した。前処理後の試験サンプルを温度130℃、湿度85%、印加電圧5.0Vの条件で連続湿中絶縁抵抗を測定した。
評価基準は、抵抗値107Ω以下を短絡とし、短絡するまでの時間が、300時間以上のものをA、100時間以下のものをCとして記載した。結果を表1及び2に示す。
Claims (33)
- ベンゾオキサジン化合物(A)と、
フラックス機能を有する有機化合物(B)と、
フェノール樹脂及びラジカル重合性を有する熱硬化性樹脂より選択される少なくとも1種の熱硬化性成分(C)と、を含有し、
前記ラジカル重合性を有する熱硬化性樹脂が、アルケニル基、マレイミド基、及び(メタ)アクリロイル基からなる群より選択される少なくとも1以上の官能基を有する樹脂又は化合物であり、
前記ベンゾオキサジン化合物(A)と熱硬化性成分(C)との質量比((A)/(C))が、20/80~90/10である、樹脂組成物。 - 前記ベンゾオキサジン化合物(A)が、400以上の分子量を有する、請求項1に記載の樹脂組成物。
- 前記ベンゾオキサジン化合物(A)が、下記式(1)、下記式(2)、下記式(3)、及び下記式(4)で表される化合物からなる群より選択される少なくとも1種を含有する、請求項1又は2に記載の樹脂組成物。
- 前記ベンゾオキサジン化合物(A)が、下記式(5)及び下記式(6)で表される化合物からなる群より選択される少なくとも1種を含有する、請求項1~3のいずれか一項に記載の樹脂組成物。
- 前記フラックス機能を有する有機化合物(B)の酸解離定数pKaが、3.8以上15.0以下である、請求項1~5のいずれか一項に記載の樹脂組成物。
- 前記フラックス機能を有する有機化合物(B)が、200以上8,000以下の分子量を有する、請求項1~6のいずれか一項に記載の樹脂組成物。
- 前記フラックス機能を有する有機化合物(B)が、アビエチン酸、ネオアビエチン酸、デヒドロアビエチン酸、ピマール酸、イソピマール酸、パラストリン酸、ジフェノール酸、ジヒドロアビエチン酸、テトラヒドロアビエチン酸、ロジン酸変性樹脂、N,N’-ビス(サリチリデン)-1,2-プロパンジアミン、N,N’-ビス(サリチリデン)-1,3-プロパンジアミン、及びフェノールフタリンからなる群より選択される少なくとも1種を含有する、請求項1~7のいずれか一項に記載の樹脂組成物。
- 前記熱硬化性成分(C)が、マレイミド化合物である、請求項1~8のいずれか一項に記載の樹脂組成物。
- 前記熱硬化性成分(C)が、2,2-ビス{4-(4-マレイミドフェノキシ)フェニル}プロパン、下記式(8)で表されるマレイミド化合物、下記式(9)で表されるマレイミド化合物、下記式(10)で表されるマレイミド化合物、下記式(11)で表されるマレイミド化合物、下記式(12)で表される化合物、及び下記式(13)で表される化合物からなる群より選択される少なくとも1種を含有する、請求項1~9のいずれか一項に記載の樹脂組成物。
- 前記樹脂組成物において、前記フラックス機能を有する有機化合物(B)の含有量が、前記ベンゾオキサジン化合物(A)及び前記熱硬化性成分(C)の合計100質量部に対して、1質量部以上50質量部以下である、請求項1~10のいずれか一項に記載の樹脂組成物。
- ラジカル重合開始剤(D)を更に含有する、請求項1~11のいずれか一項に記載の樹脂組成物。
- 前記ラジカル重合開始剤(D)の10時間半減期温度が、100℃以上である、請求項12に記載の樹脂組成物。
- 前記ラジカル重合開始剤(D)が、有機過酸化物である、請求項12又は13に記載の樹脂組成物。
- 前記ラジカル重合開始剤(D)が、パーオキシエステル、パーオキシケタール、ジアルキルパーオキサイド、又はハイドロパーオキサイド骨格を有する、請求項12~14のいずれか一項に記載の樹脂組成物。
- 前記ラジカル重合開始剤(D)が、ジクミルパーオキサイド、ジ(2-tert-ブチルペルオキシイソプロピル)ベンゼン、1,1,3,3-テトラメチルブチルハイドロパーオキサイド、2,5-ジメチル-2,5-ビス(tert-ブチルペルオキシ)ヘキシン-3、及びtert―ブチルハイドロパーオキサイドからなる群より選択される少なくとも1種を含有する、請求項12~15のいずれか一項に記載の樹脂組成物。
- 前記樹脂組成物中における前記ラジカル重合開始剤(D)の含有量が、前記ベンゾオキサジン化合物(A)及び前記熱硬化性成分(C)の合計100質量部に対して、0.05質量部以上10質量部以下である、請求項12~16のいずれか一項に記載の樹脂組成物。
- 無機充填材(E)を更に含有する、請求項1~17のいずれか一項に記載の樹脂組成物。
- 前記無機充填材(E)の平均粒子径が、3μm以下である、請求項18に記載の樹脂組成物。
- 前記無機充填材(E)が、シリカ、水酸化アルミニウム、アルミナ、ベーマイト、窒化ホウ素、窒化アルミニウム、酸化マグネシウム、及び水酸化マグネシウムからなる群より選択される少なくとも1種を含有する、請求項18又は19に記載の樹脂組成物。
- 前記無機充填材(E)が、シリカである、請求項18~20のいずれか一項に記載の樹脂組成物。
- 前記樹脂組成物中における前記無機充填材(E)の含有量が、前記ベンゾオキサジン化合物(A)及び前記熱硬化性成分(C)の合計100質量部に対して、500質量部以下である、請求項18~21のいずれか一項に記載の樹脂組成物。
- 可撓性付与成分(F)を更に含有する、請求項1~22のいずれか一項に記載の樹脂組成物。
- 前記可撓性付与成分(F)が、熱可塑性の高分子化合物を含有し、
前記高分子化合物の質量平均分子量が1,000以上1,000,000以下である、
請求項23に記載の樹脂組成物。 - 前記可撓性付与成分(F)が、(メタ)アクリルオリゴマー及び/又は(メタ)アクリルポリマーである、請求項23又は24に記載の樹脂組成物。
- 前記樹脂組成物中における前記熱硬化性成分(C)の含有量が、前記ベンゾオキサジン化合物(A)、前記熱硬化性成分(C)、及び可撓性付与成分(F)の合計100質量部に対して、10質量部以上70質量部以下である、請求項23~25のいずれか一項に記載の樹脂組成物。
- 前記樹脂組成物中における前記フラックス機能を有する有機化合物(B)の含有量が、前記ベンゾオキサジン化合物(A)、前記熱硬化性成分(C)、及び可撓性付与成分(F)の合計100質量部に対して、1質量部以上50質量部以下である、請求項23~26のいずれか一項に記載の樹脂組成物。
- 前記樹脂組成物中における前記無機充填材(E)の含有量が、前記ベンゾオキサジン化合物(A)、前記熱硬化性成分(C)、及び可撓性付与成分(F)の合計100質量部に対して、500質量部以下である、請求項23~27のいずれか一項に記載の樹脂組成物。
- プリアプライドアンダーフィル材用である、請求項1~28のいずれか一項に記載の樹脂組成物。
- 支持基材と、
前記支持基材上に積層された請求項1~29のいずれか一項に記載の樹脂組成物を含有する層と、
を備える積層体。 - 半導体ウェハと、
前記半導体ウェハに積層された請求項30に記載の積層体と、を備え、
前記樹脂組成物を含有する層が、前記半導体ウェハに積層された、
樹脂組成物層付き半導体ウェハ。 - 半導体搭載用基板と、
前記半導体搭載用基板に積層された請求項30に記載の積層体と、を備え、
前記樹脂組成物を含有する層が、前記半導体搭載用基板に積層された、
樹脂組成物層付き半導体搭載用基板。 - 請求項31に記載の樹脂組成物層付き半導体ウェハ、及び/又は、請求項32に記載の樹脂組成物層付き半導体搭載用基板を備える、半導体装置。
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EP4074740A4 (en) * | 2019-12-11 | 2023-01-11 | Mitsubishi Gas Chemical Company, Inc. | RESIN COMPOSITION, RESIN FILM, MULTILAYER CIRCUIT BOARD AND SEMICONDUCTOR DEVICE |
WO2023140154A1 (ja) * | 2022-01-18 | 2023-07-27 | パナソニックIpマネジメント株式会社 | 液状封止用樹脂組成物及び半導体装置 |
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WO2019208615A1 (ja) * | 2018-04-26 | 2019-10-31 | 三菱瓦斯化学株式会社 | 樹脂組成物、積層体、樹脂組成物層付き半導体ウェハ、樹脂組成物層付き半導体搭載用基板、及び半導体装置 |
WO2020045489A1 (ja) * | 2018-08-30 | 2020-03-05 | 三菱瓦斯化学株式会社 | 樹脂組成物、樹脂シート、多層プリント配線板、及び半導体装置 |
TW202337708A (zh) * | 2022-01-19 | 2023-10-01 | 美商羅傑斯公司 | 包含交聯醯亞胺延伸化合物的熱固性複合材料 |
CN115521411B (zh) * | 2022-11-22 | 2023-03-03 | 武汉市三选科技有限公司 | 低介电损耗的积层膜、其制备方法及电路基板结构 |
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