WO2016204183A1 - Resin composition for film formation, sealing film using same, sealing film provided with support and semiconductor device - Google Patents
Resin composition for film formation, sealing film using same, sealing film provided with support and semiconductor device Download PDFInfo
- Publication number
- WO2016204183A1 WO2016204183A1 PCT/JP2016/067817 JP2016067817W WO2016204183A1 WO 2016204183 A1 WO2016204183 A1 WO 2016204183A1 JP 2016067817 W JP2016067817 W JP 2016067817W WO 2016204183 A1 WO2016204183 A1 WO 2016204183A1
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- WO
- WIPO (PCT)
- Prior art keywords
- film
- sealing film
- resin composition
- resin
- support
- Prior art date
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- 238000007789 sealing Methods 0.000 title claims abstract description 91
- 239000011342 resin composition Substances 0.000 title claims abstract description 66
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 20
- 239000004065 semiconductor Substances 0.000 title claims description 36
- 229920005989 resin Polymers 0.000 claims abstract description 64
- 239000011347 resin Substances 0.000 claims abstract description 64
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims abstract description 28
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
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- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 230000009477 glass transition Effects 0.000 abstract description 11
- 239000010408 film Substances 0.000 description 99
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 27
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- 239000006082 mold release agent Substances 0.000 description 1
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- 239000011368 organic material Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- MOVRCMBPGBESLI-UHFFFAOYSA-N prop-2-enoyloxysilicon Chemical compound [Si]OC(=O)C=C MOVRCMBPGBESLI-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/295—Organic, e.g. plastic containing a filler
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- H—ELECTRICITY
- 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
- H01L24/93—Batch processes
- H01L24/95—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips
- H01L24/96—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips the devices being encapsulated in a common layer, e.g. neo-wafer or pseudo-wafer, said common layer being separable into individual assemblies after connecting
-
- H—ELECTRICITY
- 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
- H01L24/93—Batch processes
- H01L24/95—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips
- H01L24/97—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips the devices being connected to a common substrate, e.g. interposer, said common substrate being separable into individual assemblies after connecting
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
- H01L21/561—Batch processing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
- H01L21/568—Temporary substrate used as encapsulation process aid
-
- 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
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
- H01L2224/12105—Bump connectors formed on an encapsulation of the semiconductor or solid-state body, e.g. bumps on chip-scale packages
Definitions
- the present invention relates to a film-forming resin composition, and more particularly to a film-forming resin composition that achieves both excellent handleability and heat resistance. Furthermore, the present invention provides a sealing film using a resin composition for film formation, a sealing film with a support, which can be applied to sealing of semiconductor chips and embedding of substrates on which electronic components are mounted. The present invention relates to a semiconductor device using these.
- the film-like resin composition for sealing the semiconductor element can be produced, for example, by applying a resin varnish containing an organic solvent to a support and drying it.
- a resin varnish containing an organic solvent to a support and drying it.
- the handleability in the semi-cured state is imparted by leaving the organic solvent to some extent.
- the volatile components mainly organic solvents contained in the resin varnish are difficult to volatilize, so that there is a problem that the volatile components cannot be reduced sufficiently.
- the film-like resin composition for sealing a semiconductor element or the like is required to have a sufficiently reduced volatile component and good handleability.
- the cured resin is required to have a sufficiently high glass transition temperature from the viewpoint of heat resistance and reliability.
- the present invention has been made in view of such circumstances, and can form a sealing film with good handleability even when volatile components are reduced, and has sufficiently high heat resistance (high glass transition temperature). It aims at providing the resin composition for film formation which can form hardened
- a resin composition containing a liquid epoxy resin, a cyanate resin, and an oil gelling agent reduces volatile components in a film formed using the resin composition. Even so, it has been found that a cured product having good handleability and a sufficiently high glass transition temperature (high heat resistance) can be formed, and the present invention has been completed based on such knowledge.
- this invention provides the resin composition for film formation containing a liquid epoxy resin (A), cyanate resin (B), and an oil gelling agent (C).
- the film-forming resin composition of the present invention it is possible to obtain a sealing film that has good handleability even when the volatile components are reduced and can form a cured product having a sufficiently high glass transition temperature.
- the film-forming resin composition of the present invention can further contain a siloxane resin (D) having a phenolic hydroxyl group represented by the following general formula (1).
- each R is independently an alkylene group having 1 to 5 carbon atoms, and m is an integer of 5 to 100. ]
- the film-forming resin composition of the present invention can further contain an inorganic filler (E).
- the present invention also provides a sealing film using the film-forming resin composition according to the present invention.
- the thickness of the sealing film of the present invention can be 30 to 250 ⁇ m.
- the present invention also provides a sealing film with a support in which a support is provided on at least one surface of the sealing film according to the present invention.
- the present invention also provides a semiconductor device comprising a semiconductor element sealed with the sealing film according to the present invention or the sealing film of the sealing film with a support according to the present invention.
- the resin composition for film formation which can form the hardened
- the film-forming resin composition of the present embodiment (hereinafter sometimes referred to as a resin composition) includes a liquid epoxy resin (A) (hereinafter sometimes referred to as a component (A)), a cyanate resin (B) ( Hereinafter, the component (B) may be referred to), and the oil gelling agent (C) (hereinafter may be referred to as component (C)).
- A liquid epoxy resin
- B cyanate resin
- C oil gelling agent
- the film-forming resin composition of the present embodiment it is possible to obtain a sealing film that has good handleability even when the volatile components are reduced and can form a cured product having a sufficiently high glass transition temperature. .
- the film-forming resin composition of the present embodiment can sufficiently reduce the volatile components is not necessarily clear, but the present inventors presume as follows.
- a sealing film is produced by applying a resin varnish composed of a film-forming resin composition to a support and drying it, the resin composition on the side where the support is not provided is on the side where the support is provided. Compared to the resin composition, drying is easy to proceed. Therefore, it is considered that the drying of the resin composition on the side where the support is not provided advances and the volatilization of volatile components (mainly organic solvents) in the resin composition on the side where the support is provided is prevented. It is done.
- the resin composition of the present embodiment by blending the liquid epoxy resin (A), excessive drying of the resin composition on the side where the support is not provided can be suppressed, and the support is provided. It is considered that the volatile component of the resin composition on the side of the surface can be sufficiently volatilized. Further, by blending the oil gelling agent (C), the resin composition comprising the liquid epoxy resin (A) and the cyanate resin (B) is gelled, and excessive tack caused by the liquid resin is suppressed. It is thought that you can.
- a sealing film means the film-form resin composition used in order to seal or embed semiconductor elements, such as a semiconductor chip, and electronic components.
- the liquid epoxy resin of component (A) is not particularly limited as long as it is liquid at 25 ° C., and examples thereof include bisphenol A, bisphenol F, biphenyl, novolac, dicyclopentadiene, and many Examples include functional phenol-based, naphthalene-based, aralkyl-modified, alicyclic and alcohol-based glycidyl ethers, glycidyl amine-based, and glycidyl ester-based resins. These can be used alone or in combination of two or more. Among these, bisphenol F type epoxy resin is preferable from the viewpoint of imparting handleability.
- the epoxy resin that is liquid at 25 ° C. means one having a viscosity at 25 ° C. of 400 Pa ⁇ s or less as measured with an E-type viscometer.
- the compounding amount of the component (A) in the film-forming resin composition is based on the total amount of the components that form the cured product from the viewpoint of imparting good flexibility to the sealing film (inorganic substances such as the component (E) and volatilization. Based on the total amount of components excluding components, it is preferably 10 to 80% by mass, more preferably 15 to 75% by mass, and still more preferably 20 to 70% by mass.
- the cyanate resin of the component (B) is not particularly limited as long as it is a compound having at least two cyanato groups in one molecule, and is a phenol novolac type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, Examples thereof include bisphenol F type cyanate resin and tetramethylbisphenol F type cyanate resin. These can be used alone or in combination of two or more. Among these, bisphenol A type cyanate resin and phenol novolac type cyanate resin are preferable from the viewpoints of dielectric properties, heat resistance, flame retardancy, low thermal expansibility, and low cost.
- cyanate resins examples include bisphenol A type cyanate resin (Lonza Japan Co., Ltd .; trade name Primaset BADCy), phenol novolac type cyanate resin (Lonza Japan Co., Ltd .; trade name Primaset PT-30), and the like.
- the amount of component (B) blended is preferably 25 to 400 parts by weight, more preferably 50 to 250 parts by weight, and 60 to 150 parts by weight with respect to 100 parts by weight of component (A). More preferably.
- the blending amount of the component (B) is 25 parts by mass or more, the heat resistance, flame retardancy, and chemical resistance of the film-forming resin composition tend to be improved. It becomes easy to be secured.
- the oil gelling agent of component (C) can have a hydrocarbon group effective for oil solubility and a hydrogen bonding functional group (hydroxy group, carboxy group, amino group, amide group, etc.) effective for self-assembly.
- Component (C) oil gelling agents include hydroxystearic acid, especially hydroxy fatty acids such as 12-hydroxystearic acid, n-lauroyl-L-glutamic acid- ⁇ , ⁇ -dibutylamide, di-p-methylbenzylidene sorbitol gluci 1,3: 2,4-bis-O-benzylidene-D-glucitol, 1,3: 2,4-bis-O- (4-methylbenzylidene) -D-sorbitol, bis (2-ethylhexanoato ) Hydroxyaluminum, compounds represented by the following general formulas (2) to (14), and the like.
- At least one of 12-hydroxystearic acid, n-lauroyl-L-glutamic acid- ⁇ , ⁇ -dibutyramide, and 1,3: 2,4-bis-O-benzylidene-D-glucitol is more preferable. .
- n1 is an integer of 3 to 10
- n2 is an integer of 2 to 6
- R 1 is a saturated hydrocarbon group having 1 to 20 carbon atoms
- X 1 is a sulfur atom or an oxygen atom.
- R 2 is a saturated hydrocarbon group having 1 to 20 carbon atoms
- Y 1 is a bond (single bond) or a benzene ring (phenylene group).
- R 3 is a saturated hydrocarbon group having 1 to 20 carbon atoms, and Y 2 is a bond or a benzene ring.
- R 4 is a saturated hydrocarbon group having 1 to 20 carbon atoms.
- R 5 and R 6 are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms. ]
- R 7 is a saturated hydrocarbon group having 1 to 20 carbon atoms.
- R 8 is a saturated hydrocarbon group having 1 to 20 carbon atoms.
- Ph represents a phenyl group.
- R 9 and R 10 are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms. ]
- R 11 is a divalent saturated hydrocarbon group having 1 to 10 carbon atoms
- R 12 and R 13 are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms.
- the saturated hydrocarbon group of R 12 and R 13 may be a C 1-20 saturated hydrocarbon group having at least one hydroxyl group in the molecular skeleton.
- the blending amount of component (C) is preferably 0.1 to 30 parts by mass, more preferably 0.3 to 25 parts by mass with respect to 100 parts by mass of the sum of component (A) and component (B). 5 to 20 parts by mass is more preferable, 1 to 10 parts by mass is particularly preferable, and 2 to 8 parts by mass is extremely preferable.
- the compounding amount of the component (C) is 0.1 parts by mass or more, the resin can be sufficiently gelled, and when it is 30 parts by mass or less, the excellent heat resistance of the cyanate resin can be maintained.
- the film forming resin composition of the present embodiment may contain a curing accelerator as necessary.
- the curing accelerator include monofunctional phenols such as p- ( ⁇ -cumyl) phenol, mono ( ⁇ -methylbenzyl) phenol, and di ( ⁇ -methylbenzyl) phenol, zinc naphthenate, copper naphthenate, Examples thereof include organic metal salts such as cobalt naphthenate and tin octylate, amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and phosphorus-based catalysts such as triphenylphosphine. These may be used alone or in combination of two or more.
- the film-forming resin composition of the present embodiment may contain a siloxane resin (D) having a phenolic hydroxyl group represented by the general formula (1) (hereinafter sometimes referred to as component (D)).
- each R is independently an alkylene group having 1 to 5 carbon atoms, and m is an integer of 5 to 100. ]
- the component (D) siloxane resin is not particularly limited as long as it is a siloxane resin containing phenolic hydroxyl groups at both ends of the structure represented by the general formula (1).
- Examples of such a siloxane resin include a trade name X-22-1876 (hydroxyl value: 120 mgKOH / g), a trade name X-22-1875 (hydroxyl value: 60 mgKOH / g), a product manufactured by Shin-Etsu Chemical Co., Ltd.
- Shin-Etsu Chemical Co., Ltd. trade name X-22-1876 (hydroxyl value: 120 mgKOH / g), trade name X-22-, from the viewpoint of excellent heat resistance, low thermal expansion and solvent solubility.
- 1875 (hydroxyl value: 60 mg KOH / g), trade name X-22-1821 (hydroxyl value: 30 mg KOH / g), manufactured by Toray Dow Corning Co., Ltd., trade name BY16-752A (hydroxyl value: 30 mg KOH / g), trade name BY16-799 (hydroxyl value: 60 mgKOH / g) is preferable.
- the blending amount of component (D) is preferably 10 to 100 parts by weight, more preferably 20 to 90 parts by weight, and more preferably 30 to 80 parts by weight with respect to 100 parts by weight of the sum of component (A) and component (B). Is more preferable.
- the blending amount of component (D) is 10 parts by mass or more, the cured product of the resin composition can be sufficiently reduced in elastic modulus, and the stress relaxation property of the resin is improved.
- the outstanding heat resistance which cyanate resin has as it is 100 mass parts or less can be hold
- component (D) When the component (D) is blended, the compatibility between the resins can be improved by pre-reacting with the component (A) and the component (B). That is, after component (A) and component (D) are etherified in an organic solvent at 80 to 120 ° C., component (B) is reacted with imino carbonate and triazine cyclization. The reaction is carried out so that the reaction rate of component (B) due to this reaction (sometimes referred to as disappearance rate) is 20 to 70%.
- the reaction solvent that can be used for the pre-reaction is not particularly limited, but alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
- alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether
- ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
- Solvents such as ester solvents such as ethyl acetate and ⁇ -butyrolactone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, And sulfur atom-containing solvents such as dimethyl sulfoxide. These can be used alone or in combination of two or more.
- cyclohexanone, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, and toluene are preferable, and methyl ethyl ketone, methyl isobutyl ketone, and toluene are more preferable from the viewpoint of high volatility and difficulty in remaining a residual solvent during film production.
- a reaction catalyst can be used as necessary.
- the reaction catalyst include amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and phosphorus-based catalysts such as triphenylphosphine. These may be used alone or in combination of two or more. Among these, it is preferable to use a phosphorus catalyst such as triphenylphosphine from the viewpoint of high reactivity with the component (A) and the component (D).
- an organometallic salt can be used as a reaction catalyst.
- the organic metal salt include zinc naphthenate, manganese naphthenate, copper naphthenate, cobalt naphthenate, tin octylate, and cobalt octylate. These can be used alone or in combination of two or more. Among these, zinc naphthenate and copper naphthenate are preferable from the viewpoints of curability and solvent solubility.
- the reaction rate is 20% or more, the resin is sufficiently compatible, and if the reaction rate is 70% or less, the resulting resin is insoluble in the solvent. It can be avoided.
- the iminocarbonation reaction is a reaction in which an iminocarbonate bond (—O— (C ⁇ NH) —O—) is generated by the addition reaction of a hydroxyl group and a cyanate group, and the triazine cyclization reaction is performed using a cyanate group.
- a three-dimensional network structure is formed by a reaction in which the cyanate group is trimerized to form a triazine ring, whereby the component (A), the component (B), and the component (D) are uniformly dispersed.
- a composition is produced.
- the reaction rate of the imino carbonate reaction and the triazine cyclization reaction is obtained from the peak area disappearance rate by comparing the peak area of the component (B) at the start of the reaction with the peak area after the reaction for a predetermined time by GPC measurement. It is done.
- the film-forming resin composition of the present embodiment may include an inorganic filler (E) (hereinafter sometimes referred to as component (E)).
- the inorganic filler of component (E) is not particularly limited, but silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide , Titanium oxide, boron nitride, calcium carbonate, barium sulfate, aluminum borate, and potassium titanate. These can be used alone or in combination of two or more.
- silica is particularly preferable from the viewpoints of dielectric properties, heat resistance, and low thermal expansion.
- the silica include precipitated silica produced by a wet method and having a high water content, and dry method silica produced by a dry method and containing almost no bound water or the like.
- the dry process silica include crushed silica, fumed silica, and fused spherical silica depending on the production method. Of these, fused spherical silica is preferred because of its low thermal expansibility and high fluidity when filled in a resin.
- the average particle size is preferably 0.1 to 10 ⁇ m, more preferably 0.3 to 8 ⁇ m.
- the average particle size of the fused spherical silica is a particle diameter at a point corresponding to a volume of 50% when the cumulative frequency distribution curve by the particle diameter is obtained with the total volume of the particles being 100%, and the particle size using the laser diffraction scattering method. It can be measured with a distribution measuring device or the like.
- the compounding amount of the component (E) is 100 parts by mass when the total amount of the components forming the cured product in the resin composition for film formation is 100 parts by mass (the total amount of the components excluding inorganic substances such as the component (E) and volatile components is 100 parts by mass. 10 to 300 parts by mass, and more preferably 50 to 250 parts by mass.
- epoxy silane, mercapto silane, amino silane, vinyl silane, styryl silane Coupling agents such as methacryloxysilane, acryloxysilane, titanate, and silicone oligomer can be added as appropriate.
- additives other than the above can be blended with the film-forming resin composition according to this embodiment as long as the effects of the present invention are not impaired.
- additives include surface conditioners, flow conditioners, pigments, mold release agents, and the like.
- the surface conditioner include polyester-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane, and an acrylic polymer.
- the sealing film of the present embodiment is formed using the film-forming resin composition according to the present embodiment.
- the sealing film of the present embodiment includes, for example, a resin varnish in which the components (A) to (C) described above and, if necessary, the components (D), (E) and other components are dissolved or dispersed in an organic solvent. Can be used.
- Resin varnish can be produced by blending components (A) to (C) and, if necessary, components (D), (E) and other components with an organic solvent.
- the organic solvent used for producing the resin varnish is not particularly limited, but alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.
- alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.
- Ketone solvents examples include a solvent containing a sulfur atom-containing solvent such as dimethyl sulfoxide. These can be used alone or in combination of two or more.
- cyclohexanone, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, and toluene are preferable, and methyl ethyl ketone, methyl isobutyl ketone, and toluene are more preferable from the viewpoint of high volatility and difficulty in remaining a residual solvent during film production.
- the amount of the organic solvent used in the production of the resin varnish is 100 parts by mass of the sum of the components (A) to (C) and the components (D) and (E) and other components blended as necessary. Is preferably 8 to 50 parts by mass, more preferably 9 to 45 parts by mass, and particularly preferably 10 to 40 parts by mass.
- the resin varnish thus produced can be applied to one or both sides of the support and then dried by heating to obtain a sealing film.
- a support body for example, Polyolefin films, such as a polyethylene film and a polypropylene film, Vinyl films, such as a polyvinyl chloride film, Polyester films, such as a polyethylene terephthalate film, A polycarbonate film, An acetylcellulose film , Tetrafluoroethylene films, and metal foils such as copper foil and aluminum foil.
- Polyolefin films such as a polyethylene film and a polypropylene film
- Vinyl films such as a polyvinyl chloride film
- Polyester films such as a polyethylene terephthalate film
- a polycarbonate film such as a polycarbonate film
- An acetylcellulose film such as Tetrafluoroethylene films
- metal foils such as copper foil and aluminum foil.
- the thickness of the support is not particularly limited, but is preferably 10 to 200 ⁇ m, and more preferably 20 to 150 ⁇ m.
- the method for applying the resin varnish to one or both sides of the support is not particularly limited, but for example, a coating device such as a comma coater, bar coater, kiss coater, roll coater, gravure coater, die coater or the like is used. be able to.
- a coating device such as a comma coater, bar coater, kiss coater, roll coater, gravure coater, die coater or the like is used. be able to.
- the method of heating and drying the resin varnish applied to the support is not particularly limited, and examples thereof include a method of blowing hot air.
- the sealing film can be obtained by drying at 100 to 140 ° C. for 5 to 20 minutes.
- the thickness of the sealing film of this embodiment is preferably 30 to 250 ⁇ m. Moreover, the sealing film exceeding 250 micrometers can also be manufactured by laminating
- the content of volatile components (mainly organic solvents) in the sealing film is preferably 0.2 to 1.6% by mass, and 0.3 to 1% by mass, based on the total mass of the sealing film. It is more preferable. By setting it as such a range, malfunctions, such as a film crack, can be prevented and favorable handleability is obtained. Further, it is possible to prevent defects such as voids accompanying volatilization of volatile components during thermosetting.
- the sealing film with a support of the present embodiment is one in which a support is provided on at least one surface of the sealing film of the present embodiment.
- a support body the support body used when manufacturing the above-mentioned sealing film can be used.
- the semiconductor device of this embodiment includes a semiconductor element sealed with the sealing film of this embodiment.
- the sealing film with a support of this embodiment can also be used for sealing the semiconductor element with the sealing film.
- FIG. 1 and 2 are schematic cross-sectional views for explaining an embodiment of a method for manufacturing a semiconductor device.
- the support 1 and the sealing film 2 provided on the support 1 are provided on the semiconductor element 20 to be embedded arranged side by side on the substrate 30 having the temporary fixing material 40.
- the process of embedding the semiconductor element 20 in the sealing film 2 by making the sealing film 10 with a support provided opposite and pressing the sealing film 2 on the semiconductor element 20 under heating (FIGS. 1A and 1B)
- a step of curing the sealing film in which the semiconductor element is embedded FIG. 1C).
- a sealing molded product in which the semiconductor element 20 is embedded in the cured product 2a obtained by thermosetting the sealing film is obtained by a laminating method, but even if the sealing molded product is obtained by a compression mold, Good.
- the laminator to be used is not particularly limited, and examples thereof include roll type and balloon type laminators. Among these, from the viewpoint of embeddability, a balloon type capable of vacuum pressurization is preferable.
- the laminating temperature is usually performed below the softening point of the film-like support. Furthermore, the laminating temperature is preferably near the minimum melt viscosity of the sealing film.
- the pressure at the time of laminating varies depending on the size and density of the semiconductor element or electronic component to be embedded, but is preferably in the range of 0.2 to 1.5 MPa, more preferably in the range of 0.3 to 1.0 MPa. preferable.
- the laminating time is not particularly limited, but is preferably 20 to 600 seconds, more preferably 30 to 300 seconds, and still more preferably 40 to 120 seconds.
- the curing of the sealing film can be performed, for example, in the air or under an inert gas.
- the curing temperature is not particularly limited, but is preferably 80 to 280 ° C, more preferably 100 to 240 ° C, and still more preferably 120 to 200 ° C. If the curing temperature is 80 ° C. or higher, the curing of the sealing film proceeds sufficiently and the occurrence of defects can be suppressed. When the curing temperature is 280 ° C. or lower, the occurrence of heat damage to other materials can be suppressed.
- the curing time is not particularly limited, but is preferably 30 to 600 minutes, more preferably 45 to 300 minutes, and still more preferably 60 to 240 minutes. When the curing time is within these ranges, curing of the sealing film proceeds sufficiently, and good production efficiency is obtained. A plurality of curing conditions may be combined.
- a semiconductor device can be obtained through the following insulating layer formation, wiring pattern formation, ball mounting, and dicing steps.
- the insulating layer 50 for the rewiring material is provided on the side where the semiconductor element 20 of the sealing molding 100 peeled off from the substrate 30 is exposed (FIGS. 2A and 2B).
- ball mounting is performed to form the insulating layer 52, the wiring 54, and the ball 56.
- the sealing molded product is separated into pieces by the dicing cutter 60 to obtain the semiconductor device 200.
- thermosetting resin composition (A-1)> In a reaction vessel having a thermometer, a stirrer, and a reflux condenser with a capacity of 500 ml that can be heated and cooled, bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., JER806): 90.0 g and general formula (1) 90.0 g of a siloxane resin having a phenolic hydroxyl group (Shin-Etsu Chemical Co., Ltd., X-22-1876), 120.0 g of methyl isobutyl ketone, and 1.45 g of triphenylphosphine were added. The reaction vessel was heated to 90 ° C.
- thermosetting resin composition solution was cooled to room temperature (25 ° C.).
- 120.0 g of phenol novolac cyanate resin (Lonza Japan Co., Ltd., PT-30) was added.
- 0.06 g of an 8% by mass mineral spirit solution of zinc naphthenate was added.
- the reaction liquid was made to react at the same temperature for 4 hours. Thereafter, the reaction solution was cooled to room temperature to obtain a thermosetting resin composition solution.
- thermosetting resin composition (A-1).
- ⁇ Preparation of sealing film with support> A predetermined amount of each component shown in Table 2 was dissolved and dispersed in methyl isobutyl ketone to prepare a resin varnish having a solid content of 80% by mass.
- a resin varnish composed of the prepared resin composition for film formation is applied to one side of a polyethylene terephthalate film, and is heat-dried at 120 ° C. for 8 minutes in a drying furnace, so that the sealing film with a support in a semi-cured state (sealing film) Thickness: 100 ⁇ m).
- Liquid epoxy resin JER806 Bisphenol F type epoxy resin (Mitsubishi Chemical Corporation, JER806, trade name)
- Cyanate resin PT-30 phenol novolac type cyanate resin (Lonza Japan Co., Ltd., Primeset PT-30, trade name)
- Oil gelling agent Gelol D 1,3: 2,4-bis-O-benzylidene-D-glucitol (manufactured by Shin Nippon Chemical Co., Ltd., Gelall D, trade name)
- HSA 12-hydroxystearic acid (trade name, manufactured by Wako Pure Chemical Industries, Ltd.)
- NGB n-lauroyl-L-glutamic acid- ⁇ , ⁇ -dibutyramide (trade name, manufactured by Wako Pure Chemical Industries, Ltd.)
- Organic metal salt zinc naphthenate zinc naphthenate 8% by mass mineral spirit solution (trade name, manufactured by Wako Pure Chemical Industries, Ltd.)
- Phenol compound p- ( ⁇ -cumyl) phenol p- ( ⁇ -cumyl) phenol (trade name, manufactured by Tokyo Chemical Industry Co., Ltd.)
- Surface conditioner BYK-310 Polyester-modified polydimethylsiloxane (manufactured by BYK, trade name)
- Inorganic filler spherical silica spherical silica average particle size 0.5 ⁇ m (manufactured by Admatechs, SC-2500-SXJ, trade name)
- a bending testing machine (JIS type 1, cylindrical mandrel method, diameter 2 mm) manufactured by Yoshimitsu Seiki Co., Ltd. was prepared.
- a test piece obtained by cutting the sealing film with a support into 5 cm square was used as a test piece, and the support was applied to a bending tester to evaluate the presence or absence of cracks when the test piece was bent 180 °.
- the results are shown in Table 2.
- the evaluation result of the bending resistance is “B”, the sealing film is inferior in handleability.
- the tan ⁇ of the obtained cured plate was measured with a dynamic viscoelasticity measuring apparatus (Rheogel-E4000, manufactured by UBM Co., Ltd.) (tensile mode, frequency 10 Hz, heating rate 5 ° C./min). The maximum value of tan ⁇ was taken as the glass transition temperature. The results are shown in Table 2.
- Table 1 shows gelling properties of Examples 1 to 6 in which the oil gelling agent of component (C) was blended and Comparative Examples 1 to 2 in which no oil gelling agent was blended.
- an oil gelling agent By blending an oil gelling agent, thixotropy can be imparted to the composition, and even after 3 minutes have passed after the varnished screw tube is tilted, there is no fluidity and the shape can be maintained. From Table 1, it was shown that the gelling property can be imparted by blending the oil gelling agent (C).
- Example 7 to 8 and Comparative Examples 3 to 4 in Table 2 since the liquid epoxy resin of component (A) is commonly used, the content of volatile components is reduced even when the sealing film is thick. Can be made. When the content of volatile components is decreased, cracks or cracks due to deformation are likely to occur in the sealing film. From Examples 7 and 8 in Table 2, the content of volatile components in the film is 0.6% by mass or less. However, it was confirmed that the film exhibits good bending resistance. Furthermore, when a liquid resin is used, the sealing film tends to cause excessive tack due to the liquid resin, but from Examples 7 and 8 in Table 2, tackiness is also good (no stickiness) 100 ⁇ m. It was confirmed that a thick film could be produced.
- the sealing films of Examples 7 and 8 had a glass transition temperature (Tg) of the cured product of 200 ° C. or higher.
- Tg glass transition temperature
- the film-forming resin composition according to the present invention capable of forming a cured product having a high Tg has good heat resistance. , Can get reliability.
- the handleability is favorable, and the resin composition for film formation which can form the hardened
- SYMBOLS 1 Support body, 2 ... Sealing film, 2a ... Hardened
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Abstract
The purpose of the present invention is to provide a resin composition for film formation, said resin composition enabling the formation of a sealing film that is easy to handle even if volatile component(s) therein are reduced and, moreover, enabling the formation of a cured product that has a sufficiently high heat resistance (a high glass transition temperature). Provided is a resin composition for film formation that comprises: a liquid epoxy resin (A), a cyanate resin (B) and an oil gelling agent (C).
Description
本発明は、フィルム形成用樹脂組成物に関し、特に、優れた取り扱い性と耐熱性を両立するフィルム形成用樹脂組成物に関する。さらに、本発明は、半導体チップの封止及び電子部品を実装した基板の埋め込み等への適用を可能とした、フィルム形成用樹脂組成物を用いた封止フィルム、支持体付き封止フィルム、及びこれらを用いた半導体装置に関する。
The present invention relates to a film-forming resin composition, and more particularly to a film-forming resin composition that achieves both excellent handleability and heat resistance. Furthermore, the present invention provides a sealing film using a resin composition for film formation, a sealing film with a support, which can be applied to sealing of semiconductor chips and embedding of substrates on which electronic components are mounted. The present invention relates to a semiconductor device using these.
半導体チップ等の半導体素子の封止は、通常、固形又は液状の樹脂組成物(封止材)を用いてモールド成形で行われている。近年、より簡便に半導体素子を封止するために、基板上に搭載した複数個の半導体素子を、フィルム状樹脂組成物を用いて一度に樹脂封止することが提案されている(特許文献1)。
Sealing of semiconductor elements such as semiconductor chips is usually performed by molding using a solid or liquid resin composition (sealing material). In recent years, in order to more easily encapsulate semiconductor elements, it has been proposed to encapsulate a plurality of semiconductor elements mounted on a substrate at once using a film-like resin composition (Patent Document 1). ).
半導体素子を封止するフィルム状樹脂組成物は、例えば、有機溶媒が含まれる樹脂ワニスを支持体に塗布、乾燥することで製造できる。このように製造されるフィルム状樹脂組成物においては、有機溶媒をある程度残すことで半硬化状態での取り扱い性を付与している。
The film-like resin composition for sealing the semiconductor element can be produced, for example, by applying a resin varnish containing an organic solvent to a support and drying it. In the film-shaped resin composition manufactured in this way, the handleability in the semi-cured state is imparted by leaving the organic solvent to some extent.
しかし、フィルムの膜厚が増大すると、樹脂ワニスに含まれる揮発成分(主に有機溶媒)が揮発しづらいため、揮発成分を十分に低減できないという問題点がある。揮発成分を十分に低減できていない場合、半導体素子等を封止し、フィルム状樹脂組成物を熱硬化した際に、ボイド等の不良が発生しやすくなる。したがって、半導体素子等を封止するフィルム状樹脂組成物においては、揮発成分が十分に低減されていて、且つ取り扱い性が良好であることが要求される。他方で、半導体素子を封止するフィルム状樹脂組成物においては、耐熱性及び信頼性の観点から、硬化後の樹脂が十分に高いガラス転移温度を有することが要求される。
However, when the film thickness increases, the volatile components (mainly organic solvents) contained in the resin varnish are difficult to volatilize, so that there is a problem that the volatile components cannot be reduced sufficiently. When the volatile components are not sufficiently reduced, defects such as voids are likely to occur when the semiconductor element or the like is sealed and the film-like resin composition is thermally cured. Therefore, the film-like resin composition for sealing a semiconductor element or the like is required to have a sufficiently reduced volatile component and good handleability. On the other hand, in a film-shaped resin composition for sealing a semiconductor element, the cured resin is required to have a sufficiently high glass transition temperature from the viewpoint of heat resistance and reliability.
本発明は、このような事情に鑑みなされたものであり、揮発成分を低減しても取り扱い性が良好である封止フィルムを形成でき、且つ十分に高い耐熱性(高ガラス転移温度)を有する硬化物を形成できるフィルム形成用樹脂組成物、封止フィルム、支持体付き封止フィルム、及びこれらを用いた半導体装置を提供することを目的とする。
The present invention has been made in view of such circumstances, and can form a sealing film with good handleability even when volatile components are reduced, and has sufficiently high heat resistance (high glass transition temperature). It aims at providing the resin composition for film formation which can form hardened | cured material, a sealing film, the sealing film with a support body, and a semiconductor device using these.
上記課題を解決するために、本発明者らが検討を進めた結果、液状エポキシ樹脂、シアネート樹脂、及びオイルゲル化剤を含む樹脂組成物が、それを用いて形成したフィルム中の揮発成分を低減しても取り扱い性が良好であり、且つ十分に高いガラス転移温度(高い耐熱性)を有する硬化物を形成できることを見出し、かかる知見に基づいて本発明を完成するに至った。
As a result of investigations by the present inventors to solve the above problems, a resin composition containing a liquid epoxy resin, a cyanate resin, and an oil gelling agent reduces volatile components in a film formed using the resin composition. Even so, it has been found that a cured product having good handleability and a sufficiently high glass transition temperature (high heat resistance) can be formed, and the present invention has been completed based on such knowledge.
すなわち、本発明は、液状エポキシ樹脂(A)、シアネート樹脂(B)、及びオイルゲル化剤(C)を含むフィルム形成用樹脂組成物を提供する。
That is, this invention provides the resin composition for film formation containing a liquid epoxy resin (A), cyanate resin (B), and an oil gelling agent (C).
本発明のフィルム形成用樹脂組成物によれば、揮発成分を低減しても取り扱い性が良好であり、且つ十分に高いガラス転移温度を有する硬化物を形成できる封止フィルムを得ることができる。
According to the film-forming resin composition of the present invention, it is possible to obtain a sealing film that has good handleability even when the volatile components are reduced and can form a cured product having a sufficiently high glass transition temperature.
本発明のフィルム形成用樹脂組成物は、下記一般式(1)で示されるフェノール性水酸基を有するシロキサン樹脂(D)を更に含むことができる。
The film-forming resin composition of the present invention can further contain a siloxane resin (D) having a phenolic hydroxyl group represented by the following general formula (1).
本発明のフィルム形成用樹脂組成物は、無機充填材(E)を更に含むことができる。
The film-forming resin composition of the present invention can further contain an inorganic filler (E).
本発明は、また、上記本発明に係るフィルム形成用樹脂組成物を用いてなる封止フィルムを提供する。
The present invention also provides a sealing film using the film-forming resin composition according to the present invention.
本発明の封止フィルムの厚さは、30~250μmとすることができる。
The thickness of the sealing film of the present invention can be 30 to 250 μm.
本発明は、また、上記本発明に係る封止フィルムの少なくとも1つの面に支持体が設けられた支持体付き封止フィルムを提供する。
The present invention also provides a sealing film with a support in which a support is provided on at least one surface of the sealing film according to the present invention.
本発明は、また、上記本発明に係る封止フィルム、又は上記本発明に係る支持体付き封止フィルムの封止フィルムによって封止された半導体素子を備える半導体装置を提供する。
The present invention also provides a semiconductor device comprising a semiconductor element sealed with the sealing film according to the present invention or the sealing film of the sealing film with a support according to the present invention.
本発明によれば、揮発成分を低減しても取り扱い性が良好である封止フィルムを形成でき、且つ十分に高いガラス転移温度を有する硬化物を形成できるフィルム形成用樹脂組成物、封止フィルム、支持体付き封止フィルム、及びこれらを用いた半導体装置を提供することができる。
ADVANTAGE OF THE INVENTION According to this invention, the resin composition for film formation which can form the hardened | cured material which can form the sealing film which has favorable handleability even if it reduces a volatile component, and has a sufficiently high glass transition temperature, and a sealing film Further, it is possible to provide a sealing film with a support and a semiconductor device using these.
以下、本発明の実施形態について詳細に説明する。
Hereinafter, embodiments of the present invention will be described in detail.
本実施形態のフィルム形成用樹脂組成物(以下、樹脂組成物と呼ぶことがある)は、液状エポキシ樹脂(A)(以下、成分(A)と呼ぶことがある)、シアネート樹脂(B)(以下、成分(B)と呼ぶことがある)、及びオイルゲル化剤(C)(以下、成分(C)と呼ぶことがある)を含むものである。
The film-forming resin composition of the present embodiment (hereinafter sometimes referred to as a resin composition) includes a liquid epoxy resin (A) (hereinafter sometimes referred to as a component (A)), a cyanate resin (B) ( Hereinafter, the component (B) may be referred to), and the oil gelling agent (C) (hereinafter may be referred to as component (C)).
本実施形態のフィルム形成用樹脂組成物によれば、揮発成分を低減しても取り扱い性が良好であり、且つ十分に高いガラス転移温度を有する硬化物を形成できる封止フィルムを得ることができる。
According to the film-forming resin composition of the present embodiment, it is possible to obtain a sealing film that has good handleability even when the volatile components are reduced and can form a cured product having a sufficiently high glass transition temperature. .
本実施形態のフィルム形成用樹脂組成物が、揮発成分を十分に低減できる理由については、必ずしも明らかではないが、本発明者らは以下のように推察している。フィルム形成用樹脂組成物からなる樹脂ワニスを支持体に塗布、乾燥して封止フィルムを製造する場合、支持体が設けられていない側の樹脂組成物は、支持体が設けられている側の樹脂組成物に比べて、乾燥が進み易い。そのため、支持体が設けられていない側の樹脂組成物の乾燥が進み、支持体が設けられている側の樹脂組成物中の揮発成分(主に有機溶媒)の揮発が妨げられていると考えられる。本実施形態の樹脂組成物においては、液状エポキシ樹脂(A)を配合することで、支持体が設けられていない側の樹脂組成物の過度な乾燥を抑制することができ、支持体が設けられている側の樹脂組成物の揮発成分を十分に揮発させることができると考えられる。さらに、オイルゲル化剤(C)を配合することで、液状エポキシ樹脂(A)、及びシアネート樹脂(B)からなる樹脂組成物をゲル化させ、液状の樹脂に起因する過度なタックを抑制することができると考えられる。
The reason why the film-forming resin composition of the present embodiment can sufficiently reduce the volatile components is not necessarily clear, but the present inventors presume as follows. When a sealing film is produced by applying a resin varnish composed of a film-forming resin composition to a support and drying it, the resin composition on the side where the support is not provided is on the side where the support is provided. Compared to the resin composition, drying is easy to proceed. Therefore, it is considered that the drying of the resin composition on the side where the support is not provided advances and the volatilization of volatile components (mainly organic solvents) in the resin composition on the side where the support is provided is prevented. It is done. In the resin composition of the present embodiment, by blending the liquid epoxy resin (A), excessive drying of the resin composition on the side where the support is not provided can be suppressed, and the support is provided. It is considered that the volatile component of the resin composition on the side of the surface can be sufficiently volatilized. Further, by blending the oil gelling agent (C), the resin composition comprising the liquid epoxy resin (A) and the cyanate resin (B) is gelled, and excessive tack caused by the liquid resin is suppressed. It is thought that you can.
なお、本明細書において、封止フィルムとは、半導体チップ等の半導体素子及び電子部品などを封止又は埋め込むために用いられるフィルム状樹脂組成物のことをいう。
In addition, in this specification, a sealing film means the film-form resin composition used in order to seal or embed semiconductor elements, such as a semiconductor chip, and electronic components.
成分(A)の液状エポキシ樹脂としては、25℃にて液状を示すものであれば特に限定はされず、例えば、ビスフェノールA系、ビスフェノールF系、ビフェニル系、ノボラック系、ジシクロペンタジエン系、多官能フェノール系、ナフタレン系、アラルキル変性系、脂環式系及びアルコール系等のグリシジルエーテル、グリシジルアミン系、並びにグリシジルエステル系樹脂が挙げられる。これらは、1種を単独で又は2種以上を組み合わせて使用することができる。上記の中でも、取り扱い性付与の観点から、ビスフェノールF型エポキシ樹脂が好ましい。
The liquid epoxy resin of component (A) is not particularly limited as long as it is liquid at 25 ° C., and examples thereof include bisphenol A, bisphenol F, biphenyl, novolac, dicyclopentadiene, and many Examples include functional phenol-based, naphthalene-based, aralkyl-modified, alicyclic and alcohol-based glycidyl ethers, glycidyl amine-based, and glycidyl ester-based resins. These can be used alone or in combination of two or more. Among these, bisphenol F type epoxy resin is preferable from the viewpoint of imparting handleability.
本明細書において、25℃にて液状を示すエポキシ樹脂とは、E型粘度計で測定した25℃における粘度が400Pa・s以下であるものを指す。
In the present specification, the epoxy resin that is liquid at 25 ° C. means one having a viscosity at 25 ° C. of 400 Pa · s or less as measured with an E-type viscometer.
フィルム形成用樹脂組成物における成分(A)の配合量は、封止フィルムに良好な柔軟性を付与する観点から、硬化物を形成する成分全量を基準として((E)成分等の無機物及び揮発成分を除く成分全量を基準として)、10~80質量%であることが好ましく、15~75質量%であることがより好ましく、20~70質量%であることが更に好ましい。
The compounding amount of the component (A) in the film-forming resin composition is based on the total amount of the components that form the cured product from the viewpoint of imparting good flexibility to the sealing film (inorganic substances such as the component (E) and volatilization. Based on the total amount of components excluding components, it is preferably 10 to 80% by mass, more preferably 15 to 75% by mass, and still more preferably 20 to 70% by mass.
成分(B)のシアネート樹脂としては、1分子中に少なくとも2個のシアナト基を有する化合物であれば特に限定はされず、フェノールノボラック型シアネート樹脂、ビスフェノールA型シアネート樹脂、ビスフェノールE型シアネート樹脂、ビスフェノールF型シアネート樹脂、及びテトラメチルビスフェノールF型シアネート樹脂等が挙げられる。これらは、1種を単独で又は2種以上を組み合わせて使用することができる。上記の中でも、誘電特性、耐熱性、難燃性、低熱膨張性、及び安価である点から、ビスフェノールA型シアネート樹脂、フェノールノボラック型シアネート樹脂が好ましい。
The cyanate resin of the component (B) is not particularly limited as long as it is a compound having at least two cyanato groups in one molecule, and is a phenol novolac type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, Examples thereof include bisphenol F type cyanate resin and tetramethylbisphenol F type cyanate resin. These can be used alone or in combination of two or more. Among these, bisphenol A type cyanate resin and phenol novolac type cyanate resin are preferable from the viewpoints of dielectric properties, heat resistance, flame retardancy, low thermal expansibility, and low cost.
シアネート樹脂の市販品としては、ビスフェノールA型シアネート樹脂(ロンザジャパン株式会社製;商品名Primaset BADCy)、フェノールノボラック型シアネート樹脂(ロンザジャパン株式会社製;商品名Primaset PT-30)等が挙げられる。
Examples of commercially available cyanate resins include bisphenol A type cyanate resin (Lonza Japan Co., Ltd .; trade name Primaset BADCy), phenol novolac type cyanate resin (Lonza Japan Co., Ltd .; trade name Primaset PT-30), and the like.
成分(B)の配合量は、成分(A)100質量部に対して、25~400質量部であることが好ましく、50~250質量部であることがより好ましく、60~150質量部であることが更に好ましい。成分(B)の配合量を25質量部以上とすることで、フィルム形成用樹脂組成物の耐熱性、難燃性、耐薬品性が向上する傾向にあり、400質量部以下とすることで耐湿性が確保されやすくなる。
The amount of component (B) blended is preferably 25 to 400 parts by weight, more preferably 50 to 250 parts by weight, and 60 to 150 parts by weight with respect to 100 parts by weight of component (A). More preferably. When the blending amount of the component (B) is 25 parts by mass or more, the heat resistance, flame retardancy, and chemical resistance of the film-forming resin composition tend to be improved. It becomes easy to be secured.
成分(C)のオイルゲル化剤は、油溶性に効く炭化水素基と、自己集合性に効く水素結合性官能基(ヒドロキシ基、カルボキシ基、アミノ基、アミド基等)とを有することができる。成分(C)のオイルゲル化剤としては、ヒドロキシステアリン酸、特に12-ヒドロキシステアリン酸等のヒドロキシ脂肪酸、n-ラウロイル-L-グルタミン酸-α,γ-ジブチルアミド、ジ-p-メチルベンジリデンソルビトールグルシトール、1,3:2,4-ビス-O-ベンジリデン-D-グルシトール、1,3:2,4-ビス-O-(4-メチルベンジリデン)-D-ソルビトール、ビス(2-エチルヘキサノアト)ヒドロキシアルミニウム、下記一般式(2)~(14)で表わされる化合物等が挙げられる。これらは1種を単独で用いてもよく、2種以上を併用してもよい。これらの中でも、12-ヒドロキシステアリン酸、n-ラウロイル-L-グルタミン酸-α,γ-ジブチルアミド、及び1,3:2,4-ビス-O-ベンジリデン-D-グルシトールの少なくとも1種がより好ましい。
The oil gelling agent of component (C) can have a hydrocarbon group effective for oil solubility and a hydrogen bonding functional group (hydroxy group, carboxy group, amino group, amide group, etc.) effective for self-assembly. Component (C) oil gelling agents include hydroxystearic acid, especially hydroxy fatty acids such as 12-hydroxystearic acid, n-lauroyl-L-glutamic acid-α, γ-dibutylamide, di-p-methylbenzylidene sorbitol gluci 1,3: 2,4-bis-O-benzylidene-D-glucitol, 1,3: 2,4-bis-O- (4-methylbenzylidene) -D-sorbitol, bis (2-ethylhexanoato ) Hydroxyaluminum, compounds represented by the following general formulas (2) to (14), and the like. These may be used alone or in combination of two or more. Among these, at least one of 12-hydroxystearic acid, n-lauroyl-L-glutamic acid-α, γ-dibutyramide, and 1,3: 2,4-bis-O-benzylidene-D-glucitol is more preferable. .
成分(C)の配合量は、成分(A)、及び成分(B)の総和100質量部に対して0.1~30質量部が好ましく、0.3~25質量部がより好ましく、0.5~20質量部が更に好ましく、1~10質量部であることが特に好ましく、2~8質量部であることが極めて好ましい。成分(C)の配合量が0.1質量部以上であると、樹脂を十分にゲル化することができ、30質量部以下であるとシアネート樹脂が有する優れた耐熱性を保持できる。
The blending amount of component (C) is preferably 0.1 to 30 parts by mass, more preferably 0.3 to 25 parts by mass with respect to 100 parts by mass of the sum of component (A) and component (B). 5 to 20 parts by mass is more preferable, 1 to 10 parts by mass is particularly preferable, and 2 to 8 parts by mass is extremely preferable. When the compounding amount of the component (C) is 0.1 parts by mass or more, the resin can be sufficiently gelled, and when it is 30 parts by mass or less, the excellent heat resistance of the cyanate resin can be maintained.
本実施形態のフィルム形成用樹脂組成物には、必要に応じて硬化促進剤を配合してもよい。硬化促進剤としては、例えば、p-(α-クミル)フェノール、モノ(α-メチルベンジル)フェノール、及びジ(α-メチルベンジル)フェノール等の単官能フェノール類、ナフテン酸亜鉛、ナフテン酸銅、ナフテン酸コバルト、及びオクチル酸錫等の有機金属塩、トリエチルアミン、ピリジン、及びトリブチルアミン等のアミン類、メチルイミダゾール及びフェニルイミダゾール等のイミダゾール類、トリフェニルホスフィン等のリン系触媒などが挙げられる。これらは、1種を単独で用いても、2種以上を混合して用いてもよい。
The film forming resin composition of the present embodiment may contain a curing accelerator as necessary. Examples of the curing accelerator include monofunctional phenols such as p- (α-cumyl) phenol, mono (α-methylbenzyl) phenol, and di (α-methylbenzyl) phenol, zinc naphthenate, copper naphthenate, Examples thereof include organic metal salts such as cobalt naphthenate and tin octylate, amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and phosphorus-based catalysts such as triphenylphosphine. These may be used alone or in combination of two or more.
本実施形態のフィルム形成用樹脂組成物は、一般式(1)で示されるフェノール性水酸基を有するシロキサン樹脂(D)(以下、成分(D)と呼ぶことがある)を含んでもよい。
The film-forming resin composition of the present embodiment may contain a siloxane resin (D) having a phenolic hydroxyl group represented by the general formula (1) (hereinafter sometimes referred to as component (D)).
成分(D)のシロキサン樹脂は、上記の一般式(1)で示される構造の両末端にフェノール性水酸基を含有するシロキサン樹脂であれば特に限定されない。このようなシロキサン樹脂としては、例えば、信越化学工業株式会社製、商品名X-22-1876(水酸基価:120mgKOH/g)、商品名X-22-1875(水酸基価:60mgKOH/g)、商品名X-22-1821(水酸基価:30mgKOH/g)、商品名X-22-1822(水酸基価:20mgKOH/g)、商品名X-26-1064(水酸基価:25mgKOH/g)、東レ・ダウコーニング株式会社製、商品名BY16-752A(水酸基価:30mgKOH/g)、商品名BY16-799(水酸基価:60mgKOH/g)が挙げられる。これらは、信越化学工業株式会社又は東レ・ダウコーニング株式会社等から商業的に入手できる。これらの中で、耐熱性、低熱膨張性、及び溶剤溶解性に優れる点から、信越化学工業株式会社製、商品名X-22-1876(水酸基価:120mgKOH/g)、商品名X-22-1875(水酸基価:60mgKOH/g)、商品名X-22-1821(水酸基価:30mgKOH/g)、東レ・ダウコーニング株式会社製、商品名BY16-752A(水酸基価:30mgKOH/g)、商品名BY16-799(水酸基価:60mgKOH/g)が好ましい。
The component (D) siloxane resin is not particularly limited as long as it is a siloxane resin containing phenolic hydroxyl groups at both ends of the structure represented by the general formula (1). Examples of such a siloxane resin include a trade name X-22-1876 (hydroxyl value: 120 mgKOH / g), a trade name X-22-1875 (hydroxyl value: 60 mgKOH / g), a product manufactured by Shin-Etsu Chemical Co., Ltd. Product name X-22-1821 (Hydroxyl value: 30 mgKOH / g), Product name X-22-1822 (Hydroxyl value: 20 mgKOH / g), Product name X-26-1064 (Hydroxyl value: 25 mgKOH / g), Toray Dow Product name BY16-752A (hydroxyl value: 30 mgKOH / g), trade name BY16-799 (hydroxyl value: 60 mgKOH / g), manufactured by Corning Corporation. These are commercially available from Shin-Etsu Chemical Co., Ltd. or Toray Dow Corning Co., Ltd. Of these, Shin-Etsu Chemical Co., Ltd., trade name X-22-1876 (hydroxyl value: 120 mgKOH / g), trade name X-22-, from the viewpoint of excellent heat resistance, low thermal expansion and solvent solubility. 1875 (hydroxyl value: 60 mg KOH / g), trade name X-22-1821 (hydroxyl value: 30 mg KOH / g), manufactured by Toray Dow Corning Co., Ltd., trade name BY16-752A (hydroxyl value: 30 mg KOH / g), trade name BY16-799 (hydroxyl value: 60 mgKOH / g) is preferable.
成分(D)の配合量は、成分(A)、及び成分(B)の総和100質量部に対して、10~100質量部が好ましく、20~90質量部がより好ましく、30~80質量部が更に好ましい。成分(D)の配合量が10質量部以上であると、樹脂組成物の硬化物を十分に低弾性率化でき、樹脂の応力緩和性が向上する。100質量部以下であるとシアネート樹脂が有する優れた耐熱性を保持できる。
The blending amount of component (D) is preferably 10 to 100 parts by weight, more preferably 20 to 90 parts by weight, and more preferably 30 to 80 parts by weight with respect to 100 parts by weight of the sum of component (A) and component (B). Is more preferable. When the blending amount of component (D) is 10 parts by mass or more, the cured product of the resin composition can be sufficiently reduced in elastic modulus, and the stress relaxation property of the resin is improved. The outstanding heat resistance which cyanate resin has as it is 100 mass parts or less can be hold | maintained.
成分(D)を配合する場合、成分(A)、及び成分(B)とプレ反応させることで樹脂同士の相溶性を向上させることができる。すなわち、有機溶媒中、80~120℃で成分(A)、及び成分(D)をエーテル化反応させた後、成分(B)とイミノカーボネ-ト化反応、及びトリアジン環化反応を進行させる。この反応による成分(B)の反応率(消失率と記す場合もある)を20~70%となるように反応を行う。
When the component (D) is blended, the compatibility between the resins can be improved by pre-reacting with the component (A) and the component (B). That is, after component (A) and component (D) are etherified in an organic solvent at 80 to 120 ° C., component (B) is reacted with imino carbonate and triazine cyclization. The reaction is carried out so that the reaction rate of component (B) due to this reaction (sometimes referred to as disappearance rate) is 20 to 70%.
プレ反応に使用可能な反応溶媒としては、特に限定されないが、エタノール、プロパノール、ブタノール、メチルセロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテル等のアルコール系溶媒、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒、酢酸エチル、γ-ブチロラクトン等のエステル系溶媒、テトラヒドロフラン等のエーテル系溶媒、トルエン、キシレン、メシチレン等の芳香族系溶媒、ジメチルホルムアミド、ジメチルアセトアミド、N-メチルピロリドン等の窒素原子含有溶媒、ジメチルスルホキシド等の硫黄原子含有溶媒などが挙げられる。これらは、1種を単独で又は2種以上を組み合わせて使用することができる。上記の中でも、揮発性が高くフィルム作製時に残留溶媒が残りにくい点から、シクロヘキサノン、プロピレングリコールモノメチルエーテル、メチルエチルケトン、メチルイソブチルケトン、トルエンが好ましく、メチルエチルケトン、メチルイソブチルケトン、トルエンがより好ましい。
The reaction solvent that can be used for the pre-reaction is not particularly limited, but alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Solvents, ester solvents such as ethyl acetate and γ-butyrolactone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, And sulfur atom-containing solvents such as dimethyl sulfoxide. These can be used alone or in combination of two or more. Among these, cyclohexanone, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, and toluene are preferable, and methyl ethyl ketone, methyl isobutyl ketone, and toluene are more preferable from the viewpoint of high volatility and difficulty in remaining a residual solvent during film production.
成分(A)と成分(D)のエーテル化反応では、必要に応じて反応触媒を使用することができる。反応触媒としては、例えば、トリエチルアミン、ピリジン、及びトリブチルアミン等のアミン類、メチルイミダゾール及びフェニルイミダゾール等のイミダゾール類、トリフェニルホスフィン等のリン系触媒が挙げられる。これらは、1種を単独で用いても、2種以上を混合して用いてもよい。これらの中でも、成分(A)及び成分(D)に対する反応性が高い点から、トリフェニルホスフィン等のリン系触媒を用いることが好ましい。
In the etherification reaction of component (A) and component (D), a reaction catalyst can be used as necessary. Examples of the reaction catalyst include amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and phosphorus-based catalysts such as triphenylphosphine. These may be used alone or in combination of two or more. Among these, it is preferable to use a phosphorus catalyst such as triphenylphosphine from the viewpoint of high reactivity with the component (A) and the component (D).
エーテル化反応の後のイミノカーボネ-ト化反応、及びトリアジン環化反応では、有機金属塩を反応触媒として用いることができる。有機金属塩としては、例えば、ナフテン酸亜鉛、ナフテン酸マンガン、ナフテン酸銅、ナフテン酸コバルト、オクチル酸錫、及びオクチル酸コバルトが挙げられる。これらは、1種を単独で又は2種以上を組み合わせて使用することができる。上記の中でも、硬化性、溶媒溶解性の観点から、ナフテン酸亜鉛、ナフテン酸銅が好ましい。
In the imino carbonate reaction and triazine cyclization reaction after the etherification reaction, an organometallic salt can be used as a reaction catalyst. Examples of the organic metal salt include zinc naphthenate, manganese naphthenate, copper naphthenate, cobalt naphthenate, tin octylate, and cobalt octylate. These can be used alone or in combination of two or more. Among these, zinc naphthenate and copper naphthenate are preferable from the viewpoints of curability and solvent solubility.
イミノカーボネ-ト化反応、及びトリアジン環化反応では、反応率が20%以上であると樹脂が十分に相溶し、また、反応率が70%以下であると、得られる樹脂が溶媒に不溶となるのを避けられる。
In the imino carbonate reaction and the triazine cyclization reaction, if the reaction rate is 20% or more, the resin is sufficiently compatible, and if the reaction rate is 70% or less, the resulting resin is insoluble in the solvent. It can be avoided.
なお、イミノカーボネ-ト化反応は、水酸基とシアネート基の付加反応によりイミノカーボネ-ト結合(-O-(C=NH)-O-)が生成される反応であり、トリアジン環化反応は、シアネート基が3量化しトリアジン環を形成する反応である。また、このシアネート基が3量化しトリアジン環を形成する反応により3次元網目構造化が進行するが、これによって成分(A)、成分(B)、及び成分(D)が均一に分散された樹脂組成物が製造される。
The iminocarbonation reaction is a reaction in which an iminocarbonate bond (—O— (C═NH) —O—) is generated by the addition reaction of a hydroxyl group and a cyanate group, and the triazine cyclization reaction is performed using a cyanate group. Is a reaction to form a triazine ring by trimerization. In addition, a three-dimensional network structure is formed by a reaction in which the cyanate group is trimerized to form a triazine ring, whereby the component (A), the component (B), and the component (D) are uniformly dispersed. A composition is produced.
イミノカーボネ-ト化反応、及びトリアジン環化反応の反応率は、GPC測定により反応開始時の成分(B)のピーク面積と、所定時間反応後のピーク面積を比較し、ピーク面積の消失率から求められる。
The reaction rate of the imino carbonate reaction and the triazine cyclization reaction is obtained from the peak area disappearance rate by comparing the peak area of the component (B) at the start of the reaction with the peak area after the reaction for a predetermined time by GPC measurement. It is done.
本実施形態のフィルム形成用樹脂組成物は、無機充填材(E)(以下、成分(E)と呼ぶことがある)を含んでもよい。
The film-forming resin composition of the present embodiment may include an inorganic filler (E) (hereinafter sometimes referred to as component (E)).
成分(E)の無機充填材としては、特に限定されるものではないが、シリカ、アルミナ、タルク、マイカ、カオリン、水酸化アルミニウム、ベーマイト、水酸化マグネシウム、ホウ酸亜鉛、スズ酸亜鉛、酸化亜鉛、酸化チタン、窒化ホウ素、炭酸カルシウム、硫酸バリウム、ホウ酸アルミニウム、及びチタン酸カリウム等が挙げられる。これらは、1種を単独で又は2種以上を組み合わせて使用することができる。
The inorganic filler of component (E) is not particularly limited, but silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide , Titanium oxide, boron nitride, calcium carbonate, barium sulfate, aluminum borate, and potassium titanate. These can be used alone or in combination of two or more.
上記の中でも、誘電特性、耐熱性、低熱膨張性の点から、シリカが特に好ましい。シリカとしては、例えば、湿式法で製造され含水率の高い沈降シリカ、及び乾式法で製造され結合水等をほとんど含まない乾式法シリカが挙げられる。乾式法シリカとしては、さらに、製造法の違いにより破砕シリカ、フュームドシリカ、溶融球状シリカが挙げられる。これらの中で、低熱膨張性及び樹脂に充填した際の高流動性から、溶融球状シリカが好ましい。
Among these, silica is particularly preferable from the viewpoints of dielectric properties, heat resistance, and low thermal expansion. Examples of the silica include precipitated silica produced by a wet method and having a high water content, and dry method silica produced by a dry method and containing almost no bound water or the like. Examples of the dry process silica include crushed silica, fumed silica, and fused spherical silica depending on the production method. Of these, fused spherical silica is preferred because of its low thermal expansibility and high fluidity when filled in a resin.
成分(E)として溶融球状シリカを用いる場合、その平均粒子径は0.1~10μmであることが好ましく、0.3~8μmであることがより好ましい。溶融球状シリカの平均粒子径を0.1μm以上にすることで、樹脂に高充填した際の流動性を良好に保つことができ、10μm以下にすることで、粗大粒子の混入確率を減らし粗大粒子起因の不良の発生を抑えることができる。ここで、平均粒子径とは、粒子の全体積を100%として粒子径による累積度数分布曲線を求めたとき、体積50%に相当する点の粒子径であり、レーザ回折散乱法を用いた粒度分布測定装置等で測定することができる。
When molten spherical silica is used as component (E), the average particle size is preferably 0.1 to 10 μm, more preferably 0.3 to 8 μm. By setting the average particle size of the fused spherical silica to 0.1 μm or more, the fluidity when the resin is highly filled can be kept good, and by setting the average particle size to 10 μm or less, the mixing probability of coarse particles is reduced and coarse particles It is possible to suppress the occurrence of defects due to this. Here, the average particle diameter is a particle diameter at a point corresponding to a volume of 50% when the cumulative frequency distribution curve by the particle diameter is obtained with the total volume of the particles being 100%, and the particle size using the laser diffraction scattering method. It can be measured with a distribution measuring device or the like.
本実施形態においては、異なる粒子径のシリカを組み合わせて充填することで、さらなる高充填化が可能となり、流動性を維持したまま充填率の向上が可能となる。
In this embodiment, by combining and combining silica having different particle diameters, it becomes possible to further increase the packing, and it is possible to improve the packing rate while maintaining fluidity.
成分(E)の配合量は、フィルム形成用樹脂組成物における硬化物を形成する成分全量を100質量部としたとき((E)成分等の無機物及び揮発成分を除く成分全量を100質量部としたとき)に、10~300質量部であることが好ましく、50~250質量部であることがより好ましい。無機充填材(E)の配合量を、上記範囲内にすることで、樹脂組成物の成形性と低熱膨張性を良好に保つことができる。
The compounding amount of the component (E) is 100 parts by mass when the total amount of the components forming the cured product in the resin composition for film formation is 100 parts by mass (the total amount of the components excluding inorganic substances such as the component (E) and volatile components is 100 parts by mass. 10 to 300 parts by mass, and more preferably 50 to 250 parts by mass. By making the compounding quantity of an inorganic filler (E) into the said range, the moldability and low thermal expansibility of a resin composition can be kept favorable.
本実施形態のフィルム形成用樹脂組成物には、樹脂組成物中における無機充填材(E)の分散性を向上させるために、エポキシシラン系、メルカプトシラン系、アミノシラン系、ビニルシラン系、スチリルシラン系、メタクリロキシシラン系、アクリロキシシラン系、チタネート系、シリコーンオリゴマ等のカップリング剤を適宜添加することができる。
In the resin composition for film formation of this embodiment, in order to improve the dispersibility of the inorganic filler (E) in the resin composition, epoxy silane, mercapto silane, amino silane, vinyl silane, styryl silane Coupling agents such as methacryloxysilane, acryloxysilane, titanate, and silicone oligomer can be added as appropriate.
また、本実施形態に係るフィルム形成用樹脂組成物には、本発明の効果を損なわない範囲で、上記以外の添加剤を配合することができる。このような添加剤としては、表面調整剤、流動調整剤、顔料、離型剤等を挙げることができる。表面調整剤としては、例えば、ポリエステル変性ポリジメチルシロキサン、ポリエーテル変性ポリジメチルシロキサン、アクリル系重合物等が挙げられる。フィルム形成用樹脂組成物に表面調整剤を配合することで、フィルム形成用樹脂組成物の支持体への濡れ性が向上する傾向がある。
Moreover, additives other than the above can be blended with the film-forming resin composition according to this embodiment as long as the effects of the present invention are not impaired. Examples of such additives include surface conditioners, flow conditioners, pigments, mold release agents, and the like. Examples of the surface conditioner include polyester-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane, and an acrylic polymer. There exists a tendency for the wettability to the support body of the resin composition for film formation to improve by mix | blending a surface conditioning agent with the resin composition for film formation.
本実施形態の封止フィルムは、本実施形態に係るフィルム形成用樹脂組成物を用いてなるものである。
The sealing film of the present embodiment is formed using the film-forming resin composition according to the present embodiment.
本実施形態の封止フィルムは、例えば、上述した成分(A)~(C)、必要に応じて、成分(D)、(E)及びその他の成分が有機溶媒に溶解又は分散した樹脂ワニスを用いて製造することができる。
The sealing film of the present embodiment includes, for example, a resin varnish in which the components (A) to (C) described above and, if necessary, the components (D), (E) and other components are dissolved or dispersed in an organic solvent. Can be used.
樹脂ワニスは、成分(A)~(C)、必要に応じて、成分(D)、(E)及びその他の成分を、有機溶媒と配合し、製造することができる。
Resin varnish can be produced by blending components (A) to (C) and, if necessary, components (D), (E) and other components with an organic solvent.
樹脂ワニスを製造する際に用いる有機溶媒としては、特に制限されないが、例えばエタノール、プロパノール、ブタノール、メチルセロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテル等のアルコール系溶媒、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒、酢酸エチル、γ-ブチロラクトン等のエステル系溶媒、テトラヒドロフラン等のエーテル系溶媒、トルエン、キシレン、メシチレン等の芳香族系溶媒、ジメチルホルムアミド、ジメチルアセトアミド、N-メチルピロリドン等の窒素原子含有溶媒、ジメチルスルホキシド等の硫黄原子含有溶媒などが挙げられる。これらは、1種を単独で又は2種以上を組み合わせて使用することができる。上記の中でも、揮発性が高くフィルム作製時に残留溶媒が残りにくい点から、シクロヘキサノン、プロピレングリコールモノメチルエーテル、メチルエチルケトン、メチルイソブチルケトン、トルエンが好ましく、メチルエチルケトン、メチルイソブチルケトン、トルエンがより好ましい。
The organic solvent used for producing the resin varnish is not particularly limited, but alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone solvents, ester solvents such as ethyl acetate and γ-butyrolactone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atoms such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone Examples thereof include a solvent containing a sulfur atom-containing solvent such as dimethyl sulfoxide. These can be used alone or in combination of two or more. Among these, cyclohexanone, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, and toluene are preferable, and methyl ethyl ketone, methyl isobutyl ketone, and toluene are more preferable from the viewpoint of high volatility and difficulty in remaining a residual solvent during film production.
樹脂ワニスを製造する際の有機溶媒の配合量は、成分(A)~(C)、並びに、必要に応じて配合される成分(D)、(E)及びその他の成分の総和を100質量部としたときに、8~50質量部が好ましく、9~45質量部がより好ましく、10~40質量部が特に好ましい。有機溶媒の配合量を8質量部以上とすることで、樹脂ワニスの流動性が確保されやすくなり、50質量部以下とすることで、フィルム化において揮発させなければならない溶媒量を少なくできる。
The amount of the organic solvent used in the production of the resin varnish is 100 parts by mass of the sum of the components (A) to (C) and the components (D) and (E) and other components blended as necessary. Is preferably 8 to 50 parts by mass, more preferably 9 to 45 parts by mass, and particularly preferably 10 to 40 parts by mass. By setting the blending amount of the organic solvent to 8 parts by mass or more, the fluidity of the resin varnish is easily secured, and by setting it to 50 parts by mass or less, the amount of solvent that must be volatilized in film formation can be reduced.
このようにして製造した樹脂ワニスを、支持体の片面又は両面に塗布した後、加熱乾燥させ、封止フィルムを得ることができる。
The resin varnish thus produced can be applied to one or both sides of the support and then dried by heating to obtain a sealing film.
用いる支持体としては、特に限定されるものではないが、例えば、ポリエチレンフィルム、ポリプロピレンフィルム等のポリオレフィンフィルム、ポリ塩化ビニルフィルム等のビニルフィルム、ポリエチレンテレフタレートフィルム等のポリエステルフィルム、ポリカーボネートフィルム、アセチルセルロースフィルム、テトラフルオロエチレンフィルム、並びに、銅箔及びアルミニウム箔等の金属箔が挙げられる。これらの中でも、価格及び耐熱性の点で、ポリエステルフィルムを用いることが好ましい。
Although it does not specifically limit as a support body to be used, For example, Polyolefin films, such as a polyethylene film and a polypropylene film, Vinyl films, such as a polyvinyl chloride film, Polyester films, such as a polyethylene terephthalate film, A polycarbonate film, An acetylcellulose film , Tetrafluoroethylene films, and metal foils such as copper foil and aluminum foil. Among these, it is preferable to use a polyester film in terms of price and heat resistance.
支持体の厚みも、特に限定されるものではないが、例えば、10~200μmであることが好ましく、20~150μmであることがより好ましい。
The thickness of the support is not particularly limited, but is preferably 10 to 200 μm, and more preferably 20 to 150 μm.
支持体の片面又は両面に樹脂ワニスを塗布する方法としては、特に限定されるわけではないが、例えば、コンマコーター、バーコーター、キスコーター、ロールコーター、グラビアコーター、ダイコーター等の塗工装置を用いることができる。
The method for applying the resin varnish to one or both sides of the support is not particularly limited, but for example, a coating device such as a comma coater, bar coater, kiss coater, roll coater, gravure coater, die coater or the like is used. be able to.
支持体に塗布した樹脂ワニスを加熱乾燥させる方法としては、特に限定されるわけではないが、例えば、熱風吹きつけ等の方法が挙げられる。例えば、100~140℃で、5~20分間乾燥させることで、封止フィルムを得ることができる。
The method of heating and drying the resin varnish applied to the support is not particularly limited, and examples thereof include a method of blowing hot air. For example, the sealing film can be obtained by drying at 100 to 140 ° C. for 5 to 20 minutes.
本実施形態の封止フィルムの厚みは30~250μmであることが好ましい。また、本実施形態の封止フィルムを複数枚積層して、250μmを超える封止用フィルムを製造することもできる。
The thickness of the sealing film of this embodiment is preferably 30 to 250 μm. Moreover, the sealing film exceeding 250 micrometers can also be manufactured by laminating | stacking several sealing films of this embodiment.
封止フィルムにおける揮発成分(主に有機溶媒)の含有量は、封止フィルムの全質量基準で、0.2~1.6質量%であることが好ましく、0.3~1質量%であることがより好ましい。このような範囲とすることにより、フィルム割れ等の不具合を防止でき、良好な取扱い性が得られる。また、熱硬化時に揮発成分の揮発に伴うボイド等の不具合を防止することができる。
The content of volatile components (mainly organic solvents) in the sealing film is preferably 0.2 to 1.6% by mass, and 0.3 to 1% by mass, based on the total mass of the sealing film. It is more preferable. By setting it as such a range, malfunctions, such as a film crack, can be prevented and favorable handleability is obtained. Further, it is possible to prevent defects such as voids accompanying volatilization of volatile components during thermosetting.
本実施形態の支持体付き封止フィルムは、本実施形態の封止フィルムの少なくとも1つの面に支持体が設けられたものである。支持体としては、前述の封止フィルムを製造する際に用いられる支持体を用いることができる。
The sealing film with a support of the present embodiment is one in which a support is provided on at least one surface of the sealing film of the present embodiment. As a support body, the support body used when manufacturing the above-mentioned sealing film can be used.
本実施形態の半導体装置は、本実施形態の封止フィルムによって封止された半導体素子を備えるものである。封止フィルムによる半導体素子の封止には本実施形態の支持体付き封止フィルムを用いることもできる。
The semiconductor device of this embodiment includes a semiconductor element sealed with the sealing film of this embodiment. The sealing film with a support of this embodiment can also be used for sealing the semiconductor element with the sealing film.
図1及び図2は、半導体装置の製造方法の一実施形態を説明するための模式断面図である。本実施形態に係る方法は、仮固定材40を有する基板30上に並べて配置された被埋め込み対象である半導体素子20に、支持体1と支持体1上に設けられた封止フィルム2とを備える支持体付き封止フィルム10を対向させ、半導体素子20に封止フィルム2を加熱下で押圧することにより、封止フィルム2に半導体素子20を埋め込む工程(図1(a)及び(b))と、半導体素子が埋め込まれた封止フィルムを硬化させる工程(図1(c))とを備える。本実施形態においては、ラミネート法によって、封止フィルムが熱硬化した硬化物2aに半導体素子20が埋め込まれた封止成形物が得られているが、コンプレッションモールドにより封止成形物を得てもよい。
1 and 2 are schematic cross-sectional views for explaining an embodiment of a method for manufacturing a semiconductor device. In the method according to the present embodiment, the support 1 and the sealing film 2 provided on the support 1 are provided on the semiconductor element 20 to be embedded arranged side by side on the substrate 30 having the temporary fixing material 40. The process of embedding the semiconductor element 20 in the sealing film 2 by making the sealing film 10 with a support provided opposite and pressing the sealing film 2 on the semiconductor element 20 under heating (FIGS. 1A and 1B) ) And a step of curing the sealing film in which the semiconductor element is embedded (FIG. 1C). In the present embodiment, a sealing molded product in which the semiconductor element 20 is embedded in the cured product 2a obtained by thermosetting the sealing film is obtained by a laminating method, but even if the sealing molded product is obtained by a compression mold, Good.
使用するラミネーターとしては、特に限定されるものではないが、ロール式、バルーン式等のラミネーターが挙げられる。これらの中でも、埋め込み性の観点からは、真空加圧が可能なバルーン式が好ましい。
The laminator to be used is not particularly limited, and examples thereof include roll type and balloon type laminators. Among these, from the viewpoint of embeddability, a balloon type capable of vacuum pressurization is preferable.
ラミネート温度は、通常、フィルム状の支持体の軟化点以下で行う。更に、ラミネート温度は、封止用フィルムの最低溶融粘度付近が好ましい。ラミネート時の圧力は、埋め込む半導体素子又は電子部品のサイズ、密集度によって変わるが、0.2~1.5MPaの範囲で行うことが好ましく、0.3~1.0MPaの範囲で行うことがより好ましい。ラミネート時間も、特に限定されるものではないが、20~600秒が好ましく、30~300秒がより好ましく、40~120秒が更に好ましい。
The laminating temperature is usually performed below the softening point of the film-like support. Furthermore, the laminating temperature is preferably near the minimum melt viscosity of the sealing film. The pressure at the time of laminating varies depending on the size and density of the semiconductor element or electronic component to be embedded, but is preferably in the range of 0.2 to 1.5 MPa, more preferably in the range of 0.3 to 1.0 MPa. preferable. The laminating time is not particularly limited, but is preferably 20 to 600 seconds, more preferably 30 to 300 seconds, and still more preferably 40 to 120 seconds.
封止フィルムの硬化は、例えば、大気下又は不活性ガス下で行うことができる。硬化温度としては、特に限定されるものではないが、80~280℃が好ましく、100~240℃がより好ましく、120~200℃が更に好ましい。硬化温度が80℃以上であれば、封止フィルムの硬化が十分に進み、不具合の発生を抑制することができる。硬化温度が280℃以下の場合は、他の材料への熱害の発生を抑制することができる。硬化時間も、特に限定されるものではないが、30~600分が好ましく、45~300分がより好ましく、60~240分が更に好ましい。硬化時間がこれらの範囲であれば、封止フィルムの硬化が十分に進み、良好な生産効率が得られる。また、硬化条件は、複数を組み合わせてもよい。
The curing of the sealing film can be performed, for example, in the air or under an inert gas. The curing temperature is not particularly limited, but is preferably 80 to 280 ° C, more preferably 100 to 240 ° C, and still more preferably 120 to 200 ° C. If the curing temperature is 80 ° C. or higher, the curing of the sealing film proceeds sufficiently and the occurrence of defects can be suppressed. When the curing temperature is 280 ° C. or lower, the occurrence of heat damage to other materials can be suppressed. The curing time is not particularly limited, but is preferably 30 to 600 minutes, more preferably 45 to 300 minutes, and still more preferably 60 to 240 minutes. When the curing time is within these ranges, curing of the sealing film proceeds sufficiently, and good production efficiency is obtained. A plurality of curing conditions may be combined.
本実施形態においては、以下の絶縁層形成、配線パターン形成、ボールマウント、及びダイシングの各工程を経て、半導体装置を得ることができる。
In the present embodiment, a semiconductor device can be obtained through the following insulating layer formation, wiring pattern formation, ball mounting, and dicing steps.
まず、基板30から剥離した封止成形物100の半導体素子20が露出する側に、再配線材用の絶縁層50を設ける(図2(a)及び(b))。次に、絶縁層50に対し、配線パターン形成を行った後、ボールマウントを行い、絶縁層52、配線54、ボール56を形成する。
First, the insulating layer 50 for the rewiring material is provided on the side where the semiconductor element 20 of the sealing molding 100 peeled off from the substrate 30 is exposed (FIGS. 2A and 2B). Next, after forming a wiring pattern on the insulating layer 50, ball mounting is performed to form the insulating layer 52, the wiring 54, and the ball 56.
次に、ダイシングカッター60により、封止成形物を個片化して、半導体装置200を得る。
Next, the sealing molded product is separated into pieces by the dicing cutter 60 to obtain the semiconductor device 200.
以下、実施例により本発明をさらに具体的に説明するが、本発明はこれらの実施例に何ら限定されるものではない。
Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
<製造例1:熱硬化性樹脂組成物(A-1)の作製>
温度計、攪拌装置、還流冷却管の付いた加熱及び冷却可能な容積500ミリリットルの反応容器に、ビスフェノールF型エポキシ樹脂(三菱化学株式会社製、JER806):90.0gと、一般式(1)で示されるフェノール性水酸基を有するシロキサン樹脂(信越化学工業株式会社製、X-22-1876):90.0gと、メチルイソブチルケトン:120.0gと、トリフェニルホスフィン:1.45gを投入した。反応容器を90℃に昇温し、同温で4時間攪拌することでエーテル化反応を完結させた。次いで、反応容器を室温(25℃)まで冷却した後に、フェノールノボラック型シアネート樹脂(ロンザジャパン株式会社製、PT-30):120.0gを投入した。反応容器を110℃に昇温した後、ナフテン酸亜鉛の8質量%ミネラルスピリット溶液を0.06g投入した。そして、同温で反応液を4時間反応させた。その後、その反応液を室温に冷却し熱硬化性樹脂組成物の溶液を得た。 <Production Example 1: Production of thermosetting resin composition (A-1)>
In a reaction vessel having a thermometer, a stirrer, and a reflux condenser with a capacity of 500 ml that can be heated and cooled, bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., JER806): 90.0 g and general formula (1) 90.0 g of a siloxane resin having a phenolic hydroxyl group (Shin-Etsu Chemical Co., Ltd., X-22-1876), 120.0 g of methyl isobutyl ketone, and 1.45 g of triphenylphosphine were added. The reaction vessel was heated to 90 ° C. and stirred at the same temperature for 4 hours to complete the etherification reaction. Next, after the reaction vessel was cooled to room temperature (25 ° C.), 120.0 g of phenol novolac cyanate resin (Lonza Japan Co., Ltd., PT-30) was added. After raising the temperature of the reaction vessel to 110 ° C., 0.06 g of an 8% by mass mineral spirit solution of zinc naphthenate was added. And the reaction liquid was made to react at the same temperature for 4 hours. Thereafter, the reaction solution was cooled to room temperature to obtain a thermosetting resin composition solution.
温度計、攪拌装置、還流冷却管の付いた加熱及び冷却可能な容積500ミリリットルの反応容器に、ビスフェノールF型エポキシ樹脂(三菱化学株式会社製、JER806):90.0gと、一般式(1)で示されるフェノール性水酸基を有するシロキサン樹脂(信越化学工業株式会社製、X-22-1876):90.0gと、メチルイソブチルケトン:120.0gと、トリフェニルホスフィン:1.45gを投入した。反応容器を90℃に昇温し、同温で4時間攪拌することでエーテル化反応を完結させた。次いで、反応容器を室温(25℃)まで冷却した後に、フェノールノボラック型シアネート樹脂(ロンザジャパン株式会社製、PT-30):120.0gを投入した。反応容器を110℃に昇温した後、ナフテン酸亜鉛の8質量%ミネラルスピリット溶液を0.06g投入した。そして、同温で反応液を4時間反応させた。その後、その反応液を室温に冷却し熱硬化性樹脂組成物の溶液を得た。 <Production Example 1: Production of thermosetting resin composition (A-1)>
In a reaction vessel having a thermometer, a stirrer, and a reflux condenser with a capacity of 500 ml that can be heated and cooled, bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., JER806): 90.0 g and general formula (1) 90.0 g of a siloxane resin having a phenolic hydroxyl group (Shin-Etsu Chemical Co., Ltd., X-22-1876), 120.0 g of methyl isobutyl ketone, and 1.45 g of triphenylphosphine were added. The reaction vessel was heated to 90 ° C. and stirred at the same temperature for 4 hours to complete the etherification reaction. Next, after the reaction vessel was cooled to room temperature (25 ° C.), 120.0 g of phenol novolac cyanate resin (Lonza Japan Co., Ltd., PT-30) was added. After raising the temperature of the reaction vessel to 110 ° C., 0.06 g of an 8% by mass mineral spirit solution of zinc naphthenate was added. And the reaction liquid was made to react at the same temperature for 4 hours. Thereafter, the reaction solution was cooled to room temperature to obtain a thermosetting resin composition solution.
この反応溶液を少量取り出し、GPC測定(ポリスチレン換算、溶離液:テトラヒドロフラン)を行った。溶出時間が約12.2分付近に出現する合成原料のフェノールノボラック型シアネート樹脂のピーク面積について、反応開始時のフェノールノボッラク型シアネート樹脂のピーク面積と比較したところ、ピーク面積の消失率が33%であった。これより、フェノールノボッラク型シアネート樹脂の反応率は33%であった。さらに、反応溶液を少量取り出し、薄膜形成法によりFT-IR測定を行ったところ、重合反応によって生成されるトリアジン環の波数1560cm-1付近に出現するピークを確認することができた。また、エポキシ基の挿入反応によって生成されるイソシアヌレート及びオキサゾリジノンの波数1670cm-1及び1740cm-1付近に出現するピークをそれぞれ確認することができた。その後、所定量のメチルイソブチルケトンを添加することで樹脂分を70質量%に調整し、熱硬化性樹脂組成物(A-1)を得た。
A small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran). The peak area of the phenol novolac cyanate resin, which is a synthetic raw material that appears at around 12.2 minutes, is compared with the peak area of the phenol novolac cyanate resin at the start of the reaction. 33%. From this, the reaction rate of the phenol novolac type cyanate resin was 33%. Further, when a small amount of the reaction solution was taken out and FT-IR measurement was performed by a thin film forming method, a peak appearing near the wave number of 1560 cm −1 of the triazine ring produced by the polymerization reaction could be confirmed. It was also possible to confirm a peak appeared in the vicinity of isocyanurate and wave number 1670 cm -1 and 1740 cm -1 of the oxazolidinone produced by the insertion reaction of the epoxy groups respectively. Thereafter, a predetermined amount of methyl isobutyl ketone was added to adjust the resin content to 70% by mass to obtain a thermosetting resin composition (A-1).
<ゲル化性評価用樹脂組成物の作製>
表1に示した各成分の所定量をメチルイソブチルケトンに溶解し、固形分70質量%の樹脂ワニスを作製した。調整した樹脂ワニスを2mlのスクリュー管に加え、乾燥炉にて120℃で15分間加熱乾燥し、ゲル化評価用樹脂組成物を得た。 <Preparation of resin composition for gelation evaluation>
A predetermined amount of each component shown in Table 1 was dissolved in methyl isobutyl ketone to prepare a resin varnish having a solid content of 70% by mass. The adjusted resin varnish was added to a 2 ml screw tube and dried by heating in a drying furnace at 120 ° C. for 15 minutes to obtain a resin composition for gelation evaluation.
表1に示した各成分の所定量をメチルイソブチルケトンに溶解し、固形分70質量%の樹脂ワニスを作製した。調整した樹脂ワニスを2mlのスクリュー管に加え、乾燥炉にて120℃で15分間加熱乾燥し、ゲル化評価用樹脂組成物を得た。 <Preparation of resin composition for gelation evaluation>
A predetermined amount of each component shown in Table 1 was dissolved in methyl isobutyl ketone to prepare a resin varnish having a solid content of 70% by mass. The adjusted resin varnish was added to a 2 ml screw tube and dried by heating in a drying furnace at 120 ° C. for 15 minutes to obtain a resin composition for gelation evaluation.
<支持体付き封止フィルムの作製>
表2に示した各成分の所定量をメチルイソブチルケトンに溶解、分散させ、固形分80質量%の樹脂ワニスを調製した。調製したフィルム形成用樹脂組成物からなる樹脂ワニスをポリエチレンテレフタレートフィルムの片面に塗布して、乾燥炉にて120℃で8分間加熱乾燥し、半硬化状態の支持体付き封止フィルム(封止フィルムの厚さ:100μm)を作製した。 <Preparation of sealing film with support>
A predetermined amount of each component shown in Table 2 was dissolved and dispersed in methyl isobutyl ketone to prepare a resin varnish having a solid content of 80% by mass. A resin varnish composed of the prepared resin composition for film formation is applied to one side of a polyethylene terephthalate film, and is heat-dried at 120 ° C. for 8 minutes in a drying furnace, so that the sealing film with a support in a semi-cured state (sealing film) Thickness: 100 μm).
表2に示した各成分の所定量をメチルイソブチルケトンに溶解、分散させ、固形分80質量%の樹脂ワニスを調製した。調製したフィルム形成用樹脂組成物からなる樹脂ワニスをポリエチレンテレフタレートフィルムの片面に塗布して、乾燥炉にて120℃で8分間加熱乾燥し、半硬化状態の支持体付き封止フィルム(封止フィルムの厚さ:100μm)を作製した。 <Preparation of sealing film with support>
A predetermined amount of each component shown in Table 2 was dissolved and dispersed in methyl isobutyl ketone to prepare a resin varnish having a solid content of 80% by mass. A resin varnish composed of the prepared resin composition for film formation is applied to one side of a polyethylene terephthalate film, and is heat-dried at 120 ° C. for 8 minutes in a drying furnace, so that the sealing film with a support in a semi-cured state (sealing film) Thickness: 100 μm).
表中の配合成分としては以下のものを用いた。
(1)液状エポキシ樹脂
JER806:ビスフェノールF型エポキシ樹脂(三菱化学株式会社製、JER806、商品名)
(2)シアネート樹脂
PT-30:フェノールノボラック型シアネート樹脂(ロンザジャパン株式会社製、Primaset PT-30、商品名)
(3)オイルゲル化剤
ゲルオールD:1,3:2,4-ビス-O-ベンジリデン-D-グルシトール(新日本理化株式会社製、ゲルオールD、商品名)
HSA:12-ヒドロキシステアリン酸(和光純薬工業株式会社製、商品名)
NGB:n-ラウロイル-L-グルタミン酸-α,γ-ジブチルアミド(和光純薬工業株式会社製、商品名) The following ingredients were used as blending components in the table.
(1) Liquid epoxy resin JER806: Bisphenol F type epoxy resin (Mitsubishi Chemical Corporation, JER806, trade name)
(2) Cyanate resin PT-30: phenol novolac type cyanate resin (Lonza Japan Co., Ltd., Primeset PT-30, trade name)
(3) Oil gelling agent Gelol D: 1,3: 2,4-bis-O-benzylidene-D-glucitol (manufactured by Shin Nippon Chemical Co., Ltd., Gelall D, trade name)
HSA: 12-hydroxystearic acid (trade name, manufactured by Wako Pure Chemical Industries, Ltd.)
NGB: n-lauroyl-L-glutamic acid-α, γ-dibutyramide (trade name, manufactured by Wako Pure Chemical Industries, Ltd.)
(1)液状エポキシ樹脂
JER806:ビスフェノールF型エポキシ樹脂(三菱化学株式会社製、JER806、商品名)
(2)シアネート樹脂
PT-30:フェノールノボラック型シアネート樹脂(ロンザジャパン株式会社製、Primaset PT-30、商品名)
(3)オイルゲル化剤
ゲルオールD:1,3:2,4-ビス-O-ベンジリデン-D-グルシトール(新日本理化株式会社製、ゲルオールD、商品名)
HSA:12-ヒドロキシステアリン酸(和光純薬工業株式会社製、商品名)
NGB:n-ラウロイル-L-グルタミン酸-α,γ-ジブチルアミド(和光純薬工業株式会社製、商品名) The following ingredients were used as blending components in the table.
(1) Liquid epoxy resin JER806: Bisphenol F type epoxy resin (Mitsubishi Chemical Corporation, JER806, trade name)
(2) Cyanate resin PT-30: phenol novolac type cyanate resin (Lonza Japan Co., Ltd., Primeset PT-30, trade name)
(3) Oil gelling agent Gelol D: 1,3: 2,4-bis-O-benzylidene-D-glucitol (manufactured by Shin Nippon Chemical Co., Ltd., Gelall D, trade name)
HSA: 12-hydroxystearic acid (trade name, manufactured by Wako Pure Chemical Industries, Ltd.)
NGB: n-lauroyl-L-glutamic acid-α, γ-dibutyramide (trade name, manufactured by Wako Pure Chemical Industries, Ltd.)
(4)有機金属塩
ナフテン酸亜鉛:ナフテン酸亜鉛8質量%ミネラルスピリット溶液(和光純薬工業株式会社製、商品名)
(5)フェノール化合物
p-(α-クミル)フェノール:p-(α-クミル)フェノール(東京化成工業株式会社製、商品名)
(6)表面調整剤
BYK-310:ポリエステル変性ポリジメチルシロキサン(BYK社製、商品名)
(7)無機充填材
球状シリカ:球状シリカ 平均粒子径0.5μm(株式会社アドマテックス製、SC-2500-SXJ、商品名) (4) Organic metal salt zinc naphthenate: zinc naphthenate 8% by mass mineral spirit solution (trade name, manufactured by Wako Pure Chemical Industries, Ltd.)
(5) Phenol compound p- (α-cumyl) phenol: p- (α-cumyl) phenol (trade name, manufactured by Tokyo Chemical Industry Co., Ltd.)
(6) Surface conditioner BYK-310: Polyester-modified polydimethylsiloxane (manufactured by BYK, trade name)
(7) Inorganic filler spherical silica: spherical silica average particle size 0.5 μm (manufactured by Admatechs, SC-2500-SXJ, trade name)
ナフテン酸亜鉛:ナフテン酸亜鉛8質量%ミネラルスピリット溶液(和光純薬工業株式会社製、商品名)
(5)フェノール化合物
p-(α-クミル)フェノール:p-(α-クミル)フェノール(東京化成工業株式会社製、商品名)
(6)表面調整剤
BYK-310:ポリエステル変性ポリジメチルシロキサン(BYK社製、商品名)
(7)無機充填材
球状シリカ:球状シリカ 平均粒子径0.5μm(株式会社アドマテックス製、SC-2500-SXJ、商品名) (4) Organic metal salt zinc naphthenate: zinc naphthenate 8% by mass mineral spirit solution (trade name, manufactured by Wako Pure Chemical Industries, Ltd.)
(5) Phenol compound p- (α-cumyl) phenol: p- (α-cumyl) phenol (trade name, manufactured by Tokyo Chemical Industry Co., Ltd.)
(6) Surface conditioner BYK-310: Polyester-modified polydimethylsiloxane (manufactured by BYK, trade name)
(7) Inorganic filler spherical silica: spherical silica average particle size 0.5 μm (manufactured by Admatechs, SC-2500-SXJ, trade name)
<評価方法>
(1)樹脂組成物のゲル化性
得られたゲル化性評価用樹脂組成物が入ったスクリュー管を約60°傾けて3分間放置し、樹脂の流動の有無からゲル化性を評価した。その結果を表1に示した。
「A」;樹脂の流動無し
「B」;樹脂の流動有り <Evaluation method>
(1) Gelation property of resin composition The screw tube containing the obtained resin composition for gelation property evaluation was tilted by about 60 ° and left for 3 minutes, and the gelation property was evaluated from the presence or absence of resin flow. The results are shown in Table 1.
“A”: no resin flow “B”: resin flow
(1)樹脂組成物のゲル化性
得られたゲル化性評価用樹脂組成物が入ったスクリュー管を約60°傾けて3分間放置し、樹脂の流動の有無からゲル化性を評価した。その結果を表1に示した。
「A」;樹脂の流動無し
「B」;樹脂の流動有り <Evaluation method>
(1) Gelation property of resin composition The screw tube containing the obtained resin composition for gelation property evaluation was tilted by about 60 ° and left for 3 minutes, and the gelation property was evaluated from the presence or absence of resin flow. The results are shown in Table 1.
“A”: no resin flow “B”: resin flow
(2)支持体付き封止フィルムの揮発成分の含有量の測定
得られた支持体付き封止フィルムを5cm角にカットし、180℃で1時間乾燥させ、乾燥前と乾燥後の質量変化を求めることにより、下記式にしたがって、封止フィルムの全質量基準における揮発成分の含有量を求めた。その結果を表2に示した。
揮発成分の含有量(質量%)=[(乾燥前質量-乾燥後質量)/(乾燥前質量-支持体の質量)]×100 (2) Measurement of content of volatile component of sealing film with support The obtained sealing film with support is cut into 5 cm square, dried at 180 ° C. for 1 hour, and the mass change before and after drying is measured. By calculating | requiring, according to the following formula, content of the volatile component in the total mass reference | standard of a sealing film was calculated | required. The results are shown in Table 2.
Volatile component content (% by mass) = [(mass before drying−mass after drying) / (mass before drying−mass of support)] × 100
得られた支持体付き封止フィルムを5cm角にカットし、180℃で1時間乾燥させ、乾燥前と乾燥後の質量変化を求めることにより、下記式にしたがって、封止フィルムの全質量基準における揮発成分の含有量を求めた。その結果を表2に示した。
揮発成分の含有量(質量%)=[(乾燥前質量-乾燥後質量)/(乾燥前質量-支持体の質量)]×100 (2) Measurement of content of volatile component of sealing film with support The obtained sealing film with support is cut into 5 cm square, dried at 180 ° C. for 1 hour, and the mass change before and after drying is measured. By calculating | requiring, according to the following formula, content of the volatile component in the total mass reference | standard of a sealing film was calculated | required. The results are shown in Table 2.
Volatile component content (% by mass) = [(mass before drying−mass after drying) / (mass before drying−mass of support)] × 100
(3)封止フィルムの耐屈曲性
得られた支持体付き封止フィルムの耐屈曲性は、屈曲試験機(JIS型タイプ1、円筒型マンドレル法)を用い以下の手順で評価した。 (3) Bending resistance of sealing film The bending resistance of the obtained sealing film with support was evaluated by the following procedure using a bending tester (JIS type 1, cylindrical mandrel method).
得られた支持体付き封止フィルムの耐屈曲性は、屈曲試験機(JIS型タイプ1、円筒型マンドレル法)を用い以下の手順で評価した。 (3) Bending resistance of sealing film The bending resistance of the obtained sealing film with support was evaluated by the following procedure using a bending tester (JIS type 1, cylindrical mandrel method).
試験機として、株式会社ヨシミツ精機製の屈曲試験機(JIS型タイプ1、円筒型マンドレル法、直径2mm)を用意した。支持体付き封止フィルムを5cm角にカットしたものを試験片とし、屈曲試験機に支持体をあて、試験片を180°曲げたときのクラックの発生の有無を評価した。その結果を表2に示した。耐屈曲性の評価結果が「B」である場合、封止フィルムは取り扱い性に劣る。
As a testing machine, a bending testing machine (JIS type 1, cylindrical mandrel method, diameter 2 mm) manufactured by Yoshimitsu Seiki Co., Ltd. was prepared. A test piece obtained by cutting the sealing film with a support into 5 cm square was used as a test piece, and the support was applied to a bending tester to evaluate the presence or absence of cracks when the test piece was bent 180 °. The results are shown in Table 2. When the evaluation result of the bending resistance is “B”, the sealing film is inferior in handleability.
(4)封止フィルムのタック性
得られた支持体付き封止フィルムに指を押し当て、封止フィルムが指に張り付いた場合は「B」、張り付かない場合は「A」として評価した。その結果を表2に示した。タック性の評価結果が「B」である場合、封止フィルムは取り扱い性に劣る。 (4) Tackiness of sealing film A finger was pressed against the obtained sealing film with a support, and when the sealing film stuck to the finger, it was evaluated as "B", and when not sticking, it was evaluated as "A". . The results are shown in Table 2. When the evaluation result of tackiness is “B”, the sealing film is inferior in handleability.
得られた支持体付き封止フィルムに指を押し当て、封止フィルムが指に張り付いた場合は「B」、張り付かない場合は「A」として評価した。その結果を表2に示した。タック性の評価結果が「B」である場合、封止フィルムは取り扱い性に劣る。 (4) Tackiness of sealing film A finger was pressed against the obtained sealing film with a support, and when the sealing film stuck to the finger, it was evaluated as "B", and when not sticking, it was evaluated as "A". . The results are shown in Table 2. When the evaluation result of tackiness is “B”, the sealing film is inferior in handleability.
(5)樹脂硬化物のガラス転移温度(Tg)
得られた支持体付き封止フィルムの封止フィルム部分を削り取り、テフロン(登録商標)の型枠に所定量入れ、その両面に銅箔を、銅箔の光沢面が接するように配置し、240℃、2MPa、60分のプレス条件で加熱加圧成形した。成形後、銅箔をはがし、樹脂組成物の硬化物の板(厚さ:1mm)を作製した。 (5) Glass transition temperature (Tg) of cured resin
The sealing film portion of the obtained sealing film with support is scraped off, put in a predetermined amount in a Teflon (registered trademark) formwork, and placed on both sides of the copper foil so that the glossy surface of the copper foil is in contact with it, 240 Heat pressing was performed under the press conditions of 2 ° C. for 60 minutes. After molding, the copper foil was peeled off to produce a cured plate (thickness: 1 mm) of the resin composition.
得られた支持体付き封止フィルムの封止フィルム部分を削り取り、テフロン(登録商標)の型枠に所定量入れ、その両面に銅箔を、銅箔の光沢面が接するように配置し、240℃、2MPa、60分のプレス条件で加熱加圧成形した。成形後、銅箔をはがし、樹脂組成物の硬化物の板(厚さ:1mm)を作製した。 (5) Glass transition temperature (Tg) of cured resin
The sealing film portion of the obtained sealing film with support is scraped off, put in a predetermined amount in a Teflon (registered trademark) formwork, and placed on both sides of the copper foil so that the glossy surface of the copper foil is in contact with it, 240 Heat pressing was performed under the press conditions of 2 ° C. for 60 minutes. After molding, the copper foil was peeled off to produce a cured plate (thickness: 1 mm) of the resin composition.
得られた硬化物の板のtanδを動的粘弾性測定装置(株式会社ユービーエム製、Rheogel-E4000)により、測定した(引張モード、周波数10Hz、昇温速度5℃/min)。そのtanδの極大値をガラス転移温度とした。その結果を表2に示した。
The tan δ of the obtained cured plate was measured with a dynamic viscoelasticity measuring apparatus (Rheogel-E4000, manufactured by UBM Co., Ltd.) (tensile mode, frequency 10 Hz, heating rate 5 ° C./min). The maximum value of tan δ was taken as the glass transition temperature. The results are shown in Table 2.
表1には成分(C)のオイルゲル化剤を配合した実施例1~6と、オイルゲル化剤を配合していない比較例1~2のゲル化性を示した。オイルゲル化剤を配合することで、組成物にチクソ性を付与することができ、ワニス入りスクリュー管を傾けて3分間経過しても流動性がなく、形状を維持することができる。表1から、オイルゲル化剤(C)の配合によって、ゲル化性を付与できることが示された。
Table 1 shows gelling properties of Examples 1 to 6 in which the oil gelling agent of component (C) was blended and Comparative Examples 1 to 2 in which no oil gelling agent was blended. By blending an oil gelling agent, thixotropy can be imparted to the composition, and even after 3 minutes have passed after the varnished screw tube is tilted, there is no fluidity and the shape can be maintained. From Table 1, it was shown that the gelling property can be imparted by blending the oil gelling agent (C).
表2の実施例7~8、比較例3~4には、成分(A)の液状エポキシ樹脂を共通に用いているので、封止フィルムの厚みが厚い場合でも、揮発成分の含有率を低下させることができる。揮発成分の含有率を低下させると、封止フィルムには変形による割れ又はクラックが生じやすいが、表2の実施例7、8から、フィルム中の揮発成分の含有量が0.6質量%以下でも良好な耐屈曲性を示すことが確認された。さらに、液状の樹脂を用いた場合、封止フィルムには液状の樹脂に起因する過度なタックが生じやすいが、表2の実施例7、8から、タック性も良好(べたつきのない)な100μm厚のフィルムが作製可能であることが確認された。
In Examples 7 to 8 and Comparative Examples 3 to 4 in Table 2, since the liquid epoxy resin of component (A) is commonly used, the content of volatile components is reduced even when the sealing film is thick. Can be made. When the content of volatile components is decreased, cracks or cracks due to deformation are likely to occur in the sealing film. From Examples 7 and 8 in Table 2, the content of volatile components in the film is 0.6% by mass or less. However, it was confirmed that the film exhibits good bending resistance. Furthermore, when a liquid resin is used, the sealing film tends to cause excessive tack due to the liquid resin, but from Examples 7 and 8 in Table 2, tackiness is also good (no stickiness) 100 μm. It was confirmed that a thick film could be produced.
一方、オイルゲル化剤(C)を含まない比較例3、4の封止フィルムは、フィルムの耐屈曲性は良好であったが、過度なタックが生じ取り扱い性が悪化した。
On the other hand, the sealing films of Comparative Examples 3 and 4 that did not contain the oil gelling agent (C) had good film bending resistance, but excessive tack occurred and handling properties deteriorated.
実施例7、8の封止フィルムは、硬化物のガラス転移温度(Tg)が200℃以上であった。一般的に有機材料は、Tgを超える温度領域において物性が大きく損なわれるため、高いTgを有する硬化物を形成することができる本発明に係るフィルム形成用樹脂組成物によれば、良好な耐熱性、信頼性を得ることができる。
The sealing films of Examples 7 and 8 had a glass transition temperature (Tg) of the cured product of 200 ° C. or higher. In general, since organic materials are greatly impaired in physical properties in a temperature range exceeding Tg, the film-forming resin composition according to the present invention capable of forming a cured product having a high Tg has good heat resistance. , Can get reliability.
以上より、本発明によれば、揮発成分を低減しても取り扱い性が良好であり、且つ十分に高いガラス転移温度を有する硬化物を形成できるフィルム形成用樹脂組成物、封止フィルム及び支持体付き封止フィルムを提供することができることが分かる。
As mentioned above, according to this invention, even if it reduces a volatile component, the handleability is favorable, and the resin composition for film formation which can form the hardened | cured material which has a sufficiently high glass transition temperature, a sealing film, and a support body It turns out that an attached sealing film can be provided.
1…支持体、2…封止フィルム、2a…硬化物(封止部)、10…支持体付き封止フィルム、20…半導体素子、30…基板、40…仮固定材、50…絶縁層、52…絶縁層、54…配線、56…ボール、60…ダイシングカッター、100…封止成形物、200…半導体装置。
DESCRIPTION OF SYMBOLS 1 ... Support body, 2 ... Sealing film, 2a ... Hardened | cured material (sealing part), 10 ... Sealing film with a support body, 20 ... Semiconductor element, 30 ... Board | substrate, 40 ... Temporary fixing material, 50 ... Insulating layer, 52 ... Insulating layer, 54 ... Wiring, 56 ... Ball, 60 ... Dicing cutter, 100 ... Sealed molding, 200 ... Semiconductor device.
Claims (7)
- 液状エポキシ樹脂(A)、シアネート樹脂(B)、及びオイルゲル化剤(C)を含むフィルム形成用樹脂組成物。 Resin composition for film formation containing liquid epoxy resin (A), cyanate resin (B), and oil gelling agent (C).
- 更に、下記一般式(1)で示されるフェノール性水酸基を有するシロキサン樹脂(D)を含む請求項1に記載のフィルム形成用樹脂組成物。
- 無機充填材(E)を更に含む、請求項1又は2に記載のフィルム形成用樹脂組成物。 The resin composition for film formation according to claim 1 or 2, further comprising an inorganic filler (E).
- 請求項1~3のいずれか1項に記載のフィルム形成用樹脂組成物を用いてなる封止フィルム。 A sealing film using the film-forming resin composition according to any one of claims 1 to 3.
- 厚さが30~250μmである、請求項4に記載の封止フィルム。 The sealing film according to claim 4, wherein the thickness is 30 to 250 μm.
- 請求項4又は5に記載の封止フィルムの少なくとも1つの面に支持体が設けられた支持体付き封止フィルム。 A sealing film with a support, wherein a support is provided on at least one surface of the sealing film according to claim 4 or 5.
- 請求項4又は5に記載の封止フィルム、又は請求項6に記載の支持体付き封止フィルムの前記封止フィルムによって封止された半導体素子を備える、半導体装置。 A semiconductor device provided with the semiconductor element sealed with the sealing film of Claim 4 or 5, or the said sealing film of the sealing film with a support body of Claim 6.
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WO2023128247A1 (en) * | 2021-12-30 | 2023-07-06 | 주식회사 케이씨씨 | Granular epoxy resin composition |
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JP6747440B2 (en) | 2020-08-26 |
JPWO2016204183A1 (en) | 2018-04-05 |
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