WO2021049805A1 - Sealing sheet, and semiconductor device including same - Google Patents

Sealing sheet, and semiconductor device including same Download PDF

Info

Publication number
WO2021049805A1
WO2021049805A1 PCT/KR2020/011715 KR2020011715W WO2021049805A1 WO 2021049805 A1 WO2021049805 A1 WO 2021049805A1 KR 2020011715 W KR2020011715 W KR 2020011715W WO 2021049805 A1 WO2021049805 A1 WO 2021049805A1
Authority
WO
WIPO (PCT)
Prior art keywords
sealing
sealing sheet
repeating unit
formula
sheet
Prior art date
Application number
PCT/KR2020/011715
Other languages
French (fr)
Korean (ko)
Inventor
김선영
서흔영
윤호규
김용욱
Original Assignee
주식회사 두산
고려대학교 산학협력단
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 두산, 고려대학교 산학협력단 filed Critical 주식회사 두산
Publication of WO2021049805A1 publication Critical patent/WO2021049805A1/en

Links

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
    • 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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/562—Protection against mechanical damage

Definitions

  • the present invention relates to a sealing sheet and a semiconductor device including the same, and specifically, to a sealing sheet applicable to a large-area semiconductor package and a semiconductor device including the same.
  • An object of the present invention is to provide a sealing sheet that is applied to a large area semiconductor package and can suppress the warpage of the semiconductor package.
  • Another object of the present invention is to provide a semiconductor device with improved quality and reliability by using the above-described sealing sheet.
  • the present invention is based on; And a sealing layer disposed on at least one surface of the substrate and having a thermal expansion coefficient in the range of 5 to 15 ppm/°C and a flexural modulus in the range of 15 to 30 MPa.
  • the present invention provides a semiconductor device including the sealing layer of the above-described sealing sheet.
  • the sealing sheet according to the present invention can suppress the warpage of the semiconductor package, thereby improving the quality and reliability of the semiconductor device.
  • FIG. 1 is a cross-sectional view schematically showing a sealing sheet according to a first embodiment of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing a sealing sheet according to a second embodiment of the present invention.
  • FIG. 1 is a cross-sectional view schematically showing a sealing sheet according to an embodiment of the present invention
  • FIG. 2 is a cross-sectional view schematically showing a sealing sheet according to another embodiment of the present invention.
  • the sealing sheets 10A and 10B according to the present invention are a sheet-shaped sealing resin that has low coefficient of thermal expansion and flexural modulus, and is easy to handle, and is disposed on the substrate 11 and at least one side of the substrate, and has a coefficient of thermal expansion and bending. It includes a sealing layer 12 having a low modulus. In addition, if necessary, the present name may further include a surface protective layer 13 disposed on the outer surface of the sealing layer 12.
  • the sealing sheet of the present invention can improve the quality and reliability of a semiconductor by suppressing the warpage of a semiconductor package, particularly a large-area semiconductor package.
  • the sealing sheet 10A includes a substrate 11 and a sealing layer 12 disposed on at least one surface of the substrate.
  • the base material 11 can prevent the sealing layer 12 from being contaminated from foreign substances in the external environment while supporting the sealing layer 12.
  • This substrate 11 may be a release substrate that can be peeled off and removed before the sealing sheet 10A is applied to the semiconductor package.
  • the substrate 11 may be used without limitation as long as it is a conventionally known plastic sheet known in the art, and is not particularly limited as long as it can be peeled without damage to the sealing layer 12. Moreover, a release map can also be used for the base material 11.
  • Non-limiting examples of plastic sheets usable in the present invention include polyester sheets such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate, polyethylene sheets, polypropylene sheets, cellophane, diacetylcellulose sheets, tri Acetylcellulose sheet, acetylcellulose butyrate sheet, polyvinyl chloride sheet, polyvinylidene chloride sheet, polyvinyl alcohol sheet, ethylene-vinyl acetate copolymer sheet, polystyrene sheet, polycarbonate sheet, polymethylpentene sheet, polysulfone sheet, poly Ether ketone sheet, polyether sulfone sheet, polyetherimide sheet, polyimide sheet, fluororesin sheet, polyamide sheet, acrylic resin sheet, norbornene resin sheet, cycloolefin resin sheet, and the like.
  • These plastic sheets may be transparent or translucent, or may be colored or uncolored.
  • the substrate 11 may be polyethylene terephthalate (
  • a release layer may be disposed on the plastic sheet.
  • the release layer can be easily separated so that the sealing layer is not damaged and maintains its shape when the substrate 11 is separated from the sealing sheet 10A.
  • the release layer may be a generally used sheet-type release material (release agent).
  • the component of the release agent used in the release layer is not particularly limited, and conventional components of the release agent known in the art may be used. Non-limiting examples thereof include an epoxy-based releasing agent, a releasing agent made of a fluorine resin, a silicone-based releasing agent, an alkyd resin-based releasing agent, and a water-soluble polymer.
  • a powdered filler such as silicon or silica, may be included. At this time, the powder fillers in the form of fine particles may be mixed with two types of powder fillers, and the average particle size thereof may be appropriately selected in consideration of the surface roughness to be formed.
  • the thickness of the release layer can be appropriately adjusted within a conventional range known in the art.
  • the thickness of the substrate 11 is not particularly limited, and can be adjusted within a typical range known in the art, for example, may be about 5 to 200 ⁇ m, specifically about 10 to 150 ⁇ m, More specifically, it may be about 20 to 100 ⁇ m.
  • the sealing layer 12 is a portion disposed on at least one surface of the substrate, and during semiconductor packaging, the semiconductor device can be protected from external physical and chemical impacts.
  • the sealing layer 12 has a coefficient of thermal expansion after curing (specifically, a coefficient of linear expansion before the glass transition temperature) of about 5 to 15 ppm/°C, and a flexural modulus of about 15 to 30 MPa. If, after curing the sealing layer, the thermal expansion coefficient exceeds about 15 ppm/°C, the package may be warped. In addition, when the flexural modulus of the sealing layer exceeds about 30 MPa, the package may be warped. As described above, the sealing layer 12 having a low coefficient of thermal expansion and flexural modulus suppresses the warpage of large-area semiconductor packages such as Fan-out Wafer Level Package (FOWLP) and Panel Level Package (PLP), thereby reducing the quality of semiconductor devices and Reliability can be improved.
  • FOWLP Fan-out Wafer Level Package
  • PGP Panel Level Package
  • the sealing layer 12 of the present invention includes (a) an epoxy resin; (b) i) a copolymer comprising a styrene-based repeating unit and a glycidyl (meth)acrylate-based repeating unit, ii) a mixture of a dicarboxylic acid-based compound and a tricarboxylic acid-based compound, and iii) an acid anhydride Additives containing at least one selected; (c) a hardener; And (d) a filler.
  • the sealing resin composition may further include a curing accelerator, and may further include other additives such as ethylene-based wax.
  • the epoxy resin is cured by reacting with a curing agent by heat, and after curing, as a matrix component of the sealing layer having a three-dimensional network structure, not only improves adhesion of the sealing layer, but also heat resistance, water resistance, and resistance. It has excellent moisture and can improve the reliability of the semiconductor package.
  • epoxy resins are not only excellent in mechanical strength, electrical insulation, chemical resistance, dimensional stability, and moldability, but also excellent in compatibility with other resins.
  • the epoxy resin usable in the present invention is a polymer containing at least one epoxy group in the molecule, and is preferably an epoxy resin that does not contain halogen atoms such as bromine in the molecule.
  • the epoxy resin not only contains silicon, urethane, polyimide, polyamide, etc. in the molecule, but may also contain a phosphorus atom (P), a sulfur atom (S), a nitrogen atom (N), etc.
  • the type of such epoxy resin is not particularly limited, and for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, or hydrogenated ones thereof, phenol novolak type epoxy resin, cresol novolak type epoxy resin, etc.
  • Glycidyl ester epoxy resins such as cidyl ether epoxy resin, hexahydrophthalic acid glycidyl ester and dimer acid glycidyl ester, triglycidyl isocyanurate, tetraglycidyldiamino diphenylmethane, etc.
  • Linear aliphatic epoxy resins such as glycidylamine epoxy resin, epoxidized polybutadiene, epoxidized soybean oil, etc., and preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, creson There are novolak-type epoxy resins, biphenyl-type epoxy resins, and polyfunctional epoxy resins. These may be used alone, or two or more may be used in combination.
  • the content of the epoxy resin is not particularly limited, and may be, for example, in the range of about 3 to 20% by weight, specifically, in the range of about 5 to 15% by weight, based on the total amount of the resin composition.
  • content of the epoxy resin is within the above-described range, not only the adhesion and heat resistance of the sealing layer are improved, but also the warpage of the semiconductor package can be suppressed.
  • the additive is i) a copolymer containing a styrene-based repeating unit and a glycidyl (meth)acrylate-based repeating unit, ii) a carboxylic acid-based compound containing a dicarboxylic acid-based compound and a tricarboxylic acid-based compound, And iii) an acid anhydride.
  • the copolymer containing a styrene-based repeating unit and a glycidyl (meth)acrylate-based repeating unit not only lowers the coefficient of thermal expansion and flexural modulus of the sealing layer, but also has sheet formability when the resin composition is formed in a sheet shape. Can be improved.
  • the styrene repeating unit serves to increase the stiffness and strain of the sealing layer, and the glycidyl (meth)acrylate repeating unit improves compatibility with the epoxy resin in the sealing resin composition. It plays a role of letting go. Therefore, the copolymer of the present invention comprises a styrene-based repeating unit and a glycidyl (meth)acrylate-based repeating unit in a molar ratio of 5:95 to 95:5, specifically in a molar ratio of 60:40 to 95:5, more specifically By including it in a molar ratio of 80:20 to 95:5, it is possible to facilitate sheet formation without lowering the compatibility with the epoxy resin.
  • the weight average molecular weight (Mw) of the copolymer may be in the range of about 1,000 to 15,000 g/mol, specifically about 5,000 to 13,000 g/mol, and more specifically about 8,000 to 12,000 g/mol. If the weight average molecular weight of the copolymer is out of the above-described range, compatibility with the epoxy resin may decrease.
  • the copolymer may be a polymer including a styrenic repeating unit represented by Formula 1 below and a glycidyl (meth)acrylate repeating unit represented by Formula 2 below, but is not limited thereto.
  • the copolymer may be a random copolymer.
  • a is an integer from 0 to 5
  • a plurality of R 3 are the same as or different from each other,
  • R 1 to R 5 may be the same as or different from each other, and each independently hydrogen or a C 1 to C 12 alkyl group, specifically hydrogen or a C 1 to C 6 alkyl group, and more specifically hydrogen.
  • the styrene repeating unit of Formula 1 and the glycidyl (meth)acrylate repeating unit of Formula 2 are in a molar ratio of 5:95 to 95:5, specifically 80:20 to 95 It is a random polymer that is irregularly arranged in a linear shape at a molar ratio of :5, and may be a random copolymer represented by Formula 3 below.
  • R 1 to R 5 are as defined in Formulas 1 and 2, respectively,
  • n are each an integer of 1 to 90
  • the additive according to the present invention may include a carboxylic acid-based compound.
  • the carboxylic acid-based compound contains a dicarboxylic acid-based compound and a tricarboxylic acid-based compound.
  • Such a carboxylic acid-based compound not only reduces the stress of the sealing layer to lower the thermal expansion coefficient and the flexural modulus of the sealing layer, but also can cure the epoxy resin by imparting a polyester group to the epoxy group of the epoxy resin.
  • the dicarboxylic acid-based compound is an aromatic carboxylic acid having two carboxyl groups in the molecule, and may be, for example, a compound represented by the following formula (4).
  • R 6 to R 9 are the same as or different from each other, and each independently selected from the group consisting of a C 1 to C 12 hydrocarbon group, a C 2 to C 14 unsaturated hydrocarbon group, and a C 2 to C 14 hydrocarbon group substituted with a carboxyl group And, specifically, a C 1 to C 12 alkyl group, a C 2 to C 14 alkenyl group, a C 2 to C 14 alkynyl group, and a C 2 to C 14 alkyl group substituted with a carboxyl group. ,
  • R 6 to R 9 are C 2 to C 14 hydrocarbon groups substituted with a carboxyl group, and at least one of the remaining ones is a C 2 to C 14 unsaturated hydrocarbon group.
  • R 6 and R 7 are the same as or different from each other, and are each independently a hydrocarbon group of C 2 to C 14 substituted with a carboxyl group, and specifically C 2 substituted with a carboxyl group ⁇ C can be a 14 alkyl group
  • R 8 is C 2 ⁇ unsaturated hydrocarbon group of C 14, and specifically, C 2 ⁇ and an alkynyl group of C 14 alkenyl group, C 2 ⁇ C 14 of, more specifically, C 2 ⁇ It may be a C 14 alkenyl group
  • R 9 may be a C 1 to C 12 hydrocarbon group, and specifically a C 1 to C 12 alkyl group.
  • the tricarboxylic acid-based compound is an aromatic carboxylic acid having three carboxyl groups in the molecule, and may be, for example, a compound represented by the following formula (5).
  • R 10 to R 15 are the same as or different from each other, and each independently selected from the group consisting of a C 1 to C 12 hydrocarbon group, a C 2 to C 14 unsaturated hydrocarbon group, and a C 2 to C 14 hydrocarbon group substituted with a carboxyl group And, specifically, a C 1 to C 12 alkyl group, a C 2 to C 14 alkenyl group, a C 2 to C 14 alkynyl group, and a C 2 to C 14 alkyl group substituted with a carboxyl group. ,
  • R 10 to R 15 are C 2 to C 14 hydrocarbon groups substituted with a carboxyl group, and at least one of the others is a C 2 to C 14 unsaturated hydrocarbon group.
  • R 10 to R 12 are the same as or different from each other, and are each independently a C 2 to C 14 hydrocarbon group substituted with a carboxyl group, and specifically C 2 substituted with a carboxyl group ⁇ C can be a 14 alkyl group
  • R 13 is C 2 ⁇ unsaturated hydrocarbon group of C 14, and specifically, C 2 ⁇ and an alkynyl group of C 14 alkenyl group, C 2 ⁇ C 14 of, more specifically, C 2 ⁇
  • R 14 and R 15 are the same as or different from each other, and each independently a C 1 to C 12 hydrocarbon group, and specifically may be a C 1 to C 12 alkyl group.
  • the mixing ratio of the dicarboxylic acid compound and the tricarboxylic acid compound is not particularly limited. According to an example, the mixing ratio of the dicarboxylic acid-based compound and the tricarboxylic acid-based compound may be 10:90 ⁇ 30:70 weight ratio. According to another example, the mixing ratio of the dicarboxylic acid-based compound and the tricarboxylic acid-based compound may be a weight ratio of 70:30 to 99:1.
  • the additive according to the present invention may contain an acid anhydride.
  • the acid anhydride not only lowers the coefficient of thermal expansion and flexural modulus of the sealing layer, but also can cure the epoxy resin.
  • the acid anhydride may be one or more selected from the group consisting of a compound represented by the following formula (6) and a compound represented by the following formula (7), but is not limited thereto.
  • X 1 and X 2 are the same as or different from each other, each independently selected from the group consisting of O, S, and NAr 1, and may be specifically O,
  • Ar 1 is hydrogen or a C 1 to C 12 hydrocarbon group, specifically hydrogen or a C 1 to C 12 alkyl group,
  • the content of the additive is not particularly limited, for example, about 0.01 to 20% by weight, specifically about 0.05 to 15% by weight, more specifically about 0.1 to 10, based on the total amount of the resin composition. It may be weight percent.
  • the additive is i) a copolymer comprising a styrene-based repeating unit and a glycidyl (meth)acrylate-based repeating unit; ii) a carboxylic acid compound containing a dicarboxylic acid compound and a tricarboxylic acid compound; And iii) When including one selected from the group consisting of an acid anhydride, the content of the additive may be about 0.1 to 2% by weight, specifically about 0.3 to 1.5% by weight.
  • the additive is a carboxylic acid-based compound or an acid anhydride containing a dicarboxylic acid-based compound and a tricarboxylic acid-based compound together with a copolymer containing a styrene-based repeating unit and a glycidyl (meth)acrylate-based repeating unit.
  • the content of the additive may be about 0.3 to 10% by weight, specifically about 0.5 to 5% by weight, and more specifically about 0.5 to 2.5% by weight.
  • the curing agent is a component that reacts with the epoxy resin to proceed with curing of the composition.
  • the curing agent usable in the present invention includes a curing agent component commonly known in the art, such as a phenolic curing agent, an acid anhydride curing agent, an amine curing agent, and the like.
  • Non-limiting examples of the phenolic curing agent include a biphenyl curing agent, a naphthalene curing agent, a phenol novolak curing agent, a naphthylene ether curing agent, a triazine skeleton-containing-phenolic curing agent, and the like, specifically, MEH-7700 , A biphenyl-based curing agent such as MEH-7810, MEH-7851 (made by Meiwa Kasei Co., Ltd.); NHN, CBN, GPH (manufactured by Nihon Kayaku Co., Ltd.), SN-170, SN-180, SN-190, SN-475, SN-485, SN-495, SN-375, SN-395 (Shinnittetsuka) A naphthalene-based curing agent such as Gaku Corporation) and EXB9500 (manufactured by DIC Corporation); Phenol novolak-based curing agents such
  • Non-limiting examples of the acid anhydride-based curing agent include tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, hexahydrophthalic anhydride, trialkyl tetrahydrophthalic anhydride, methyl cyclohexenedicarboxylic anhydride, phthalic acid There are anhydride, maleic anhydride, pyromellitic anhydride, and the like, which may be used alone or in combination of two or more.
  • amine-based curing agent examples include aromatic amine-based curing agents such as metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone; There are aliphatic amine-based curing agents such as diethylenetriamine and triethylenetetraamine, and these may be used alone or in combination of two or more.
  • latent curing agents such as dicyandiamide, but are not limited thereto.
  • the curing agent may be a phenol-based curing agent, specifically a naphthalene-based curing agent, and more specifically, a curing agent represented by Formula 8 below.
  • b and c are each an integer of 1 to 2
  • Ar 1 and Ar 2 are the same as or different from each other, and each independently a C 1 to C 6 hydrocarbon group, specifically a C 1 to C 6 alkylene group, more specifically a methylene group,
  • n1 is an integer from 1 to 20).
  • the content of the curing agent is not particularly limited, and for example, may be in the range of about 1 to 10% by weight, specifically in the range of about 2 to 8% by weight based on the total amount of the sealing resin composition.
  • the filler can improve heat resistance, insulation, mechanical properties (eg, strength, etc.), and low stress of the sealing layer.
  • Non-limiting examples of the fillers usable in the present invention include silica such as natural silica, fused silica, amorphous silica, crystalline silica, and the like; Aluminum hydroxide (ATH), boehmite, alumina, talc, glass (e.g. spherical glass), calcium carbonate, magnesium carbonate, magnesia, clay, calcium silicate, magnesium oxide (MgO), Titanium oxide, antimony oxide, glass fiber, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titania (e.g.
  • silica such as natural silica, fused silica, amorphous silica, crystalline silica, and the like
  • the filler may be silica.
  • the silica may be surface-treated with the following surface treatment agent, in particular, a silane-based coupling agent, specifically an epoxy-based silane coupling agent.
  • the average particle diameter (D50) of such a filler is not particularly limited, and different types of fillers may be mixed and used. For example, a filler having an average particle diameter (D50) of about 1 to 20 ⁇ m and a filler having an average particle diameter (D50) of about 15 to 50 ⁇ m may be mixed and used. As another example, a filler having an average particle diameter (D50) of about 0.1 to 10 ⁇ m and a second filler having an average particle diameter (D50) of about 15 to 30 ⁇ m may be mixed and used. As another example, a filler having an average particle diameter (D50) of about 0.5 to 3 ⁇ m and a filler having an average particle diameter (D50) of about 20 to 25 ⁇ m may be mixed and used. The ratio of these fillers may be 1:9 to 3:7 weight ratio. In this case, it is advantageous in dispersibility of the filler, and mechanical properties of the sealing layer may be further improved.
  • the shape of the filler is not particularly limited, and includes, for example, a spherical shape, a flake, a dendrite, a conical shape, a pyramid shape, and an amorphous shape.
  • the filler may be surface treated with a surface treatment agent.
  • the filler has improved compatibility between the epoxy resins by the surface treatment agent, so that the molding processability and rigidity of the sealing layer may be improved.
  • a surface treatment agent may coat the surface of the filler, or may be included as a component of the resin composition together with the filler.
  • the surface treatment agent usable in the present invention is not particularly limited as long as it is known in the art, and is, for example, a silane-based compound (silane-based coupling agent), and specifically, 3-(glycidyloxy)propyltrimethoxysilane, 3-(glycidyloxy) Cydyloxy)propyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl triethoxysilane, epoxyproxoxypropyl trime Epoxy-based silane coupling agents such as oxysilane and the like; Amino-based silane coupling agents such as 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-2-(aminoethyl)-3-aminopropyltrimethoxysilane
  • the content of the surface treatment agent is not particularly limited, and may be, for example, about 0.5 to 20 parts by weight, specifically about 1 to 15 parts by weight based on 100 parts by weight of the filler. In this case, compatibility between the filler and the epoxy resin may be improved.
  • the content of the filler may be about 75 to 90% by weight, specifically about 80 to 90% by weight, based on the total amount of the sealing resin composition.
  • the filler by applying the filler, the effect of reducing the coefficient of thermal expansion and reducing the modulus characteristics can be expected. Due to the reduction in these characteristics, it is possible to suppress the warpage of the semiconductor package.
  • the sealing resin composition according to the present invention may further include a curing accelerator, if necessary.
  • the curing accelerator is a catalyst that shortens the curing time so that the components in the resin composition can be completely cured, and is not particularly limited as long as it is known in the art.
  • organic phosphine-based compounds such as imidazole-based compounds, phosphonium-based compounds, amine-based compounds, organometallic compounds, and the like, which may be used alone or in combination of two or more.
  • the organic phosphine-based compound is tris-4-methoxy phosphine, triphenyl phosphine, tributyl phosphine, methyldiphenyl phosphine, dimethylphosphine, phenyl phosphine, octylphosphine, diphenylphosphine, Triphenylphosphine, triphenylphosphine triphenylborane, triphenylphosphine-1,4-benzoquinone adducts, and the like, but are not limited thereto. These may be used alone or in combination of two or more.
  • Non-limiting examples of the imidazole-based compound include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-decylimidazole, 2-hectylimidazole, 2-isopropylimidazole, 2-undecyl imidazole, 2-heptanedecyl imidazole, 2-methyl-4-methyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenylimidazole, 2-phenyl-4-methyl imidazole , 1-benzyl-2-methyl imidazole, 1-benzyl-2-phenyl imidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole , 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazo
  • Non-limiting examples of the phosphonium-based compound include benzyltriphenylphosphonium chloride, butyltriphenylphosphonium chloride, butyltriphenylphosphonium bromide, ethyltriphenylphosphonium acetate, ethyltriphenylphosphonium bromide, ethyltriphenylphos
  • benzyltriphenylphosphonium chloride butyltriphenylphosphonium chloride, butyltriphenylphosphonium bromide, ethyltriphenylphosphonium acetate, ethyltriphenylphosphonium bromide, ethyltriphenylphos
  • phonium iodide tetraphenylphosphonium bromide, tetraphenylphosphonium chloride or tetraphenylphosphonium iodide, and these may be used alone or in combination of two or more.
  • Non-limiting examples of the amine-based compound include triethylamine, triethylenediamine, tetramethyl-1,3-butanediamine, ethylmorpholine, diazabicycloundecene, diazabicyclononene, and the like. It may be used or may be used in combination of two or more.
  • the organometallic compound is an organometallic complex or organometallic salt such as cobalt, copper, zinc, iron, nickel, manganese, and tin.
  • organometallic complex include organic cobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate; Organic copper complexes such as copper (II) acetylacetonate, and organic zinc complexes such as zinc (II) acetylacetonate; Organic iron complexes such as iron (III) acetylacetonate; Organic nickel complexes such as nickel (II) acetylacetonate; And organic manganese complexes such as manganese (II) acetylacetonate.
  • organometallic salt examples include, but are not limited to, zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like. These may be used alone or in combination of two or more.
  • the content of the curing accelerator is not particularly limited, and for example, may be in the range of about 0.01 to 3% by weight, specifically about 0.05 to 1.0% by weight, based on the total amount of the sealing resin composition.
  • the content of the curing accelerator is within the above-described range, flowability may be improved without overcuring.
  • the sealing resin composition according to the present invention may optionally further include other additives commonly known in the art, in addition to the above-described components, depending on the purpose of use and the environment of use of the composition.
  • Examples of the other additives include release agents such as higher fatty acids, higher fatty acid metal salts, natural fatty acids, paraffin waxes, ethylene waxes (eg, polyethylene waxes), ester waxes, and the like; Coloring agents such as carbon black, organic dyes, and inorganic dyes; Coupling agents such as epoxysilane, aminosilane, alkylsilane, mercaptosilane, and alkoxysilane; Modified silicone oil, silicone powder, silicone resin, organopolysiloxane; Flame retardants such as phosphazene, zinc borate, aluminum hydroxide, and magnesium hydroxide; Antifoam; Pigment; There are dyes and the like, and these may be used alone or in combination of two or more.
  • release agents such as higher fatty acids, higher fatty acid metal salts, natural fatty acids, paraffin waxes, ethylene waxes (eg, polyethylene waxes), ester waxes, and the like
  • Coloring agents such
  • the content of these other additives is not particularly limited, and may be, for example, in the range of about 0.01 to 10% by weight, specifically about 0.1 to 5% by weight, based on the total amount of the resin composition.
  • the content of the other additive may be about 0.05 to 3% by weight, specifically about 0.01 to 1% by weight, based on the total amount of the resin composition.
  • the above-described sealing resin composition can be prepared by a method commonly known in the art, such as a known melt-kneading method using a two-roll mill, a three-roll mill, a kneader, a single-screw or twin-screw extruder, and a cone.
  • a method commonly known in the art such as a known melt-kneading method using a two-roll mill, a three-roll mill, a kneader, a single-screw or twin-screw extruder, and a cone.
  • melt-mixing at a temperature of about 100 to 130°C using a two-roll mill, cooling to room temperature, and then through a general process of obtaining a product in a powder state.
  • the composition of the present invention can be obtained.
  • Such a sealing resin composition is superior to conventional sealing resin compositions in heat resistance, moldability, flowability, reliability, warpage properties, and crack resistance. Accordingly, the present invention can lower the molding defect rate of the semiconductor device when sealing the semiconductor device.
  • the thickness of the sealing layer according to the present invention is not particularly limited, and is adjusted according to the height of the semiconductor device. For example, it may be about 1 to 800 ⁇ m, specifically about 5 to 500 ⁇ m, and more specifically about 5 to 350 ⁇ m.
  • the sealing sheet 10B of the present invention comprises a base material 11; A sealing layer 12 disposed on at least one surface of the substrate 11 and having a thermal expansion coefficient of 5 to 15 ppm/°C after curing, and a flexural modulus of 15 to 30 MPa; And a surface protective layer 13 disposed on the outer surface of the sealing layer 12.
  • sealing sheet 10B In the sealing sheet 10B according to the second embodiment, descriptions of the base material 11 and the sealing layer 12 are the same as those described in the first embodiment, and thus will be omitted.
  • the surface protective layer 13 is a portion disposed on the other surface of the sealing layer 12, that is, the outer surface, and the sealing layer 12 is contaminated by external foreign substances. And protects the surface of the sheet, in particular the surface of the sealing layer, when the sealing sheet is applied to the semiconductor package through the lamination process. When the sealing sheet is applied to a semiconductor package, the surface protection layer 13 may be peeled off and removed as needed.
  • the material of the surface protective layer that can be used in the present invention is not particularly limited as long as it is a protective sheet commonly known in the art.
  • a polyester sheet such as polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate, polyethylene Sheet, polypropylene sheet, cellophane, diacetylcellulose sheet, triacetylcellulose sheet, acetylcellulose butyrate sheet, polyvinyl chloride sheet, polyvinylidene chloride sheet, polyvinyl alcohol sheet, ethylene-vinyl acetate copolymer sheet, polystyrene sheet, Polycarbonate sheet, polymethylpentene sheet, polysulfone sheet, polyetheretherketone sheet, polyethersulfone sheet, polyetherimide sheet, polyimide sheet, fluororesin sheet, polyamide sheet, acrylic resin sheet, Novo There are ene-based resin sheets, cycloolefin resin sheets, and the like, but are not limited thereto.
  • At least one surface of the surface protective layer 13, specifically, a surface in contact with the sealing layer 12 may be a matte surface.
  • the surface protection layer 13 can be easily peeled off and removed from the sealing layer after the sealing layer of the sealing sheet is attached to the semiconductor package.
  • the thickness of the surface protective layer is not particularly limited, and may be, for example, about 20 to 80 ⁇ m, and specifically, about 40 to 60 ⁇ m.
  • the sealing sheets 10A and 10B of the present invention can be manufactured by a conventional method known in the art, except for forming the sealing layer using the above-described sealing resin composition.
  • the above-described sealing resin composition is coated on one surface of a substrate and thermally cured to form a sealing layer, and if necessary, a surface protective layer is laminated on the outer surface of the sealing layer. It can be manufactured by doing.
  • the coating method of the sealing resin composition is a conventional coating method in the field, for example, a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, a comma coating method, a slot coating method, etc. Can be lifted.
  • thermal curing process may be appropriately performed within conventional conditions known in the art.
  • thermal curing may be performed at about 80 to 200° C. for about 5 to 60 minutes.
  • the sealing layer formed through such thermal curing may be in a semi-cured state and a degree of cure of about 5 to 35%.
  • the sealing sheet of the present invention includes a sealing layer having a low coefficient of thermal expansion and flexural elasticity, it is possible to suppress the warpage of the semiconductor package during semiconductor packaging, and further improve the quality and reliability of the semiconductor device. have.
  • the present invention provides a semiconductor device manufactured using the above-described sealing sheet.
  • warpage of the semiconductor package is suppressed by the sealing layer of the above-described sealing sheet during semiconductor packaging, so that quality and reliability can be improved.
  • a semiconductor device includes a substrate including a semiconductor element; And a sealing layer disposed on the substrate so as to contact the semiconductor device.
  • the sealing layer is a part of the sealing layer of the sealing sheet, and is in a state separated from the base material and/or the surface protective layer. This sealing layer seals the semiconductor device without warping of the semiconductor package.
  • the semiconductor devices include transistors, diodes, microprocessors, and semiconductor memories.
  • the semiconductor device of the present invention can be manufactured through the semiconductor packaging process using the above-described sealing sheet.
  • semiconductor packaging processes such as Fan-out Wafer Level Package (FOWLP) and Panel Level Package (PLP).
  • FOWLP Fan-out Wafer Level Package
  • PGP Panel Level Package
  • Each component was mixed according to the composition shown in Table 1 to prepare the sealing resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3.
  • the content unit of each component listed in Table 1 was weight %, based on the total amount of the resin composition.
  • Example 1-1 Each sealing resin composition prepared in Example 1-1 was subjected to a press process, and then dried at 180° C. for 4 hours to form a fully cured sealing layer (thickness: 300 ⁇ m), and Examples 1 to 6 and Comparative Examples 1 to 3 sealing sheets were prepared.
  • the sealing sheet was manufactured in a size of 6.5 mm ⁇ 12.5 mm ⁇ 125 mm to prepare a specimen, and then the flexural strength, flexural modulus, and elongation of each specimen were measured according to the ASTM D790 method.
  • the glass transition temperature of the sealing sheet was measured using a Dynamic Mechanical Analyzer (DMA). At this time, the DMA was set to a condition of measuring up to 250°C by increasing the temperature by 5°C per minute at 25°C.
  • DMA Dynamic Mechanical Analyzer
  • Examples 1 to 6 and Comparative Examples 1 to 3 A sealing layer (thickness: 0.5 mm) of each sealing sheet manufactured in was applied to measure the warpage characteristics.

Abstract

The present invention relates to a sealing sheet, and a semiconductor package including same, the sealing sheet including: a substrate; and a sealing layer which is disposed on at least one surface of the substrate, and has a post-curing thermal expansion coefficient range of 5-15 ppm/°C, and a flexural modulus range of 15-30 MPa.

Description

밀봉 시트 및 이를 포함하는 반도체 장치Sealing sheet and semiconductor device including the same
본 발명은 밀봉 시트 및 이를 포함하는 반도체 장치에 관한 것이고, 구체적으로 대면적 반도체 패키지에 적용 가능한 밀봉 시트 및 이를 포함하는 반도체 장치에 관한 것이다.The present invention relates to a sealing sheet and a semiconductor device including the same, and specifically, to a sealing sheet applicable to a large-area semiconductor package and a semiconductor device including the same.
최근 전자기기 제품의 경량화, 소형화, 고속화, 다기능화, 고성능화 등 복합화 추세에 따라, 전자기기 내 탑재되는 반도체 장치에 대한 높은 신뢰성을 요구하고 있다. 이러한 복합화 추세에 따라 반도체 패키지의 크기 및 두께가 칩 크기에 가깝게 제조되는 팬-아웃 웨이퍼 레벨 패키지(Fan-out Wafer Level Package, FOWLP)나 패널 레벨 패키지(Panel Level Package, PLP)에 대한 연구가 진행되고 있다. 이러한 반도체 패키지 공정의 변화로 인해 새로운 봉지 소재에 대한 개발이 필요하다.In recent years, according to the trend of complexization such as weight reduction, miniaturization, high speed, multi-function, and high performance of electronic equipment products, high reliability is required for semiconductor devices mounted in electronic equipment. In accordance with this trend of complexation, research on a fan-out wafer level package (FOWLP) or a panel level package (PLP) in which the size and thickness of semiconductor packages are manufactured close to the chip size is in progress. Has become. Due to this change in semiconductor package process, it is necessary to develop a new encapsulation material.
본 발명의 목적은 대면적 반도체 패키지에 적용되어 반도체 패키지의 휨 현상을 억제할 수 있는 밀봉 시트를 제공하는 것이다.An object of the present invention is to provide a sealing sheet that is applied to a large area semiconductor package and can suppress the warpage of the semiconductor package.
또, 본 발명의 다른 목적은 전술한 밀봉 시트를 이용하여 품질 및 신뢰성이 향상된 반도체 장치를 제공하는 것이다.Another object of the present invention is to provide a semiconductor device with improved quality and reliability by using the above-described sealing sheet.
상기한 기술적 과제를 달성하고자, 본 발명은 기재; 및 상기 기재의 적어도 일면에 배치되고, 경화 후의 열팽창계수가 5 내지 15 ppm/℃ 범위이고, 굴곡 탄성률이 15 내지 30 MPa 범위인 밀봉층을 포함하는 밀봉 시트를 제공한다.In order to achieve the above technical problem, the present invention is based on; And a sealing layer disposed on at least one surface of the substrate and having a thermal expansion coefficient in the range of 5 to 15 ppm/°C and a flexural modulus in the range of 15 to 30 MPa.
또, 본 발명은 전술한 밀봉 시트의 밀봉층을 포함하는 반도체 장치를 제공한다.Further, the present invention provides a semiconductor device including the sealing layer of the above-described sealing sheet.
본 발명에 따른 밀봉 시트는 반도체 패키지의 휨 현상을 억제할 수 있어 반도체 장치의 품질 및 신뢰성을 향상시킬 수 있다.The sealing sheet according to the present invention can suppress the warpage of the semiconductor package, thereby improving the quality and reliability of the semiconductor device.
도 1은 본 발명의 제1 실시 형태에 따른 밀봉 시트를 개략적으로 나타낸 단면도이다.1 is a cross-sectional view schematically showing a sealing sheet according to a first embodiment of the present invention.
도 2는 본 발명의 제2 실시 형태에 따른 밀봉 시트를 개략적으로 나타낸 단면도이다.2 is a cross-sectional view schematically showing a sealing sheet according to a second embodiment of the present invention.
** 부호의 설명 **** Explanation of sign **
10A, 10B: 밀봉 시트,10A, 10B: sealing sheet,
11: 기재,11: substrate,
12: 밀봉층,12: sealing layer,
13: 표면 보호층13: surface protective layer
이하, 첨부된 도면을 참조하여 본 발명의 바람직한 실시형태들을 설명한다. 그러나 본 발명의 실시형태는 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 이하 설명하는 실시형태로 한정되는 것은 아니다. 또한, 본 발명의 실시형태는 당해 기술분야에서 평균적인 지식을 가진 자에게 본 발명을 더욱 완전하게 설명하기 위해서 제공되는 것이다.Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, embodiments of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below. In addition, embodiments of the present invention are provided in order to more completely explain the present invention to those with average knowledge in the art.
<밀봉 시트><Sealed sheet>
도 1은 본 발명의 일 실시예에 따른 밀봉 시트를 개략적으로 나타낸 단면도이고, 도 2는 본 발명의 다른 실시예에 따른 밀봉 시트를 개략적으로 나타낸 단면도이다.1 is a cross-sectional view schematically showing a sealing sheet according to an embodiment of the present invention, and FIG. 2 is a cross-sectional view schematically showing a sealing sheet according to another embodiment of the present invention.
본 발명에 따른 밀봉 시트(10A, 10B)는 열팽창계수 및 굴곡 모듈러스가 낮고, 핸들링이 용이한 시트 형태의 밀봉 수지로, 기재(11), 및 상기 기재의 적어도 일면에 배치되고, 열팽창계수 및 굴곡 모듈러스가 낮은 밀봉층(12)을 포함한다. 또, 필요에 따라, 본 명은 상기 밀봉층(12)의 외면에 배치된 표면 보호층(13)을 더 포함할 수 있다. 이러한 본 발명의 밀봉 시트는 반도체 패키지, 특히 대면적 반도체 패키지의 휨 현상을 억제하여 반도체의 품질 및 신뢰성을 향상시킬 수 있다.The sealing sheets 10A and 10B according to the present invention are a sheet-shaped sealing resin that has low coefficient of thermal expansion and flexural modulus, and is easy to handle, and is disposed on the substrate 11 and at least one side of the substrate, and has a coefficient of thermal expansion and bending. It includes a sealing layer 12 having a low modulus. In addition, if necessary, the present name may further include a surface protective layer 13 disposed on the outer surface of the sealing layer 12. The sealing sheet of the present invention can improve the quality and reliability of a semiconductor by suppressing the warpage of a semiconductor package, particularly a large-area semiconductor package.
이하, 도 1를 참조하여, 본 발명의 일 실시예에 따른 밀봉 시트(10A)에 대해 설명한다.Hereinafter, a sealing sheet 10A according to an embodiment of the present invention will be described with reference to FIG. 1.
도 1에 도시된 바와 같이, 본 발명의 일 실시예에 따른 밀봉 시트(10A)는 기재(11), 및 상기 기재의 적어도 일면에 배치된 밀봉층(12)을 포함한다. As shown in FIG. 1, the sealing sheet 10A according to an embodiment of the present invention includes a substrate 11 and a sealing layer 12 disposed on at least one surface of the substrate.
(1) 기재(1) description
본 발명에 따른 밀봉 시트(10)에서, 기재(11)는 밀봉층(12)을 지지하면서 밀봉층(12)을 외부 환경의 이물질로부터 오염되는 것을 방지할 수 있다. 이러한 기재(11)는 밀봉 시트(10A)가 반도체 패키지에 적용되기 전에 박리되어 제거될 수 있는 이형 기재일 수 있다.In the sealing sheet 10 according to the present invention, the base material 11 can prevent the sealing layer 12 from being contaminated from foreign substances in the external environment while supporting the sealing layer 12. This substrate 11 may be a release substrate that can be peeled off and removed before the sealing sheet 10A is applied to the semiconductor package.
이러한 기재(11)로는 당 업계에 알려진 통상적으로 알려진 플라스틱 시트라면 제한 없이 사용할 수 있으며, 특히 밀봉층(12)의 손상 없이 박리될 수 있는 것이라면 특별히 제한되지 않는다. 또, 기재(11)로 이형지도 사용할 수 있다. The substrate 11 may be used without limitation as long as it is a conventionally known plastic sheet known in the art, and is not particularly limited as long as it can be peeled without damage to the sealing layer 12. Moreover, a release map can also be used for the base material 11.
본 발명에서 사용 가능한 플라스틱 시트의 비제한적인 예로는 폴리에틸렌테레프탈레이트(PET), 폴리부틸렌테레프탈레이트, 폴리에틸렌나프탈레이트 등의 폴리에스터 시트, 폴리에틸렌 시트, 폴리프로필렌 시트, 셀로판, 다이아세틸셀룰로스 시트, 트라이아세틸셀룰로스 시트, 아세틸셀룰로스부티레이트 시트, 폴리염화비닐 시트, 폴리염화비닐리덴 시트, 폴리비닐알코올 시트, 에틸렌-아세트산비닐 공중합체 시트, 폴리스타이렌 시트, 폴리카보네이트 시트, 폴리메틸펜텐 시트, 폴리설폰 시트, 폴리에터에터케톤 시트, 폴리에터설폰 시트, 폴리에터이미드 시트, 폴리이미드 시트, 불소수지 시트, 폴리아마이드 시트, 아크릴수지 시트, 노보넨계 수지 시트, 사이클로올레핀 수지 시트 등이 있다. 이러한 플라스틱 시트는 투명 혹은 반투명일 수 있고, 또는 착색되어 있거나 혹은 무착색된 것일 수도 있다. 일례에 따르면, 기재(11)는 폴리에틸렌테레프탈레이트(PET)일 수 있다. 다른 일례에 따르면, 기재(11)는 폴리이미드(PI)일 수 있다.Non-limiting examples of plastic sheets usable in the present invention include polyester sheets such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate, polyethylene sheets, polypropylene sheets, cellophane, diacetylcellulose sheets, tri Acetylcellulose sheet, acetylcellulose butyrate sheet, polyvinyl chloride sheet, polyvinylidene chloride sheet, polyvinyl alcohol sheet, ethylene-vinyl acetate copolymer sheet, polystyrene sheet, polycarbonate sheet, polymethylpentene sheet, polysulfone sheet, poly Ether ketone sheet, polyether sulfone sheet, polyetherimide sheet, polyimide sheet, fluororesin sheet, polyamide sheet, acrylic resin sheet, norbornene resin sheet, cycloolefin resin sheet, and the like. These plastic sheets may be transparent or translucent, or may be colored or uncolored. According to an example, the substrate 11 may be polyethylene terephthalate (PET). According to another example, the substrate 11 may be polyimide (PI).
이러한 플라스틱 시트 상에는 이형층이 배치되어 있을 수 있다. 이형층은 기재(11)가 밀봉 시트(10A)으로부터 분리될 때 밀봉층이 손상되지 않고 형상을 유지할 수 있도록 쉽게 분리시킬 수 있다. 여기서, 이형층은 일반적으로 사용되는 시트 타입의 이형 물질(이형제)일 수 있다. A release layer may be disposed on the plastic sheet. The release layer can be easily separated so that the sealing layer is not damaged and maintains its shape when the substrate 11 is separated from the sealing sheet 10A. Here, the release layer may be a generally used sheet-type release material (release agent).
이형층에 사용되는 이형제의 성분으로는 특별히 한정되지 않으며, 당 업계에 알려진 통상적인 이형제 성분을 사용할 수 있다. 이의 비제한적인 예로는, 에폭시 기반 이형제, 불소 수지로 이루어진 이형제, 실리콘계 이형제, 알키드 수지계 이형제, 수용성 고분자 등을 들 수 있다. 또, 필요에 따라 이형층의 성분으로 분말형 필러, 예컨대 실리콘, 실리카 등을 포함할 수 있다. 이때, 미립자 형태의 분말 필러는 2 타입의 분말 필러를 혼용할 수 있으며, 이때 이들의 평균 입도는 형성되는 표면조도를 고려하여 적절히 선택할 수 있다. The component of the release agent used in the release layer is not particularly limited, and conventional components of the release agent known in the art may be used. Non-limiting examples thereof include an epoxy-based releasing agent, a releasing agent made of a fluorine resin, a silicone-based releasing agent, an alkyd resin-based releasing agent, and a water-soluble polymer. In addition, as a component of the release layer, if necessary, a powdered filler, such as silicon or silica, may be included. At this time, the powder fillers in the form of fine particles may be mixed with two types of powder fillers, and the average particle size thereof may be appropriately selected in consideration of the surface roughness to be formed.
이러한 이형층의 두께는 당 업계에 알려진 통상적인 범위 내에서 적절히 조절할 수 있다. The thickness of the release layer can be appropriately adjusted within a conventional range known in the art.
본 발명에서, 기재(11)의 두께는 특별히 한정되지 않으며, 당 업계에 알려진 통상적인 범위 내에서 조절 가능하며, 예컨대 약 5내지 200 ㎛일 수 있고, 구체적으로 약 10 내지 150 ㎛일 수 있고, 더 구체적으로 약 20 내지 100 ㎛일 수 있다. In the present invention, the thickness of the substrate 11 is not particularly limited, and can be adjusted within a typical range known in the art, for example, may be about 5 to 200 μm, specifically about 10 to 150 μm, More specifically, it may be about 20 to 100 μm.
(2) 밀봉층(2) sealing layer
본 발명에 따른 밀봉 시트(10)에서, 밀봉층(12)은 기재의 적어도 일면에 배치되는 부분으로, 반도체 패키징 시, 반도체 장치를 외부의 물리적, 화학적 충격으로부터 보호할 수 있다.In the sealing sheet 10 according to the present invention, the sealing layer 12 is a portion disposed on at least one surface of the substrate, and during semiconductor packaging, the semiconductor device can be protected from external physical and chemical impacts.
이러한 밀봉층(12)은 경화 후의 열팽창계수(구체적으로, 유리전이온도 이전의 선팽창계수)가 약 5 내지 15 ppm/℃ 범위이고, 굴곡 탄성률이 약 15 내지 30 MPa 범위이다. 만약, 밀봉층의 경화 후 열팽창계수가 약 15 ppm/℃를 초과할 경우, 패키지의 휨 현상이 심해질 수 있다. 또한, 밀봉층의 굴곡 탄성률이 약 30 MPa를 초과할 경우, 패키지의 휨 현상이 심해질 수 있다. 이와 같이, 낮은 열팽창계수 및 굴곡 탄성률을 갖는 밀봉층(12)은 FOWLP(Fan-out Wafer Level Package), PLP(Panel Level Package)와 같은 대면적 반도체 패키지의 휨 현상을 억제하여 반도체 장치의 품질 및 신뢰성을 향상시킬 수 있다.The sealing layer 12 has a coefficient of thermal expansion after curing (specifically, a coefficient of linear expansion before the glass transition temperature) of about 5 to 15 ppm/°C, and a flexural modulus of about 15 to 30 MPa. If, after curing the sealing layer, the thermal expansion coefficient exceeds about 15 ppm/°C, the package may be warped. In addition, when the flexural modulus of the sealing layer exceeds about 30 MPa, the package may be warped. As described above, the sealing layer 12 having a low coefficient of thermal expansion and flexural modulus suppresses the warpage of large-area semiconductor packages such as Fan-out Wafer Level Package (FOWLP) and Panel Level Package (PLP), thereby reducing the quality of semiconductor devices and Reliability can be improved.
일례에 따르면, 본 발명의 밀봉층(12)은 (a) 에폭시 수지; (b) i) 스티렌계 반복단위 및 글리시딜 (메트)아크릴레이트계 반복단위를 포함하는 공중합체, ii) 디카르복시산계 화합물과 트리카르복시산계 화합물의 혼합물, 및 iii) 산무수물로 이루어진 군에서 선택된 1종 이상을 함유하는 첨가제; (c) 경화제; 및 (d) 충진제를 포함하는 밀봉 수지 조성물로 형성될 수 있다. 필요에 따라, 상기 밀봉 수지 조성물은 경화촉진제를 추가로 더 포함할 수 있고, 또 에틸렌계 왁스 등과 같은 기타 첨가제를 더 포함할 수 있다.According to an example, the sealing layer 12 of the present invention includes (a) an epoxy resin; (b) i) a copolymer comprising a styrene-based repeating unit and a glycidyl (meth)acrylate-based repeating unit, ii) a mixture of a dicarboxylic acid-based compound and a tricarboxylic acid-based compound, and iii) an acid anhydride Additives containing at least one selected; (c) a hardener; And (d) a filler. If necessary, the sealing resin composition may further include a curing accelerator, and may further include other additives such as ethylene-based wax.
이하, 밀봉 수지 조성물의 각 성분에 대해 설명한다.Hereinafter, each component of the sealing resin composition will be described.
(a) 에폭시 수지(a) epoxy resin
상기 밀봉 수지 조성물에서, 에폭시 수지는 열에 의해 경화제와 반응하여 경화되고, 경화 후 삼차원 망상 구조를 갖는 밀봉층의 매트릭스(matrix) 성분으로, 밀봉층의 접착력을 향상시킬 뿐만 아니라, 내열성, 내수성, 내습성이 우수하여 반도체 패키지의 신뢰성을 향상시킬 수 있다. 또, 에폭시 수지는 기계적 강도, 전기절연성, 내화학약품성, 치수 안정성, 성형성이 우수할 뿐만 아니라, 다른 수지와의 상용성도 우수하다.In the above sealing resin composition, the epoxy resin is cured by reacting with a curing agent by heat, and after curing, as a matrix component of the sealing layer having a three-dimensional network structure, not only improves adhesion of the sealing layer, but also heat resistance, water resistance, and resistance. It has excellent moisture and can improve the reliability of the semiconductor package. In addition, epoxy resins are not only excellent in mechanical strength, electrical insulation, chemical resistance, dimensional stability, and moldability, but also excellent in compatibility with other resins.
본 발명에서 사용 가능한 에폭시 수지는 분자 내 적어도 1 이상의 에폭시기(epoxide group)를 함유하는 고분자로, 분자 내 브롬 등의 할로겐 원자를 포함하지 않는 에폭시 수지인 것이 바람직하다. 또한, 에폭시 수지는 분자 내 실리콘, 우레탄, 폴리이미드, 폴리아미드 등을 함유하고 있을 뿐만 아니라, 분자 내 인 원자(P), 황 원자(S), 질소 원자(N) 등을 포함할 수 있다.The epoxy resin usable in the present invention is a polymer containing at least one epoxy group in the molecule, and is preferably an epoxy resin that does not contain halogen atoms such as bromine in the molecule. In addition, the epoxy resin not only contains silicon, urethane, polyimide, polyamide, etc. in the molecule, but may also contain a phosphorus atom (P), a sulfur atom (S), a nitrogen atom (N), etc.
이러한 에폭시 수지의 종류는 특별히 제한되지 않으며, 예를 들어 비스페놀 A형 에폭시 수지, 비스페놀 F형 에폭시 수지, 또는 이들에 수소 첨가한 것, 페놀 노볼락형 에폭시 수지, 크레졸 노볼락형 에폭시 수지 등의 글리시딜에테르계 에폭시 수지, 헥사히드로프탈산 글리시딜에스테르, 다이머산 글리시딜에스테르 등의 글리시딜에스테르계 에폭시 수지, 트리글리시딜이소시아누레이트, 테트라글리시딜디아미노 디페닐메탄 등의 글리시딜아민계 에폭시 수지, 에폭시화 폴리부타디엔, 에폭시화 대두유 등의 선상 지방족 에폭시 수지 등이 있고, 바람직하게는 비스페놀 A형 에폭시 수지, 비스페놀 F형 에폭시 수지, 페놀 노볼락형 에폭시 수지, 크레종 노볼락형 에폭시 수지, 바이페닐(Biphenyl)형 에폭시 수지, 다관능 에폭시(Epoxy) 수지 등이 있다. 이들은 단독으로 사용될 수 있으며, 또는 2종 이상이 혼합하여 사용될 수 잇다.The type of such epoxy resin is not particularly limited, and for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, or hydrogenated ones thereof, phenol novolak type epoxy resin, cresol novolak type epoxy resin, etc. Glycidyl ester epoxy resins such as cidyl ether epoxy resin, hexahydrophthalic acid glycidyl ester and dimer acid glycidyl ester, triglycidyl isocyanurate, tetraglycidyldiamino diphenylmethane, etc. Linear aliphatic epoxy resins such as glycidylamine epoxy resin, epoxidized polybutadiene, epoxidized soybean oil, etc., and preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, creson There are novolak-type epoxy resins, biphenyl-type epoxy resins, and polyfunctional epoxy resins. These may be used alone, or two or more may be used in combination.
이러한 에폭시 수지의 함량은 특별히 한정되지 않으며, 예컨대 당해 수지 조성물의 총량을 기준으로 약 3 내지 20 중량% 범위, 구체적으로 약 5 내지 15 중량% 범위일 수 있다. 상기 에폭시 수지의 함량이 전술한 범위를 가질 경우, 밀봉층의 접착성, 내열성이 향상될 뿐만 아니라, 반도체 패키지의 휨 현상을 억제할 수 있다.The content of the epoxy resin is not particularly limited, and may be, for example, in the range of about 3 to 20% by weight, specifically, in the range of about 5 to 15% by weight, based on the total amount of the resin composition. When the content of the epoxy resin is within the above-described range, not only the adhesion and heat resistance of the sealing layer are improved, but also the warpage of the semiconductor package can be suppressed.
(b) 첨가제(b) additive
상기 밀봉 수지 조성물에서, 첨가제는 i) 스티렌계 반복단위 및 글리시딜 (메트)아크릴레이트계 반복단위를 포함하는 공중합체, ii) 디카르복시산계 화합물 및 트리카르복시산계 화합물을 함유하는 카르복시산계 화합물, 및 iii) 산무수물로 이루어진 군에서 선택된 1종 이상을 함유한다. 이러한 첨가제는 밀봉층의 열팽창계수 및 굴곡 탄성률을 낮출 수 있다.In the sealing resin composition, the additive is i) a copolymer containing a styrene-based repeating unit and a glycidyl (meth)acrylate-based repeating unit, ii) a carboxylic acid-based compound containing a dicarboxylic acid-based compound and a tricarboxylic acid-based compound, And iii) an acid anhydride. These additives can lower the coefficient of thermal expansion and flexural modulus of the sealing layer.
여기서, 스티렌계 반복단위 및 글리시딜 (메트)아크릴레이트계 반복단위를 포함하는 공중합체는 밀봉층의 열팽창계수 및 굴곡 탄성률을 낮출 뿐만 아니라, 수지 조성물을 시트형으로 형성할 경우의 시트 형성성을 향상시킬 수 있다.Here, the copolymer containing a styrene-based repeating unit and a glycidyl (meth)acrylate-based repeating unit not only lowers the coefficient of thermal expansion and flexural modulus of the sealing layer, but also has sheet formability when the resin composition is formed in a sheet shape. Can be improved.
이러한 공중합체에서, 스티렌계 반복단위는 밀봉층의 강직성 및 변형율(strain)을 증가시키는 역할을 하고, 글리시딜 (메트)아크릴레이트계 반복단위는 밀봉 수지 조성물 내 에폭시 수지와의 상용성을 향상시키는 역할을 한다. 따라서, 본 발명의 공중합체는 스티렌계 반복단위와 글리시딜 (메트)아크릴레이트계 반복단위를 5:95 ~ 95:5 몰비율, 구체적으로 60:40 ~ 95:5 몰비율, 더 구체적으로 80:20 ~ 95:5 몰비율로 포함함으로써, 에폭시 수지와의 상용성 저하 없이, 시트 형성성을 용이하게 할 수 있다. In such a copolymer, the styrene repeating unit serves to increase the stiffness and strain of the sealing layer, and the glycidyl (meth)acrylate repeating unit improves compatibility with the epoxy resin in the sealing resin composition. It plays a role of letting go. Therefore, the copolymer of the present invention comprises a styrene-based repeating unit and a glycidyl (meth)acrylate-based repeating unit in a molar ratio of 5:95 to 95:5, specifically in a molar ratio of 60:40 to 95:5, more specifically By including it in a molar ratio of 80:20 to 95:5, it is possible to facilitate sheet formation without lowering the compatibility with the epoxy resin.
상기 공중합체의 중량평균분자량(Mw)은 약 1,000 내지 15,000 g/mol 범위, 구체적으로 약 5,000 내지 13,000 g/mol, 더 구체적으로 약 8,000 내지 12,000 g/mol일 수 있다. 만약, 상기 공중합체의 중량평균분자량이 전술한 범위를 벗어날 경우, 에폭시 수지와의 상용성이 저하될 수 있다.The weight average molecular weight (Mw) of the copolymer may be in the range of about 1,000 to 15,000 g/mol, specifically about 5,000 to 13,000 g/mol, and more specifically about 8,000 to 12,000 g/mol. If the weight average molecular weight of the copolymer is out of the above-described range, compatibility with the epoxy resin may decrease.
상기 공중합체는 하기 화학식 1로 표시되는 스티렌계 반복단위 및 하기 화학식 2로 표시되는 글리시딜 (메트)아크릴레이트계 반복단위를 포함하는 고분자일 수 있으나, 이에 한정되지 않는다. 이때, 상기 공중합체는 랜덤 공중합체일 수 있다.The copolymer may be a polymer including a styrenic repeating unit represented by Formula 1 below and a glycidyl (meth)acrylate repeating unit represented by Formula 2 below, but is not limited thereto. In this case, the copolymer may be a random copolymer.
Figure PCTKR2020011715-appb-C000001
Figure PCTKR2020011715-appb-C000001
Figure PCTKR2020011715-appb-C000002
Figure PCTKR2020011715-appb-C000002
상기 화학식 1 및 2에서,In Formulas 1 and 2,
a는 0 내지 5의 정수이고, a is an integer from 0 to 5,
복수의 R3는 서로 동일하거나 상이하며,A plurality of R 3 are the same as or different from each other,
R1 내지 R5는 서로 동일하거나 상이하고, 각각 독립적으로 수소 또는 C1~C12의 알킬기이고, 구체적으로 수소 또는 C1~C6의 알킬기일 수 있고, 더 구체적으로 수소일 수 있다.R 1 to R 5 may be the same as or different from each other, and each independently hydrogen or a C 1 to C 12 alkyl group, specifically hydrogen or a C 1 to C 6 alkyl group, and more specifically hydrogen.
구체적으로, 상기 공중합체는 상기 화학식 1의 스티렌계 반복단위와 상기 화학식 2의 글리시딜 (메트)아크릴레이트계 반복단위가 5:95 ~ 95:5의 몰비율, 구체적으로 80:20 ~ 95:5의 몰비율로 선상으로 불규칙하게 배열된 랜덤 고분자로, 하기 화학식 3으로 표시되는 랜덤 공중합체일 수 있다. Specifically, in the copolymer, the styrene repeating unit of Formula 1 and the glycidyl (meth)acrylate repeating unit of Formula 2 are in a molar ratio of 5:95 to 95:5, specifically 80:20 to 95 It is a random polymer that is irregularly arranged in a linear shape at a molar ratio of :5, and may be a random copolymer represented by Formula 3 below.
Figure PCTKR2020011715-appb-C000003
Figure PCTKR2020011715-appb-C000003
상기 화학식 3에서, In Chemical Formula 3,
a 및 R1 내지 R5는 각각 화학식 1 및 2에 정의한 바와 같고,a and R 1 to R 5 are as defined in Formulas 1 and 2, respectively,
m 및 n은 각각 1 내지 90의 정수이고,m and n are each an integer of 1 to 90,
다만 m : n = 5:95 ~ 95:5의 몰비율이고, 구체적으로 m : n = 80:20 ~ 95:5의 몰비율일 수 있다.However, it may be a molar ratio of m:n = 5:95 to 95:5, and specifically m:n = 80:20 to 95:5.
본 발명에 따른 첨가제는 카르복시산계 화합물을 포함할 수 있다. 상기 카르복시산계 화합물은 디카르복시산계 화합물 및 트리카르복시산계 화합물을 함유한다. 이러한 카르복시산계 화합물은 밀봉층의 응력을 완화시켜 밀봉층의 열팽창계수 및 굴곡 탄성률을 낮출 뿐만 아니라, 에폭시 수지의 에폭시기에 폴리에스테르기를 부여하여 에폭시 수지를 경화시킬 수 있다. The additive according to the present invention may include a carboxylic acid-based compound. The carboxylic acid-based compound contains a dicarboxylic acid-based compound and a tricarboxylic acid-based compound. Such a carboxylic acid-based compound not only reduces the stress of the sealing layer to lower the thermal expansion coefficient and the flexural modulus of the sealing layer, but also can cure the epoxy resin by imparting a polyester group to the epoxy group of the epoxy resin.
이러한 카르복시산계 화합물에서, 디카르복시산계 화합물은 분자 내 카르복시기를 2개 갖는 방향족 카르복시산으로, 예컨대 하기 화학식 4로 표시되는 화합물일 수 있다. In such a carboxylic acid-based compound, the dicarboxylic acid-based compound is an aromatic carboxylic acid having two carboxyl groups in the molecule, and may be, for example, a compound represented by the following formula (4).
Figure PCTKR2020011715-appb-C000004
Figure PCTKR2020011715-appb-C000004
상기 화학식 4에서, In Chemical Formula 4,
R6 내지 R9는 서로 동일하거나 상이하고, 각각 독립적으로 C1~C12의 탄화수소기, C2~C14의 불포화 탄화수소기 및 카르복실기로 치환된 C2~C14의 탄화수소기로 이루어진 군에서 선택되고, 구체적으로 C1~C12의 알킬기, C2~C14의 알케닐기, C2~C14의 알키닐기, 및 카르복실기로 치환된 C2~C14의 알킬기로 이루어진 군에서 선택될 수 있으며,R 6 to R 9 are the same as or different from each other, and each independently selected from the group consisting of a C 1 to C 12 hydrocarbon group, a C 2 to C 14 unsaturated hydrocarbon group, and a C 2 to C 14 hydrocarbon group substituted with a carboxyl group And, specifically, a C 1 to C 12 alkyl group, a C 2 to C 14 alkenyl group, a C 2 to C 14 alkynyl group, and a C 2 to C 14 alkyl group substituted with a carboxyl group. ,
다만, 상기 R6 내지 R9 중 적어도 2개는 카르복실기로 치환된 C2~C14의 탄화수소기이고, 나머지 중 적어도 1개는 C2~C14의 불포화 탄화수소기이다. However, at least two of R 6 to R 9 are C 2 to C 14 hydrocarbon groups substituted with a carboxyl group, and at least one of the remaining ones is a C 2 to C 14 unsaturated hydrocarbon group.
일례에 따르면, 상기 화학식 4로 표시되는 화합물에서, R6 및 R7은 서로 동일하거나 상이하고, 각각 독립적으로 카르복실기로 치환된 C2~C14의 탄화수소기이고, 구체적으로 카르복실기로 치환된 C2~C14의 알킬기일 수 있고, R8은 C2~C14의 불포화 탄화수소기이고, 구체적으로 C2~C14의 알케닐기, C2~C14의 알키닐기이고, 더 구체적으로 C2~C14의 알케닐기일 수 있으며, R9는 C1~C12의 탄화수소기이고, 구체적으로 C1~C12의 알킬기일 수 있다.According to an example, in the compound represented by Formula 4, R 6 and R 7 are the same as or different from each other, and are each independently a hydrocarbon group of C 2 to C 14 substituted with a carboxyl group, and specifically C 2 substituted with a carboxyl group ~ C can be a 14 alkyl group, R 8 is C 2 ~ unsaturated hydrocarbon group of C 14, and specifically, C 2 ~ and an alkynyl group of C 14 alkenyl group, C 2 ~ C 14 of, more specifically, C 2 ~ It may be a C 14 alkenyl group, and R 9 may be a C 1 to C 12 hydrocarbon group, and specifically a C 1 to C 12 alkyl group.
본 발명의 카르복시산계 화합물에서, 트리카르복시산계 화합물은 분자 내 카르복시기를 3개 갖는 방향족 카르복시산으로, 예컨대 하기 화학식 5로 표시되는 화합물일 수 있다.In the carboxylic acid-based compound of the present invention, the tricarboxylic acid-based compound is an aromatic carboxylic acid having three carboxyl groups in the molecule, and may be, for example, a compound represented by the following formula (5).
Figure PCTKR2020011715-appb-C000005
Figure PCTKR2020011715-appb-C000005
상기 화학식 5에서, In Chemical Formula 5,
R10 내지 R15는 서로 동일하거나 상이하고, 각각 독립적으로 C1~C12의 탄화수소기, C2~C14의 불포화 탄화수소기 및 카르복실기로 치환된 C2~C14의 탄화수소기로 이루어진 군에서 선택되고, 구체적으로 C1~C12의 알킬기, C2~C14의 알케닐기, C2~C14의 알키닐기, 및 카르복실기로 치환된 C2~C14의 알킬기로 이루어진 군에서 선택될 수 있으며,R 10 to R 15 are the same as or different from each other, and each independently selected from the group consisting of a C 1 to C 12 hydrocarbon group, a C 2 to C 14 unsaturated hydrocarbon group, and a C 2 to C 14 hydrocarbon group substituted with a carboxyl group And, specifically, a C 1 to C 12 alkyl group, a C 2 to C 14 alkenyl group, a C 2 to C 14 alkynyl group, and a C 2 to C 14 alkyl group substituted with a carboxyl group. ,
다만, 상기 R10 내지 R15 중 적어도 3개는 카르복실기로 치환된 C2~C14의 탄화수소기이고, 나머지 중 적어도 1개는 C2~C14의 불포화 탄화수소기이다.However, at least three of R 10 to R 15 are C 2 to C 14 hydrocarbon groups substituted with a carboxyl group, and at least one of the others is a C 2 to C 14 unsaturated hydrocarbon group.
일례에 따르면, 상기 화학식 5로 표시되는 화합물에서, R10 내지 R12는 서로 동일하거나 상이하고, 각각 독립적으로 카르복실기로 치환된 C2~C14의 탄화수소기이고, 구체적으로 카르복실기로 치환된 C2~C14의 알킬기일 수 있고, R13은 C2~C14의 불포화 탄화수소기이고, 구체적으로 C2~C14의 알케닐기, C2~C14의 알키닐기이고, 더 구체적으로 C2~C14의 알케닐기일 수 있으며, R14 및 R15는 서로 동일하거나 상이하고, 각각 독립적으로 C1~C12의 탄화수소기이고, 구체적으로 C1~C12의 알킬기일 수 있다.According to an example, in the compound represented by Formula 5, R 10 to R 12 are the same as or different from each other, and are each independently a C 2 to C 14 hydrocarbon group substituted with a carboxyl group, and specifically C 2 substituted with a carboxyl group ~ C can be a 14 alkyl group, R 13 is C 2 ~ unsaturated hydrocarbon group of C 14, and specifically, C 2 ~ and an alkynyl group of C 14 alkenyl group, C 2 ~ C 14 of, more specifically, C 2 ~ It may be a C 14 alkenyl group, R 14 and R 15 are the same as or different from each other, and each independently a C 1 to C 12 hydrocarbon group, and specifically may be a C 1 to C 12 alkyl group.
이러한 디카르복시산계 화합물과 트리카르복시산계 화합물의 혼합 비율은 특별히 한정되지 않는다. 일례에 따르면, 상기 디카르복시산계 화합물과 트리카르복시산계 화합물의 혼합 비율은 10:90 ~ 30:70 중량 비율일 수 있다. 다른 일례에 따르면, 상기 디카르복시산계 화합물과 트리카르복시산계 화합물의 혼합 비율은 70:30 ~ 99:1 중량비율일 수 있다. The mixing ratio of the dicarboxylic acid compound and the tricarboxylic acid compound is not particularly limited. According to an example, the mixing ratio of the dicarboxylic acid-based compound and the tricarboxylic acid-based compound may be 10:90 ~ 30:70 weight ratio. According to another example, the mixing ratio of the dicarboxylic acid-based compound and the tricarboxylic acid-based compound may be a weight ratio of 70:30 to 99:1.
본 발명에 따른 첨가제는 산무수물을 포함할 수 있다. 산무수물은 밀봉층의 열팽창계수 및 굴곡 탄성률을 낮출 뿐만 아니라, 에폭시 수지를 경화시킬 수 있다.The additive according to the present invention may contain an acid anhydride. The acid anhydride not only lowers the coefficient of thermal expansion and flexural modulus of the sealing layer, but also can cure the epoxy resin.
일례에 따르면, 산무수물은 하기 화학식 6으로 표시되는 화합물 및 하기 화학식 7로 표시되는 화합물로 이루어진 군에서 선택된 1종 이상일 수 있는데, 이에 한정되지 않는다.According to an example, the acid anhydride may be one or more selected from the group consisting of a compound represented by the following formula (6) and a compound represented by the following formula (7), but is not limited thereto.
Figure PCTKR2020011715-appb-C000006
Figure PCTKR2020011715-appb-C000006
Figure PCTKR2020011715-appb-C000007
Figure PCTKR2020011715-appb-C000007
상기 화학식 6 및 7에서, In Chemical Formulas 6 and 7,
X1 및 X2는 서로 동일하거나 상이하고, 각각 독립적으로 O, S, 및 NAr1으로 이루어진 군에서 선택되고, 구체적으로 O일 수 있고, X 1 and X 2 are the same as or different from each other, each independently selected from the group consisting of O, S, and NAr 1, and may be specifically O,
Ar1은 수소 또는 C1~C12의 탄화수소기이며, 구체적으로 수소 또는 C1~C12의 알킬기이고,Ar 1 is hydrogen or a C 1 to C 12 hydrocarbon group, specifically hydrogen or a C 1 to C 12 alkyl group,
Y1 및 Y2는 각각 이중결합 산소(=O)이다.Y 1 and Y 2 are each a double bond oxygen (=O).
본 발명에 따른 밀봉 수지 조성물에서, 첨가제의 함량은 특별히 한정되지 않으며, 예컨대 당해 수지 조성물의 총량을 기준으로 약 0.01 내지 20 중량%, 구체적으로 약 0.05 내지 15 중량%, 더 구체적으로 약 0.1 내지 10 중량%일 수 있다.In the sealing resin composition according to the present invention, the content of the additive is not particularly limited, for example, about 0.01 to 20% by weight, specifically about 0.05 to 15% by weight, more specifically about 0.1 to 10, based on the total amount of the resin composition. It may be weight percent.
일례에 따르면, 첨가제가 i) 스티렌계 반복단위 및 글리시딜 (메트)아크릴레이트계 반복단위를 포함하는 공중합체; ii) 디카르복시산계 화합물 및 트리카르복시산계 화합물을 함유하는 카르복시산계 화합물; 및 iii) 산무수물로 이루어진 군에서 선택된 1종을 포함할 경우, 첨가제의 함량은 약 0.1 내지 2 중량%, 구체적으로 약 0.3 내지 1.5 중량%일 수 있다.According to an example, the additive is i) a copolymer comprising a styrene-based repeating unit and a glycidyl (meth)acrylate-based repeating unit; ii) a carboxylic acid compound containing a dicarboxylic acid compound and a tricarboxylic acid compound; And iii) When including one selected from the group consisting of an acid anhydride, the content of the additive may be about 0.1 to 2% by weight, specifically about 0.3 to 1.5% by weight.
다른 일례에 따르면, 첨가제가 스티렌계 반복단위 및 글리시딜 (메트)아크릴레이트계 반복단위를 포함하는 공중합체와 함께, 디카르복시산계 화합물 및 트리카르복시산계 화합물을 함유하는 카르복시산계 화합물 또는 산무수물을 포함하는 경우, 첨가제의 함량은 약 0.3 내지 10 중량%, 구체적으로 약 0.5 내지 5 중량%, 더 구체적으로 약 0.5 내지 2.5 중량%일 수 있다. According to another example, the additive is a carboxylic acid-based compound or an acid anhydride containing a dicarboxylic acid-based compound and a tricarboxylic acid-based compound together with a copolymer containing a styrene-based repeating unit and a glycidyl (meth)acrylate-based repeating unit. When included, the content of the additive may be about 0.3 to 10% by weight, specifically about 0.5 to 5% by weight, and more specifically about 0.5 to 2.5% by weight.
(c) 경화제(c) hardener
본 발명에 따른 밀봉 수지 조성물에서, 경화제는 에폭시 수지와 반응하여 조성물의 경화를 진행시키는 성분이다.In the sealing resin composition according to the present invention, the curing agent is a component that reacts with the epoxy resin to proceed with curing of the composition.
본 발명에서 사용 가능한 경화제로는 당해 기술분야에서 통상적으로 알려진 경화제 성분, 예컨대 페놀계 경화제, 산무수물계 경화제, 아민(Amine)계 경화제 등이 있다.The curing agent usable in the present invention includes a curing agent component commonly known in the art, such as a phenolic curing agent, an acid anhydride curing agent, an amine curing agent, and the like.
상기 페놀계 경화제의 비제한적인 예로는 비페닐계 경화제, 나프탈렌계 경화제, 페놀노볼락계 경화제, 나프틸렌에테르계 경화제, 트리아진 골격 함유-페놀계 경화제 등이 있고, 구체적으로는, MEH-7700, MEH-7810, MEH-7851(메이와카세이(주) 제조) 등과 같은 비페닐계 경화제; NHN, CBN, GPH(니혼카야쿠(주) 제조), SN-170, SN-180, SN-190, SN-475, SN-485, SN-495, SN-375, SN-395(신닛테츠카가쿠(주) 제조), EXB9500(DIC(주) 제조) 등과 같은 나프탈렌계 경화제; TD2090(DIC(주) 제조) 등과 같은 페놀노볼락계 경화제; EXB-6000(DIC(주) 제조) 등과 같은 나프틸렌에테르계 경화제; LA3018, LA7052, LA7054, LA1356(DIC(주) 제조) 등과 같은 트리아진 골격 함유-페놀계 경화제 등이 있다. 이들은 단독으로 또는 2종 이상이 혼합되어 사용될 수 있다.Non-limiting examples of the phenolic curing agent include a biphenyl curing agent, a naphthalene curing agent, a phenol novolak curing agent, a naphthylene ether curing agent, a triazine skeleton-containing-phenolic curing agent, and the like, specifically, MEH-7700 , A biphenyl-based curing agent such as MEH-7810, MEH-7851 (made by Meiwa Kasei Co., Ltd.); NHN, CBN, GPH (manufactured by Nihon Kayaku Co., Ltd.), SN-170, SN-180, SN-190, SN-475, SN-485, SN-495, SN-375, SN-395 (Shinnittetsuka) A naphthalene-based curing agent such as Gaku Corporation) and EXB9500 (manufactured by DIC Corporation); Phenol novolak-based curing agents such as TD2090 (manufactured by DIC Corporation); Naphthylene ether curing agents such as EXB-6000 (manufactured by DIC Corporation); There are triazine skeleton-containing-phenolic curing agents such as LA3018, LA7052, LA7054, LA1356 (manufactured by DIC Corporation), and the like. These may be used alone or in combination of two or more.
상기 산무수물계 경화제의 비제한적인 예로는 테트라하이드로 프탈산 무수물, 메틸 테트라하이드로프탈산 무수물, 메틸 헥사하이드로 프탈산 무수물, 헥사하이드로 프탈산 무수물, 트리알킬 테트라하이드로프탈산 무수물, 메틸 사이클로헥센디카르복실산 무수물, 프탈산 무수물, 말레산 무수물, 피로멜리트산 무수물 등이 있는데, 이들은 단독으로 또는 2종 이상이 혼합되어 사용될 수 있다.Non-limiting examples of the acid anhydride-based curing agent include tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, hexahydrophthalic anhydride, trialkyl tetrahydrophthalic anhydride, methyl cyclohexenedicarboxylic anhydride, phthalic acid There are anhydride, maleic anhydride, pyromellitic anhydride, and the like, which may be used alone or in combination of two or more.
또, 상기 아민계 경화제의 비제한적인 예로는 메타페닐렌디아민, 디아미노디페닐메탄, 디아미노디페닐설폰 등의 방향족 아민계 경화제; 디에틸렌트리아민, 트리에틸렌테트라아민 등의 지방족 아민계 경화제 등이 있는데, 이들은 단독으로 또는 2종 이상이 혼합되어 사용될 수 있다.In addition, non-limiting examples of the amine-based curing agent include aromatic amine-based curing agents such as metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone; There are aliphatic amine-based curing agents such as diethylenetriamine and triethylenetetraamine, and these may be used alone or in combination of two or more.
그 외에, 디시안디아미드(dicyandiamide) 등과 같은 잠재성 경화제 등이 있는데, 이에 한정되지 않는다. In addition, there are latent curing agents such as dicyandiamide, but are not limited thereto.
일례에 따르면, 경화제는 페놀계 경화제, 구체적으로 나프탈렌계 경화제, 더 구체적으로 하기 화학식 8로 표시되는 경화제일 수 있다.According to an example, the curing agent may be a phenol-based curing agent, specifically a naphthalene-based curing agent, and more specifically, a curing agent represented by Formula 8 below.
Figure PCTKR2020011715-appb-C000008
Figure PCTKR2020011715-appb-C000008
(상기 화학식 8에서,(In Chemical Formula 8,
b 및 c는 각각 1 내지 2의 정수이고, b and c are each an integer of 1 to 2,
Ar1 및 Ar2는 서로 동일하거나 상이하고, 각각 독립적으로 C1~C6의 탄화수소기, 구체적으로 C1~C6의 알킬렌기, 더 구체적으로 메틸렌기이고, Ar 1 and Ar 2 are the same as or different from each other, and each independently a C 1 to C 6 hydrocarbon group, specifically a C 1 to C 6 alkylene group, more specifically a methylene group,
n1은 1 내지 20의 정수임).n1 is an integer from 1 to 20).
본 발명의 밀봉 수지 조성물에서, 경화제의 함량은 특별히 한정되지 않으며, 예를 들어 밀봉 수지 조성물의 총량을 기준으로 약 1 내지 10 중량% 범위, 구체적으로 약 2 내지 8 중량%범위일 수 있다.In the sealing resin composition of the present invention, the content of the curing agent is not particularly limited, and for example, may be in the range of about 1 to 10% by weight, specifically in the range of about 2 to 8% by weight based on the total amount of the sealing resin composition.
(d) 충진제(d) filler
본 발명에 따른 밀봉 수지 조성물에서, 충진제는 밀봉층의 내열성, 절연성, 기계적 물성(예, 강도 등), 저응력성을 향상시킬 수 있다. In the sealing resin composition according to the present invention, the filler can improve heat resistance, insulation, mechanical properties (eg, strength, etc.), and low stress of the sealing layer.
본 발명에서 사용 가능한 충진제의 비제한적인 예로는, 천연 실리카(natural silica), 용융 실리카(Fused silica), 비결정질 실리카(amorphous silica), 결정 실리카(crystalline silica) 등과 같은 실리카; 수산화알루미늄(Aluminum hydroxide, ATH), 보에마이트(boehmite), 알루미나, 탈크(Talc), 유리(예, 구형 유리), 탄산칼슘, 탄산마그네슘, 마그네시아, 클레이, 규산칼슘, 산화마그네슘(MgO), 산화티탄, 산화안티몬, 유리섬유, 붕산알루미늄, 티탄산바륨, 티탄산스트론튬, 티탄산칼슘, 티탄산마그네슘, 티탄산비스무스, 티타니아(예, TiO2), 지르콘산바륨, 지르콘산칼슘, 질화붕소, 질화규소, 활석(talc), 운모(mica) 등이 포함된다. 이러한 충진제는 단독 또는 2개 이상으로 혼용하여 사용될 수 있다. 일례로, 충진제는 실리카일 수 있다. 이때, 실리카는 하기 표면 처리제, 특히 실란계 커플링제, 구체적으로 에폭시계 실란 커플링제로 표면 처리된 것일 수 있다.Non-limiting examples of the fillers usable in the present invention include silica such as natural silica, fused silica, amorphous silica, crystalline silica, and the like; Aluminum hydroxide (ATH), boehmite, alumina, talc, glass (e.g. spherical glass), calcium carbonate, magnesium carbonate, magnesia, clay, calcium silicate, magnesium oxide (MgO), Titanium oxide, antimony oxide, glass fiber, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titania (e.g. TiO 2 ), barium zirconate, calcium zirconate, boron nitride, silicon nitride, talc ( talc), mica, and the like. These fillers may be used alone or in combination of two or more. For example, the filler may be silica. In this case, the silica may be surface-treated with the following surface treatment agent, in particular, a silane-based coupling agent, specifically an epoxy-based silane coupling agent.
이러한 충진제의 평균 입경(D50)은 특별히 제한되지 않으며, 이종의 충진제를 혼합하여 사용할 수 있다. 일례로, 평균 입경(D50)이 약 1 내지 20 ㎛인 충진제 및 평균 입경(D50)이 약 15 내지 50 ㎛인 충진제를 혼합 사용할 수 있다. 다른 일례로, 평균 입경(D50)이 약 0.1 내지 10 ㎛인 충진제와 평균 입경(D50)이 약 15 내지 30 ㎛인 제2 충진제를 혼합 사용할 수 있다. 또 다른 일례로, 평균 입경(D50)이 약 0.5 내지 3 ㎛ 범위의 충진제와 평균 입경(D50)이 약 20 내지 25 ㎛ 범위의 충진제를 혼합 사용할 수 있다. 이러한 충진재들의 비율은 1:9 ~ 3:7 중량 비율일 수 있다. 이러한 경우, 충진제의 분산성에서 유리하고, 밀봉층의 기계적 물성이 더 향상될 수 있다.The average particle diameter (D50) of such a filler is not particularly limited, and different types of fillers may be mixed and used. For example, a filler having an average particle diameter (D50) of about 1 to 20 μm and a filler having an average particle diameter (D50) of about 15 to 50 μm may be mixed and used. As another example, a filler having an average particle diameter (D50) of about 0.1 to 10 μm and a second filler having an average particle diameter (D50) of about 15 to 30 μm may be mixed and used. As another example, a filler having an average particle diameter (D50) of about 0.5 to 3 μm and a filler having an average particle diameter (D50) of about 20 to 25 μm may be mixed and used. The ratio of these fillers may be 1:9 to 3:7 weight ratio. In this case, it is advantageous in dispersibility of the filler, and mechanical properties of the sealing layer may be further improved.
또한, 충진제의 형상은 특별히 한정되지 않으며, 예컨대 구형, 플레이크, 침상형(dendrite), 원뿔형, 피라미드형, 무정형(無定形) 등이 있다.In addition, the shape of the filler is not particularly limited, and includes, for example, a spherical shape, a flake, a dendrite, a conical shape, a pyramid shape, and an amorphous shape.
한편, 필요에 따라, 충진제는 표면 처리제로 표면 처리될 수 있다. 이 경우, 충진제는 표면 처리제에 의해 에폭시 수지 간의 상용성이 향상되어 밀봉층의 성형 가공성 및 강성이 향상될 수 있다. 이러한 표면 처리제는 충진제의 표면을 코팅하거나, 또는 충진제와 함께 수지 조성물의 일 성분으로 포함될 수 있다.Meanwhile, if necessary, the filler may be surface treated with a surface treatment agent. In this case, the filler has improved compatibility between the epoxy resins by the surface treatment agent, so that the molding processability and rigidity of the sealing layer may be improved. Such a surface treatment agent may coat the surface of the filler, or may be included as a component of the resin composition together with the filler.
본 발명에서 사용 가능한 표면 처리제는 당 업계에 알려진 것이라면 특별히 제한되지 않으며, 예컨대 실란계 화합물(실란계 커플링제) 등이고, 구체적으로 3-(글리시딜록시)프로필트리메톡시실란, 3-(글리시딜록시)프로필트리에톡시실란, 2-(3,4-에폭시사이클로헥실)에틸 트리메톡시실란, 2-(3,4-에폭시사이클로헥실)에틸 트리에톡시실란, 에폭시프록폭시프로필 트리메톡시실란 등과 같은 에폭시계 실란 커플링제; 3-아미노프로필트리에톡시실란, N-페닐-3-아미노프로필트리메톡시실란 및 N-2-(아미노에틸)-3-아미노프로필트리메톡시실란과 같은 아미노계 실란 커플링제; 3-메타크릴옥시프로필 트리메톡시실란과 같은 비닐계 실란 커플링제 등이 있다. 일례에 따르면, 표면 처리제는 에폭시계 실란 커플링제일 수 있다.The surface treatment agent usable in the present invention is not particularly limited as long as it is known in the art, and is, for example, a silane-based compound (silane-based coupling agent), and specifically, 3-(glycidyloxy)propyltrimethoxysilane, 3-(glycidyloxy) Cydyloxy)propyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl triethoxysilane, epoxyproxoxypropyl trime Epoxy-based silane coupling agents such as oxysilane and the like; Amino-based silane coupling agents such as 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-2-(aminoethyl)-3-aminopropyltrimethoxysilane; And vinyl-based silane coupling agents such as 3-methacryloxypropyl trimethoxysilane. According to an example, the surface treatment agent may be an epoxy-based silane coupling agent.
이러한 표면 처리제의 함량은 특별히 한정되지 않으며, 예컨대 충진제의 100 중량부를 기준으로 약 0.5 내지 20 중량부, 구체적으로 약 1 내지 15 중량부일 수 있다. 이 경우, 충진제와 에폭시 수지 간의 상용성이 향상될 수 있다.The content of the surface treatment agent is not particularly limited, and may be, for example, about 0.5 to 20 parts by weight, specifically about 1 to 15 parts by weight based on 100 parts by weight of the filler. In this case, compatibility between the filler and the epoxy resin may be improved.
본 발명에 따른 밀봉 수지 조성물에서, 충진제의 함량은 밀봉 수지 조성물의 총량을 기준으로 약 75 내지 90 중량%, 구체적으로 약 80 내지 90 중량%일 수 있다. 이 경우 충진재를 적용함으로써 열팽창 계수의 감소 및 모듈러스 특성의 감소효과를 기대할 수 있다. 이러한 특성의 감소로 인하여 반도체 패키지의 휨 현상을 억제할 수 있다. In the sealing resin composition according to the present invention, the content of the filler may be about 75 to 90% by weight, specifically about 80 to 90% by weight, based on the total amount of the sealing resin composition. In this case, by applying the filler, the effect of reducing the coefficient of thermal expansion and reducing the modulus characteristics can be expected. Due to the reduction in these characteristics, it is possible to suppress the warpage of the semiconductor package.
(e) 경화촉진제(e) hardening accelerator
본 발명에 따른 밀봉 수지 조성물은 필요에 따라, 경화촉진제를 추가로 더 포함할 수 있다. 경화촉진제는 수지 조성물 내 성분들이 완전히 경화될 수 있도록 경화 시간을 단축시키는 촉매로, 당 기술 분야에서 통상적으로 알려진 것이라면 특별히 제한되지 않는다. 예를 들어, 유기 포스핀계 화합물, 이미다졸계 화합물, 포스포늄계 화합물, 아민계 화합물, 유기 금속계 화합물 등이 있는데, 이들은 단독으로 사용하거나 2종 이상이 혼합되어 사용될 수 있다.The sealing resin composition according to the present invention may further include a curing accelerator, if necessary. The curing accelerator is a catalyst that shortens the curing time so that the components in the resin composition can be completely cured, and is not particularly limited as long as it is known in the art. For example, there are organic phosphine-based compounds, imidazole-based compounds, phosphonium-based compounds, amine-based compounds, organometallic compounds, and the like, which may be used alone or in combination of two or more.
구체적으로, 유기 포스핀계 화합물은 트리스-4-메톡시 포스핀, 트리페닐 포스핀, 트리부틸 포스핀, 메틸디페닐 포스핀, 디메틸포스핀, 페닐 포스핀, 옥틸포스핀, 디페닐포스핀, 트리페닐포스핀, 트리페닐포스핀트리페닐보란, 트리페닐포스핀-1,4-벤조퀴논 부가물 등이 있는데, 이에 한정되지 않는다. 이들은 단독으로 사용되거나 또는 2종 이상이 혼합되어 사용될 수 있다.Specifically, the organic phosphine-based compound is tris-4-methoxy phosphine, triphenyl phosphine, tributyl phosphine, methyldiphenyl phosphine, dimethylphosphine, phenyl phosphine, octylphosphine, diphenylphosphine, Triphenylphosphine, triphenylphosphine triphenylborane, triphenylphosphine-1,4-benzoquinone adducts, and the like, but are not limited thereto. These may be used alone or in combination of two or more.
상기 이미다졸계 화합물의 비제한적인 예로는 이미다졸, 2-메틸이미다졸, 2-에틸이미다졸, 2-데실이미다졸, 2-헥틸이미다졸, 2-이소프로필이미다졸, 2-운데실 이미다졸, 2-헵탄데실 이미다졸, 2-메틸-4-메틸 이미다졸, 2-에틸-4-메틸 이미다졸, 2-페닐이미다졸, 2-페닐-4-메틸 이미다졸, 1-벤질-2-메틸 이미다졸, 1-벤질-2-페닐 이미다졸, 1-시아노에틸-2-메틸이미다졸, 1-시아노에틸-2-에틸-4-메틸이미다졸, 1-시아노에틸-2-운데실이미다졸, 1-시아노에틸-2-페닐이미다졸, 1-시아노에틸-2-운데실-이미다졸 트리멜리테이트, 1-시아노에틸-2-페닐 이미다졸트리멜리테이트, 2,4-디아미노-6-(2'-메틸이미다졸-(1')-에틸-s-트리아진, 2-페실-4,5-디하이드록시메틸이미다졸, 2-페실-4-메틸-5-하이드록시메틸이미다졸, 2-페실-4-벤질-5-하이드록시메틸이미다졸, 4,4'-메틸렌-비스-(2-에틸-5-메틸이미다졸), 2-아미노에틸-2-메틸 이미다졸, 1-시아노에틸-2-페닐-4,5-디(시아노에톡시 메틸)이미다졸, 1-도데실-2-메틸-3-벤질이미다졸리늄클로라이드, 이미다졸 함유 폴리아미드 등이 있는데, 이들은 단독으로 사용되거나 또는 2종 이상이 혼합되어 사용될 수 있다.Non-limiting examples of the imidazole-based compound include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-decylimidazole, 2-hectylimidazole, 2-isopropylimidazole, 2-undecyl imidazole, 2-heptanedecyl imidazole, 2-methyl-4-methyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenylimidazole, 2-phenyl-4-methyl imidazole , 1-benzyl-2-methyl imidazole, 1-benzyl-2-phenyl imidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole , 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecyl-imidazole trimellitate, 1-cyanoethyl -2-phenyl imidazole trimellitate, 2,4-diamino-6-(2'-methylimidazole-(1')-ethyl-s-triazine, 2-fesyl-4,5-dihyde Roxymethylimidazole, 2-fesyl-4-methyl-5-hydroxymethylimidazole, 2-fesyl-4-benzyl-5-hydroxymethylimidazole, 4,4'-methylene-bis-( 2-ethyl-5-methylimidazole), 2-aminoethyl-2-methyl imidazole, 1-cyanoethyl-2-phenyl-4,5-di(cyanoethoxy methyl)imidazole, 1- There are dodecyl-2-methyl-3-benzylimidazolinium chloride, imidazole-containing polyamide, and the like, and these may be used alone or in combination of two or more.
상기 포스포늄계 화합물의 비제한적인 예로는 벤질트리페닐포스포늄 클로라이드, 부틸트리페닐포스포늄 클로라이드, 부틸트리페닐포스포늄 브로마이드, 에틸트리페닐포스포늄 아세테이트, 에틸트리페닐포스포늄 브로마이드, 에틸트리페닐포스포늄 아이오다이드, 테트라페닐포스포늄 브로마이드, 테트라페닐포스포늄 클로라이드 또는 테트라페닐포스포늄 아이오다이드 등이 있는데, 이들은 단독으로 사용되거나 또는 2종 이상이 혼합되어 사용될 수 있다.Non-limiting examples of the phosphonium-based compound include benzyltriphenylphosphonium chloride, butyltriphenylphosphonium chloride, butyltriphenylphosphonium bromide, ethyltriphenylphosphonium acetate, ethyltriphenylphosphonium bromide, ethyltriphenylphos There are phonium iodide, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride or tetraphenylphosphonium iodide, and these may be used alone or in combination of two or more.
상기 아민계 화합물의 비제한적인 예로는, 트리에틸아민, 트리에틸렌디아민, 테트라메틸-1,3-부탄디아민, 에틸모르폴린, 디아자비시클로운데센, 디아자비시클로노넨 등이 있는데, 이들은 단독으로 사용되거나 또는 2종 이상이 혼합되어 사용될 수 있다.Non-limiting examples of the amine-based compound include triethylamine, triethylenediamine, tetramethyl-1,3-butanediamine, ethylmorpholine, diazabicycloundecene, diazabicyclononene, and the like. It may be used or may be used in combination of two or more.
상기 유기 금속계 화합물은 코발트, 구리, 아연, 철, 니켈, 망간, 주석 등의 유기 금속 착체 또는 유기 금속염이다. 상기 유기 금속 착체의 예로는 코발트(Ⅱ) 아세틸아세토네이트, 코발트(Ⅲ) 아세틸아세토네이트 등의 유기 코발트 착체; 구리(Ⅱ) 아세틸아세토네이트 등의 유기 구리 착체, 아연(Ⅱ) 아세틸아세토네이트 등의 유기 아연 착체; 철(Ⅲ) 아세틸아세토네이트 등의 유기 철 착체; 니켈(Ⅱ) 아세틸아세토네이트 등의 유기 니켈 착체; 망간(Ⅱ) 아세틸아세토네이트 등의 유기 망간 착체 등이 있다. 한편, 상기 유기 금속 염의 예로는, 옥틸산 아연, 옥틸산 주석, 나프텐산 아연, 나프텐산 코발트, 스테아르산 주석, 스테아르산 아연 등을 들 수 있는데, 이에 한정되지는 않는다. 이들은 단독으로 사용되거나 또는 2종 이상이 혼합되어 사용될 수 있다.The organometallic compound is an organometallic complex or organometallic salt such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Examples of the organometallic complex include organic cobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate; Organic copper complexes such as copper (II) acetylacetonate, and organic zinc complexes such as zinc (II) acetylacetonate; Organic iron complexes such as iron (III) acetylacetonate; Organic nickel complexes such as nickel (II) acetylacetonate; And organic manganese complexes such as manganese (II) acetylacetonate. Meanwhile, examples of the organometallic salt include, but are not limited to, zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like. These may be used alone or in combination of two or more.
본 발명의 밀봉 수지 조성물에서, 경화촉진제의 함량은 특별히 한정되지 않으며, 예컨대 밀봉 수지 조성물의 총량을 기준으로 약 0.01 내지 3 중량% 범위, 구체적으로 약 0.05 내지 1.0 중량% 범위일 수 있다. 상기 경화촉진제의 함량이 전술한 범위일 경우, 과경화없이 흐름성을 향상시킬 수 있다.In the sealing resin composition of the present invention, the content of the curing accelerator is not particularly limited, and for example, may be in the range of about 0.01 to 3% by weight, specifically about 0.05 to 1.0% by weight, based on the total amount of the sealing resin composition. When the content of the curing accelerator is within the above-described range, flowability may be improved without overcuring.
(f) 기타 첨가제(f) other additives
선택적으로, 본 발명에 따른 밀봉 수지 조성물은 전술한 성분들 이외에, 당 분야에서 통상적으로 알려진 기타 첨가제를 당해 조성물의 사용 목적 및 사용 환경에 따라 선택적으로 더 포함할 수 있다. Optionally, the sealing resin composition according to the present invention may optionally further include other additives commonly known in the art, in addition to the above-described components, depending on the purpose of use and the environment of use of the composition.
상기 기타 첨가제의 예로는 고급 지방산, 고급 지방산 금속염, 천연 지방산, 파라핀계 왁스, 에틸렌계 왁스(예, 폴리에틸렌 왁스), 에스테르계 왁스 등의 이형제; 카본블랙, 유기염료, 무기염료 등의 착색제; 에폭시실란, 아미노실란, 알킬실란, 머캡토실란, 알콕시실란 등의 커플링제; 변성 실리콘 오일, 실리콘 파우더, 실리콘 레진, 오르가노폴리실록산(organopolysiloxane); 포스파젠, 붕산아연, 수산화알루미늄, 수산화마그네슘 등의 난연제; 소포제; 안료; 염료 등이 있는데, 이들은 단독으로 사용되거나, 또는 2종 이상이 혼합되어 사용될 수 있다.Examples of the other additives include release agents such as higher fatty acids, higher fatty acid metal salts, natural fatty acids, paraffin waxes, ethylene waxes (eg, polyethylene waxes), ester waxes, and the like; Coloring agents such as carbon black, organic dyes, and inorganic dyes; Coupling agents such as epoxysilane, aminosilane, alkylsilane, mercaptosilane, and alkoxysilane; Modified silicone oil, silicone powder, silicone resin, organopolysiloxane; Flame retardants such as phosphazene, zinc borate, aluminum hydroxide, and magnesium hydroxide; Antifoam; Pigment; There are dyes and the like, and these may be used alone or in combination of two or more.
이러한 기타 첨가제의 함량은 특별히 한정되지 않으며, 예컨대 당해 수지 조성물의 총량을 기준으로 약 0.01 내지 10 중량%, 구체적으로 약 0.1 내지 5 중량% 범위일 수 있다. 일례로, 기타 첨가제로 에틸렌계 왁스를 포함할 경우, 기타 첨가제의 함량은 당해 수지 조성물의 총량을 기준으로 약 0.05 내지 3 중량%, 구체적으로 약 0.01 내지 1 중량%일 수 있다.The content of these other additives is not particularly limited, and may be, for example, in the range of about 0.01 to 10% by weight, specifically about 0.1 to 5% by weight, based on the total amount of the resin composition. For example, when the ethylene-based wax is included as the other additive, the content of the other additive may be about 0.05 to 3% by weight, specifically about 0.01 to 1% by weight, based on the total amount of the resin composition.
전술한 밀봉 수지 조성물은 당해 기술분야에 통상적으로 알려진 방법, 예컨대 투롤밀, 쓰리롤밀, 니더, 단축 또는 이축의 압출기 및 코니더 등을 이용한 공지된 용융 혼련 방법으로 제조될 수 있다. 예를 들어, 상술한 바와 같은 각 성분들을 균일하게 섞은 후, 투롤밀을 이용하여 약 100 내지 130℃의 온도에서 용융 혼합하고, 상온으로 냉각시킨 다음, 분말상태로 제품을 수득하는 일반적인 과정을 거쳐 본 발명의 조성물을 수득할 수 있다. The above-described sealing resin composition can be prepared by a method commonly known in the art, such as a known melt-kneading method using a two-roll mill, a three-roll mill, a kneader, a single-screw or twin-screw extruder, and a cone. For example, after uniformly mixing each component as described above, melt-mixing at a temperature of about 100 to 130°C using a two-roll mill, cooling to room temperature, and then through a general process of obtaining a product in a powder state. The composition of the present invention can be obtained.
이와 같은 밀봉 수지 조성물은 종래 밀봉 수지 조성물에 비해 내열성, 성형성, 흐름성, 신뢰성, 휨 특성 및 내크랙성이 우수하다. 따라서, 본 발명은 반도체 장치를 밀봉시, 반도체 장치의 성형 불량율을 낮출 수 있다.Such a sealing resin composition is superior to conventional sealing resin compositions in heat resistance, moldability, flowability, reliability, warpage properties, and crack resistance. Accordingly, the present invention can lower the molding defect rate of the semiconductor device when sealing the semiconductor device.
본 발명에 따른 밀봉층의 두께는 특별히 한정하지 않으며, 반도체 장치의 높이에 따라 조절한다. 예컨대 약 1 내지 800 ㎛, 구체적으로 약 5 내지 500 ㎛, 더 구체적으로 약 5 내지 350 ㎛일 수 있다.The thickness of the sealing layer according to the present invention is not particularly limited, and is adjusted according to the height of the semiconductor device. For example, it may be about 1 to 800 µm, specifically about 5 to 500 µm, and more specifically about 5 to 350 µm.
이하, 도 2에 도시된 본 발명의 제2 실시 형태에 따른 밀봉 시트(10B)에 대하여 설명한다.Hereinafter, a sealing sheet 10B according to a second embodiment of the present invention shown in Fig. 2 will be described.
도 2에 도시된 바와 같이, 본 발명의 밀봉 시트(10B)은 기재(11); 상기 기재(11)의 적어도 일면에 배치되고, 경화 후 열팽창계수가 5~15 ppm/℃이고, 굴곡 탄성률이 15 내지 30 MPa 범위인 밀봉층(12); 및 상기 밀봉층(12)의 외면에 배치된 표면 보호층(13)을 포함한다. As shown in Fig. 2, the sealing sheet 10B of the present invention comprises a base material 11; A sealing layer 12 disposed on at least one surface of the substrate 11 and having a thermal expansion coefficient of 5 to 15 ppm/°C after curing, and a flexural modulus of 15 to 30 MPa; And a surface protective layer 13 disposed on the outer surface of the sealing layer 12.
제2 실시 형태에 따른 밀봉 시트(10B)에서, 기재(11) 및 밀봉층(12)에 대한 설명은 제1 실시 형태에 기재된 바와 동일하기 때문에, 생략한다.In the sealing sheet 10B according to the second embodiment, descriptions of the base material 11 and the sealing layer 12 are the same as those described in the first embodiment, and thus will be omitted.
제2 실시 형태에 따른 밀봉 시트(10B)에서, 표면 보호층(13)는 밀봉층(12)의 타면, 즉 외부 표면 상에 배치되는 부분으로, 밀봉층(12)이 외부 이물질에 의해 오염되는 것을 방지하고, 밀봉 시트가 라미네이트 공정을 통해 반도체 패키지에 적용될 때 시트의 표면, 특히 밀봉층의 표면을 보호한다. 이러한 표면 보호층(13)는 밀봉 시트가 반도체 패키지에 적용시 필요에 따라 박리되어 제거될 수 있다.In the sealing sheet 10B according to the second embodiment, the surface protective layer 13 is a portion disposed on the other surface of the sealing layer 12, that is, the outer surface, and the sealing layer 12 is contaminated by external foreign substances. And protects the surface of the sheet, in particular the surface of the sealing layer, when the sealing sheet is applied to the semiconductor package through the lamination process. When the sealing sheet is applied to a semiconductor package, the surface protection layer 13 may be peeled off and removed as needed.
본 발명에서 사용 가능한 표면 보호층의 재료로는 당 분야에서 통상적으로 알려진 보호 시트라면 특별히 제한되지 않으며, 예컨대 폴리에틸렌테레프탈레이트(PET), 폴리부틸렌테레프탈레이트, 폴리에틸렌나프탈레이트 등의 폴리에스터 시트, 폴리에틸렌 시트, 폴리프로필렌 시트, 셀로판, 다이아세틸셀룰로스 시트, 트라이아세틸셀룰로스 시트, 아세틸셀룰로스부티레이트 시트, 폴리염화비닐 시트, 폴리염화비닐리덴 시트, 폴리비닐알코올 시트, 에틸렌-아세트산비닐 공중합체 시트, 폴리스타이렌 시트, 폴리카보네이트 시트, 폴리메틸펜텐 시트, 폴리설폰 시트, 폴리에터에터케톤 시트, 폴리에터설폰 시트, 폴리에터이미드 시트, 폴리이미드 시트, 불소수지 시트, 폴리아마이드 시트, 아크릴수지 시트, 노보넨계 수지 시트, 사이클로올레핀 수지 시트 등이 있는데, 이에 한정되지 않는다. The material of the surface protective layer that can be used in the present invention is not particularly limited as long as it is a protective sheet commonly known in the art. For example, a polyester sheet such as polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate, polyethylene Sheet, polypropylene sheet, cellophane, diacetylcellulose sheet, triacetylcellulose sheet, acetylcellulose butyrate sheet, polyvinyl chloride sheet, polyvinylidene chloride sheet, polyvinyl alcohol sheet, ethylene-vinyl acetate copolymer sheet, polystyrene sheet, Polycarbonate sheet, polymethylpentene sheet, polysulfone sheet, polyetheretherketone sheet, polyethersulfone sheet, polyetherimide sheet, polyimide sheet, fluororesin sheet, polyamide sheet, acrylic resin sheet, Novo There are ene-based resin sheets, cycloolefin resin sheets, and the like, but are not limited thereto.
또, 표면 보호층(13)는 적어도 일면, 구체적으로 밀봉층(12)과 접촉하는 표면이 매트(matt)한 표면일 수 있다. 이러한 표면 보호층(13)은 밀봉 시트의 밀봉층이 반도체 패키지에 부착된 후 밀봉층으로부터 용이하게 박리되어 제거될 수 있다. In addition, at least one surface of the surface protective layer 13, specifically, a surface in contact with the sealing layer 12 may be a matte surface. The surface protection layer 13 can be easily peeled off and removed from the sealing layer after the sealing layer of the sealing sheet is attached to the semiconductor package.
또, 표면 보호층의 두께는 특별히 한정되지 않으며, 예컨대 약 20 내지 80 ㎛일 수 있고, 구체적으로 약 40 내지 60 ㎛일 수 있다.Further, the thickness of the surface protective layer is not particularly limited, and may be, for example, about 20 to 80 µm, and specifically, about 40 to 60 µm.
본 발명의 밀봉 시트(10A, 10B)는 전술한 밀봉 수지 조성물을 이용하여 밀봉층을 형성하는 것을 제외하고는, 당 분야에 알려진 통상적인 방법에 의해 제조될 수 있다.The sealing sheets 10A and 10B of the present invention can be manufactured by a conventional method known in the art, except for forming the sealing layer using the above-described sealing resin composition.
일례로, 본 발명에 따른 밀봉 시트의 제조방법은 기재의 일면 상에 전술한 밀봉 수지 조성물을 코팅하고 열경화하여 밀봉층을 형성하고, 필요에 따라 상기 밀봉층의 외부 표면에 표면 보호층을 라미네이션하여 제조할 수 있다.As an example, in the method of manufacturing a sealing sheet according to the present invention, the above-described sealing resin composition is coated on one surface of a substrate and thermally cured to form a sealing layer, and if necessary, a surface protective layer is laminated on the outer surface of the sealing layer. It can be manufactured by doing.
상기 밀봉 수지 조성물의 도포 방법은, 당 분야의 통상적인 도포 방법, 일례로 딥 코트법, 에어나이프 코트법, 커튼 코트법, 와이어 바 코트법, 그라비아 코트법, 콤마 코트법, 슬롯 코트법 등을 들 수 있다.The coating method of the sealing resin composition is a conventional coating method in the field, for example, a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, a comma coating method, a slot coating method, etc. Can be lifted.
상기 열경화 공정은 당 분야에 알려진 통상적인 조건 내에서 적절히 실시할 수 있다. 일례로, 열경화는 약 80~200 ℃에서 약 5~60분 동안 수행될 수 있다. 이러한 열경화를 통해 형성된 밀봉층은 반경화된 상태로, 경화도가 약 5~35 %일 수 있다.The thermal curing process may be appropriately performed within conventional conditions known in the art. For example, thermal curing may be performed at about 80 to 200° C. for about 5 to 60 minutes. The sealing layer formed through such thermal curing may be in a semi-cured state and a degree of cure of about 5 to 35%.
전술한 바와 같이, 본 발명의 밀봉 시트는 열팽창계수 및 굴곡 탄성률이 낮은 밀봉층을 포함하기 때문에, 반도체 패키징시 반도체 패키지의 휨 현상을 억제할 수 있고, 나아가 반도체 장치의 품질 및 신뢰성을 향상시킬 수 있다.As described above, since the sealing sheet of the present invention includes a sealing layer having a low coefficient of thermal expansion and flexural elasticity, it is possible to suppress the warpage of the semiconductor package during semiconductor packaging, and further improve the quality and reliability of the semiconductor device. have.
<반도체 장치><Semiconductor device>
한편, 본 발명은 전술한 밀봉 시트를 이용하여 제조된 반도체 장치를 제공한다. 이러한 반도체 장치는 반도체 패키징시 전술한 밀봉 시트의 밀봉층에 의해 반도체 패키지의 휨 현상이 억제되어, 품질 및 신뢰성이 향상될 수 있다.On the other hand, the present invention provides a semiconductor device manufactured using the above-described sealing sheet. In such a semiconductor device, warpage of the semiconductor package is suppressed by the sealing layer of the above-described sealing sheet during semiconductor packaging, so that quality and reliability can be improved.
일례에 따르면, 반도체 장치는 반도체 소자를 구비한 기판; 및 상기 반도체 소자에 접하도록 상기 기판 상에 배치된 밀봉층을 포함한다. 이때, 밀봉층은 밀봉 시트의 밀봉층 부분으로, 기재 및/또는 표면 보호층과 분리된 상태이다. 이러한 밀봉층은 반도체 패키지의 휨 현상 없이 반도체 소자를 밀봉한다.According to an example, a semiconductor device includes a substrate including a semiconductor element; And a sealing layer disposed on the substrate so as to contact the semiconductor device. At this time, the sealing layer is a part of the sealing layer of the sealing sheet, and is in a state separated from the base material and/or the surface protective layer. This sealing layer seals the semiconductor device without warping of the semiconductor package.
상기 반도체 소자는 트랜지스터, 다이오드, 마이크로프로세서, 반도체 메모리 등이 있다. The semiconductor devices include transistors, diodes, microprocessors, and semiconductor memories.
본 발명의 반도체 장치는 전술한 밀봉 시트를 이용한 반도체 패키징 공정을 통해 제조될 수 있다. 예컨대, FOWLP(Fan-out Wafer Level Package), PLP(Panel Level Package) 등과 같은 대면적의 반도체 패키징 공정이 있다. The semiconductor device of the present invention can be manufactured through the semiconductor packaging process using the above-described sealing sheet. For example, there are large-area semiconductor packaging processes such as Fan-out Wafer Level Package (FOWLP) and Panel Level Package (PLP).
이하, 본 발명을 실시예를 통하여 상세히 설명하면 다음과 같다. 다만, 하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail through examples. However, the following examples are only illustrative of the present invention, and the present invention is not limited by the following examples.
<실시예 1~6 및 비교예 1~3> - 밀봉 시트의 제조<Examples 1 to 6 and Comparative Examples 1 to 3>-Preparation of sealing sheet
1-1. 밀봉 수지 조성물의 제조1-1. Preparation of sealing resin composition
하기 표 1에 기재된 조성에 따라 각 성분들을 혼합하여 실시예 1~6 및 비교예 1~3의 밀봉 수지 조성물을 제조하였다. 표 1에 기재된 각 성분의 함량 단위는 중량%로, 당해 수지 조성물의 총량을 기준으로 하였다.Each component was mixed according to the composition shown in Table 1 to prepare the sealing resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3. The content unit of each component listed in Table 1 was weight %, based on the total amount of the resin composition.
1-2. 밀봉 시트의 제조1-2. Production of sealing sheet
실시예 1-1에서 제조된 각 밀봉 수지 조성물을 프레스 공정 진행한 다음, 180 ℃에서 4 시간 동안 건조하여 완전 경화 상태의 밀봉층(두께: 300 ㎛)을 형성하여 실시예 1~6 및 비교예 1~3의 밀봉 시트를 제조하였다.Each sealing resin composition prepared in Example 1-1 was subjected to a press process, and then dried at 180° C. for 4 hours to form a fully cured sealing layer (thickness: 300 μm), and Examples 1 to 6 and Comparative Examples 1 to 3 sealing sheets were prepared.
Figure PCTKR2020011715-appb-T000001
Figure PCTKR2020011715-appb-T000001
<실험예 1> - 밀봉 시트의 물성 평가<Experimental Example 1>-Evaluation of physical properties of the sealing sheet
실시예 1~6 및 비교예 1~3에서 각각 제조된 밀봉 시트에 대하여, 하기 물성 평가를 각각 수행하였고, 그 결과를 표 2에 나타내었다.For the sealing sheets prepared in Examples 1 to 6 and Comparative Examples 1 to 3, respectively, the following physical property evaluation was performed, and the results are shown in Table 2.
1) 선팽창 계수1) Coefficient of linear expansion
실시예 1~6 및 비교예 1~3의 밀봉 수지 조성물을 가열 이송 성형기에서 몰딩한 후, TMA(Thermo Mechanical Analyzer)를 이용하여 유리전이온도 이전의 선팽창 계수(α1) 및 유리전이온도 이후의 선팽창 계수(α2)를 각각 측정하였다.After molding the sealing resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3 in a heat transfer molding machine, the linear expansion coefficient (α1) before the glass transition temperature and linear expansion after the glass transition temperature using a Thermo Mechanical Analyzer (TMA) The coefficients (α2) were measured respectively.
2) 굴곡강도, 굴곡탄성률 및 신율2) Flexural strength, flexural modulus and elongation
밀봉 시트를 6.5 mm×12.5 mm×125 mm의 크기로 제작하여 시편을 제조한 다음, ASTM D790 방법에 따라 각 시편의 굴곡강도, 굴곡탄성률 및 신율을 각각 측정하였다.The sealing sheet was manufactured in a size of 6.5 mm×12.5 mm×125 mm to prepare a specimen, and then the flexural strength, flexural modulus, and elongation of each specimen were measured according to the ASTM D790 method.
3) 유리전이온도(Tg)3) Glass transition temperature (Tg)
동적 열특성 분석기(Dynamic Mechanical Analyzer, DMA)를 이용하여 밀봉 시트의 유리전이온도를 측정하였다. 이때, DMA는 25℃에서 분당 5 ℃씩 온도를 상승시켜 250℃까지 측정하는 조건으로 설정하였다.The glass transition temperature of the sealing sheet was measured using a Dynamic Mechanical Analyzer (DMA). At this time, the DMA was set to a condition of measuring up to 250°C by increasing the temperature by 5°C per minute at 25°C.
4) 휨 특성(Warpage)4) Warpage
캐리어 웨이퍼(지름: 200㎜, 두께: 1㎜) 위에, 접착 테이프(두께: 0.058㎜)를 이용하여 QFP Chip(두께: 0.2㎜)을 부착한 후, 실시예 1~6 및 비교예 1~3에서 제조된 각 밀봉 시트의 밀봉층(두께: 0.5㎜)을 적용하여, 휨 특성을 측정하였다. On the carrier wafer (diameter: 200 mm, thickness: 1 mm), after attaching the QFP Chip (thickness: 0.2 mm) using an adhesive tape (thickness: 0.058 mm), Examples 1 to 6 and Comparative Examples 1 to 3 A sealing layer (thickness: 0.5 mm) of each sealing sheet manufactured in was applied to measure the warpage characteristics.
Figure PCTKR2020011715-appb-T000002
Figure PCTKR2020011715-appb-T000002

Claims (16)

  1. 기재; 및materials; And
    상기 기재의 적어도 일면에 배치되고, 경화 후의 열팽창계수가 5 내지 15 ppm/℃ 범위이고, 굴곡 탄성률이 15 내지 30 MPa 범위인 밀봉층A sealing layer disposed on at least one side of the substrate and having a thermal expansion coefficient in the range of 5 to 15 ppm/°C after curing, and a flexural modulus in the range of 15 to 30 MPa
    을 포함하는 밀봉 시트.Sealing sheet comprising a.
  2. 제1항에 있어서,The method of claim 1,
    상기 밀봉층은 신율이 0.5 내지 0.7 % 범위인, 밀봉 시트.The sealing layer has an elongation in the range of 0.5 to 0.7%, the sealing sheet.
  3. 제1항에 있어서,The method of claim 1,
    상기 밀봉층은 The sealing layer
    (a) 에폭시 수지;(a) epoxy resin;
    (b) i) 스티렌계 반복단위 및 글리시딜 (메트)아크릴레이트계 반복단위를 포함하는 공중합체, ii) 디카르복시산계 화합물과 트리카르복시산계 화합물을 함유하는 카르복시산계 화합물, 및 iii) 산무수물로 이루어진 군에서 선택된 1종 이상을 함유하는 첨가제;(b) i) a copolymer containing a styrene-based repeating unit and a glycidyl (meth)acrylate-based repeating unit, ii) a carboxylic acid-based compound containing a dicarboxylic acid-based compound and a tricarboxylic acid-based compound, and iii) an acid anhydride Additives containing at least one selected from the group consisting of;
    (c) 경화제; 및(c) a hardener; And
    (d) 충진제; (d) fillers;
    를 포함하는 밀봉 수지 조성물로 형성된 밀봉 시트. A sealing sheet formed of a sealing resin composition comprising a.
  4. 제3항에 있어서,The method of claim 3,
    상기 공중합체는 1,000 내지 15,000 g/mol 범위의 중량평균분자량을 갖는, 밀봉 시트.The copolymer has a weight average molecular weight in the range of 1,000 to 15,000 g / mol, sealing sheet.
  5. 제3항에 있어서,The method of claim 3,
    상기 공중합체는 상기 스티렌계 반복단위와 상기 글리시딜 (메트)아크릴레이트계 반복단위를 5:95 ~ 95:5 몰비율로 포함하는 것인, 밀봉 시트.The copolymer includes the styrene-based repeating unit and the glycidyl (meth)acrylate-based repeating unit in a molar ratio of 5:95 to 95:5.
  6. 제5항에 있어서,The method of claim 5,
    상기 공중합체는 상기 스티렌계 반복단위와 상기 글리시딜 (메트)아크릴레이트계 반복단위를 80:20 ~ 95:5 몰비율로 포함하는 것인, 밀봉 시트.The copolymer includes the styrene-based repeating unit and the glycidyl (meth)acrylate-based repeating unit in a molar ratio of 80:20 to 95:5.
  7. 제3항에 있어서,The method of claim 3,
    상기 공중합체에서, 상기 스티렌계 반복단위는 하기 화학식 1로 표시되는 반복단위이고, 상기 글리시딜 (메트)아크릴레이트계 반복단위는 하기 화학식 2로 표시되는 반복단위인, 밀봉 시트:In the copolymer, the styrene-based repeating unit is a repeating unit represented by the following formula (1), and the glycidyl (meth)acrylate-based repeating unit is a repeating unit represented by the following formula (2), sealing sheet:
    [화학식 1][Formula 1]
    Figure PCTKR2020011715-appb-I000001
    Figure PCTKR2020011715-appb-I000001
    [화학식 2][Formula 2]
    Figure PCTKR2020011715-appb-I000002
    Figure PCTKR2020011715-appb-I000002
    (상기 식에서,(In the above formula,
    a는 1 내지 5의 정수이고,a is an integer from 1 to 5,
    R1 내지 R5는 서로 동일하거나 상이하고, 각각 독립적으로 수소 또는 C1~C12의 알킬기임).R 1 to R 5 are the same as or different from each other, and each independently hydrogen or a C 1 to C 12 alkyl group).
  8. 제7항에 있어서,The method of claim 7,
    상기 공중합체는 하기 화학식 3으로 표시되는 랜덤 고분자인, 밀봉 시트:The copolymer is a random polymer represented by the following formula (3), a sealing sheet:
    [화학식 3][Formula 3]
    Figure PCTKR2020011715-appb-I000003
    Figure PCTKR2020011715-appb-I000003
    (상기 식에서, (In the above formula,
    a, R1 내지 R5는 각각 제3항에 정의한 바와 같고,a, R 1 to R 5 are each as defined in claim 3,
    m 및 n은 각각 1 내지 90이고, 다만 m : n = 5:95 ~ 95:5의 몰비율임).m and n are each 1 to 90, provided that m:n = 5:95 to 95:5 molar ratio).
  9. 제3항에 있어서,The method of claim 3,
    상기 카르복시산계 화합물에서, In the carboxylic acid-based compound,
    상기 디카르복시산계 화합물은 하기 화학식 4로 표시되는 화합물이고, The dicarboxylic acid-based compound is a compound represented by the following formula (4),
    상기 트리카르복시산계 화합물은 하기 화학식 5로 표시되는 화합물인, 밀봉 시트:The tricarboxylic acid-based compound is a compound represented by the following formula (5), a sealing sheet:
    [화학식 4][Formula 4]
    Figure PCTKR2020011715-appb-I000004
    Figure PCTKR2020011715-appb-I000004
    (상기 식에서, (In the above formula,
    R6 내지 R9는 서로 동일하거나 상이하고, 각각 독립적으로 C1~C12의 탄화수소기, C2~C14의 불포화 탄화수소기 및 카르복실기로 치환된 C2~C14의 탄화수소기로 이루어진 군에서 선택되고,R 6 to R 9 are the same as or different from each other, and each independently selected from the group consisting of a C 1 to C 12 hydrocarbon group, a C 2 to C 14 unsaturated hydrocarbon group, and a C 2 to C 14 hydrocarbon group substituted with a carboxyl group Become,
    다만, 상기 R6 내지 R9 중 적어도 2개는 카르복실기로 치환된 C2~C14의 탄화수소기이고, 나머지 중 적어도 1개는 C2~C14의 불포화 탄화수소기임);However, at least two of R 6 to R 9 are C 2 to C 14 hydrocarbon groups substituted with a carboxyl group, and at least one of the others is a C 2 to C 14 unsaturated hydrocarbon group);
    [화학식 5][Formula 5]
    Figure PCTKR2020011715-appb-I000005
    Figure PCTKR2020011715-appb-I000005
    (상기 식에서, (In the above formula,
    R10 내지 R15는 서로 동일하거나 상이하고, 각각 독립적으로 C1~C12의 탄화수소기, C2~C14의 불포화 탄화수소기 및 카르복실기로 치환된 C2~C14의 탄화수소기로 이루어진 군에서 선택되고,R 10 to R 15 are the same as or different from each other, and each independently selected from the group consisting of a C 1 to C 12 hydrocarbon group, a C 2 to C 14 unsaturated hydrocarbon group, and a C 2 to C 14 hydrocarbon group substituted with a carboxyl group Become,
    다만, 상기 R10 내지 R15 중 적어도 2개는 카르복실기로 치환된 C2~C14의 탄화수소기이고, 나머지 중 적어도 1개는 C2~C14의 불포화 탄화수소기임).However, at least two of R 10 to R 15 are C 2 to C 14 hydrocarbon groups substituted with a carboxyl group, and at least one of the others is a C 2 to C 14 unsaturated hydrocarbon group).
  10. 제3항에 있어서,The method of claim 3,
    상기 카르복시산계 화합물에서, 상기 디카르복시산계 화합물과 트리카르복시산계 화합물의 혼합 비율은 10:90 ~ 30:70 중량 비율인, 밀봉 시트.In the carboxylic acid-based compound, the mixing ratio of the dicarboxylic acid-based compound and the tricarboxylic acid-based compound is 10:90 to 30:70 weight ratio, sealing sheet.
  11. 제3항에 있어서,The method of claim 3,
    상기 산무수물은 지환식 산무수물인 밀봉 시트.The acid anhydride is an alicyclic acid anhydride sealing sheet.
  12. 제11항에 있어서,The method of claim 11,
    상기 산무수물은 하기 화학식 6로 표시되는 화합물 및 하기 화학식 7로 표시되는 화합물로 이루어진 군에서 선택된 1종 이상인, 밀봉 시트:The acid anhydride is at least one selected from the group consisting of a compound represented by the following formula (6) and a compound represented by the following formula (7), a sealing sheet:
    [화학식 6][Formula 6]
    Figure PCTKR2020011715-appb-I000006
    Figure PCTKR2020011715-appb-I000006
    [화학식 7][Formula 7]
    Figure PCTKR2020011715-appb-I000007
    Figure PCTKR2020011715-appb-I000007
    (상기 식에서, (In the above formula,
    X1 및 X2는 서로 동일하거나 상이하고, 각각 독립적으로 O, S, 및 NAr1으로 이루어진 군에서 선택되고,X 1 and X 2 are the same as or different from each other, and each independently selected from the group consisting of O, S, and NAr 1,
    Ar1은 수소 또는 C1~C12의 탄화수소기이며,Ar 1 is hydrogen or a hydrocarbon group of C 1 to C 12,
    Y1 및 Y2는 각각 이중결합 산소(=O)임).Y 1 and Y 2 are each a double bond oxygen (=O)).
  13. 제3항에 있어서,The method of claim 3,
    상기 에폭시 수지는 비스페놀 A형 에폭시 수지이고,The epoxy resin is a bisphenol A type epoxy resin,
    상기 경화제는 나프탈렌계 경화제인, 밀봉 시트.The curing agent is a naphthalene-based curing agent, sealing sheet.
  14. 제3항에 있어서,The method of claim 3,
    상기 밀봉 수지 조성물은 경화촉진제를 추가로 더 포함하는 밀봉 시트.The sealing resin composition is a sealing sheet further comprising a curing accelerator.
  15. 제1항에 있어서,The method of claim 1,
    상기 밀봉층의 표면 상에 배치된 표면 보호층을 추가로 더 포함하는 밀봉 시트.A sealing sheet further comprising a surface protective layer disposed on the surface of the sealing layer.
  16. 제1항 내지 제15항 중 어느 한 항에 기재된 밀봉 시트의 밀봉층을 포함하는 반도체 패키지. A semiconductor package comprising the sealing layer of the sealing sheet according to any one of claims 1 to 15.
PCT/KR2020/011715 2019-09-09 2020-09-01 Sealing sheet, and semiconductor device including same WO2021049805A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2019-0111419 2019-09-09
KR1020190111419A KR102658294B1 (en) 2019-09-09 2019-09-09 Encapsulation sheet and semiconductor device having the same

Publications (1)

Publication Number Publication Date
WO2021049805A1 true WO2021049805A1 (en) 2021-03-18

Family

ID=74866741

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2020/011715 WO2021049805A1 (en) 2019-09-09 2020-09-01 Sealing sheet, and semiconductor device including same

Country Status (2)

Country Link
KR (1) KR102658294B1 (en)
WO (1) WO2021049805A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100079280A (en) * 2008-12-31 2010-07-08 제일모직주식회사 Liquid epoxy resin composition for encapsulating semiconductor device and semiconductor device using the same
KR20120026473A (en) * 2009-04-30 2012-03-19 스미토모덴키고교가부시키가이샤 Adhesive resin composition, laminate using same, and flexible printed wiring board
KR20150014775A (en) * 2013-07-30 2015-02-09 삼성디스플레이 주식회사 Organic light emitting display device and method of manufacturing the same
KR20160129218A (en) * 2015-04-29 2016-11-09 삼성에스디아이 주식회사 Composition for encapsulating semiconductor device and semiconductor device encapsulated by using the same
KR20190081986A (en) * 2017-12-29 2019-07-09 삼성에스디아이 주식회사 Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated by using the same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104870515B (en) * 2012-12-21 2017-07-07 三井化学株式会社 Sheet type epoxy composition, the manufacture method using its organic EL device, organic EL device and organic EL display panel

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100079280A (en) * 2008-12-31 2010-07-08 제일모직주식회사 Liquid epoxy resin composition for encapsulating semiconductor device and semiconductor device using the same
KR20120026473A (en) * 2009-04-30 2012-03-19 스미토모덴키고교가부시키가이샤 Adhesive resin composition, laminate using same, and flexible printed wiring board
KR20150014775A (en) * 2013-07-30 2015-02-09 삼성디스플레이 주식회사 Organic light emitting display device and method of manufacturing the same
KR20160129218A (en) * 2015-04-29 2016-11-09 삼성에스디아이 주식회사 Composition for encapsulating semiconductor device and semiconductor device encapsulated by using the same
KR20190081986A (en) * 2017-12-29 2019-07-09 삼성에스디아이 주식회사 Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated by using the same

Also Published As

Publication number Publication date
KR20210030017A (en) 2021-03-17
KR102658294B1 (en) 2024-04-16

Similar Documents

Publication Publication Date Title
WO2010058988A2 (en) Laminated plastic substrate, and a production method for the same
WO2013100502A1 (en) Insulating adhesive composition for metal-based copper clad laminate (mccl), coated metal plate using same, and method for manufacturing same
KR102295921B1 (en) Resin composition, resin film, and semiconductor device and method for manufacturing same
US20130158165A1 (en) Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated with the same
CN105566913B (en) Silicone resin, resin composition, resin film, semiconductor device, and method for manufacturing semiconductor device
US9673120B2 (en) Epoxy resin composition for encapsulating semiconductor device and semiconductor package encapsulated using the same
KR20120042643A (en) Sheet for forming semiconductor wafer protecting film
WO2016175385A1 (en) Epoxy resin composition for sealing semiconductor device, and semiconductor device sealed by using same
KR20170127363A (en) Base-attached encapsulant for semiconductor encapsulation, semiconductor apparatus, and method for manufacturing semiconductor apparatus
TWI401270B (en) Epoxy. A polysiloxane mixed resin composition, and a light emitting semiconductor device
JP3261907B2 (en) Epoxy resin composition for semiconductor encapsulation and semiconductor device
WO2010058987A2 (en) Multilayer film and a production method for same
WO2020262980A1 (en) Adhesive composition, coverlay film comprising same, and printed circuit board
WO2021049805A1 (en) Sealing sheet, and semiconductor device including same
WO2017142251A1 (en) Epoxy resin composition for sealing semiconductor device, and semiconductor device sealed by using same
WO2019066605A1 (en) Method for encapsulating organic electronic element
WO2018117373A1 (en) Film-type semiconductor sealing member, semiconductor package manufactured using same, and method for manufacturing same
KR102253432B1 (en) Resin composition, resin film, method for producing resin film, method for producing semiconductor device, and semiconductor device
JP2009124133A (en) Bonding member, support member for mounting semiconductor device and semiconductor device
WO2018117374A1 (en) Film-type semiconductor sealing member, semiconductor package manufactured using same, and method for manufacturing same
US9890307B2 (en) Phosphonium compound, epoxy resin composition including the same and semiconductor device prepared using the same
WO2023282590A1 (en) Heat dissipation composite composition, heat dissipation composite using same, and method for producing same
WO2022014863A1 (en) High-heat dissipation igbt power semiconductor package and manufacturing method therefor
KR20150015317A (en) Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated by using the same
JP2842226B2 (en) Semiconductor device

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20863762

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20863762

Country of ref document: EP

Kind code of ref document: A1