WO2015080098A1 - 半導体用樹脂組成物および半導体用樹脂フィルムならびにこれらを用いた半導体装置 - Google Patents
半導体用樹脂組成物および半導体用樹脂フィルムならびにこれらを用いた半導体装置 Download PDFInfo
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- WO2015080098A1 WO2015080098A1 PCT/JP2014/081097 JP2014081097W WO2015080098A1 WO 2015080098 A1 WO2015080098 A1 WO 2015080098A1 JP 2014081097 W JP2014081097 W JP 2014081097W WO 2015080098 A1 WO2015080098 A1 WO 2015080098A1
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- polyimide
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- 0 *c(ccc(*c(cc1NC(c(cc2C(O3)=O)ccc2C3=O)=O)ccc1O*)c1)c1NC(c(cc1)cc(C(O2)=O)c1C2=O)=O Chemical compound *c(ccc(*c(cc1NC(c(cc2C(O3)=O)ccc2C3=O)=O)ccc1O*)c1)c1NC(c(cc1)cc(C(O2)=O)c1C2=O)=O 0.000 description 5
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- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- H—ELECTRICITY
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- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
- C08G73/1017—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)amine
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
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- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
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- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
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- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
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Definitions
- the present invention relates to an electronic component used in a personal computer, a portable terminal, a heat sink and a printed circuit board, a flexible resin substrate, a semiconductor resin composition and a semiconductor resin film that can be used for adhesion between substrates and wafer protection, and a semiconductor film.
- the present invention relates to the semiconductor device used.
- the present invention relates to the bonding of semiconductor chips such as IC and LSI to circuit boards such as flexible substrates, glass epoxy substrates, glass substrates, ceramic substrates, silicon interposers, and bonding between semiconductor chips.
- the present invention relates to a resin composition for semiconductors, a resin film for semiconductors, and a semiconductor device using these.
- an underfill material is filled between the chip and the substrate.
- a method of filling the underfill material a method of filling between the chip and the substrate using a capillary phenomenon is common, but there is a problem that unfilling is likely to occur and the manufacturing cost is increased.
- a technique for solving these problems a technique has been devised in which an underfill material is formed on a wafer and individual semiconductor chips are bonded to a substrate.
- a method of forming on a wafer there are a method of forming a resin composition formed into a film on a wafer by vacuum heat laminating treatment, a method of forming a resin coating material directly on a wafer, etc. .
- An epoxy resin is generally used for the underfill material in order to impart adhesiveness, but the epoxy resin alone has a large difference in coefficient of linear expansion from the chip to be joined. For this reason, it is difficult to maintain connection reliability in the case where a process requiring a greater durability with a large temperature change such as a moisture absorption reflow process and a thermal cycle process is performed. Therefore, a large amount of inorganic particles may be blended in the underfill material for the purpose of reducing the difference in coefficient of linear expansion from the chip.
- Patent Document 1 a technique for blending polyimide for the purpose of imparting heat resistance to the underfill material (see Patent Document 1) and a technique for blending rubber particles for the purpose of relaxing stress applied to the underfill material after curing (Patent Document) 2).
- the inorganic particles to be blended since the underfill material needs to fill the gaps between the fine structures formed on the substrate or chip, the inorganic particles to be blended must also be fine. However, when a large amount of fine inorganic particles are blended in the underfill material, there is a problem that the inorganic particles are unevenly distributed in the film thickness direction when the film is formed. This is because if the distribution of the inorganic particles is not uniform, a difference occurs in the thermal stress in the film thickness direction, which may reduce the connection reliability when the chips are joined to each other.
- Patent Document 1 a technique for blending polyimide for the purpose of imparting heat resistance to the underfill material (see Patent Document 1) and a technique for blending rubber particles for the purpose of relaxing stress applied to the underfill material after curing (Patent Document) 2)
- Patent Document 2 a technique for blending polyimide for the purpose of imparting heat resistance to the underfill material
- Patent Document 2 a technique for blending rubber particles for the purpose of relaxing stress applied to the underfill material after curing
- the present invention provides inorganic particles in the film thickness direction of a semi-cured film that has a sufficiently small linear expansion coefficient of a cured product while imparting heat resistance and relaxing stress.
- the present invention is a resin composition for a semiconductor comprising (a) an epoxy compound, (b) inorganic particles, (c) a polyimide, and (d) a solvent, wherein the above (d) is calculated from the total weight of the semiconductor resin composition. (B) The ratio of the inorganic particles (b) to 60 wt% or more and 92 wt% or less of the total solid weight excluding the weight of the solvent, and (e) containing rubber particles Resin composition.
- the present invention is a resin film for a semiconductor having a semiconductor resin layer containing (a) an epoxy compound, (b) inorganic particles, (c) polyimide and (e) rubber particles on a support,
- the semiconductor resin film wherein the proportion of the inorganic particles (b) in the weight of the semiconductor resin layer is 60% by weight or more and 92% by weight or less.
- the linear expansion coefficient of the cured product is sufficiently small and the distribution of inorganic particles in the film thickness direction of the formed semi-cured film is uniform while imparting heat resistance and relaxing stress.
- a resin composition for semiconductor, a resin film for semiconductor, and a semiconductor device using these are obtained.
- the present invention is a resin composition for a semiconductor comprising (a) an epoxy compound, (b) inorganic particles, (c) a polyimide, and (d) a solvent, wherein the above (d) is calculated from the total weight of the semiconductor resin composition. (B) The ratio of the inorganic particles (b) to 60 wt% or more and 92 wt% or less of the total solid weight excluding the weight of the solvent, and (e) containing rubber particles Resin composition.
- the resin composition for a semiconductor of the present invention contains (a) an epoxy compound.
- the epoxy compound here refers to a compound containing two or more glycidyl groups or epoxycyclohexyl groups in one molecule.
- (A) The epoxy compound is obtained because (c) the polyimide has a phenolic hydroxyl group, sulfonic acid group or thiol group in the side chain, and reacts with these to form a cured product having a network structure with higher density.
- the cured resin composition for semiconductors exhibits excellent resistance to various chemicals. Therefore, resistance to various solvents, particularly N-methylpyrrolidone can be increased.
- an epoxy compound is generally cured by a ring-opening reaction that is not accompanied by shrinkage, it is possible to reduce shrinkage during curing of the resin composition for a semiconductor.
- an epoxy compound that whose epoxy equivalent is 100 or more is preferable. By setting the epoxy equivalent to 100 or more, the strength of the cured resin composition for a semiconductor can be increased.
- the (a) epoxy compound used in the present invention is not particularly limited as long as it is bifunctional or higher.
- jER828, jER1750, jER152, jER1001, jER1002, jER1004AF, jER1007, jER1009, jER1010, YX4000H, jER4004P, jER5050, jER154, jER157S70, jER180S70, YX4000H, YL980 (trade name, Mitsubishi S) Tepic G, Tepic P (trade names, manufactured by Nissan Chemical Industries, Ltd.), Epototo YH-434L (trade names, manufactured by Nippon Steel Chemical Co., Ltd.), EPPN502H, NC3000, NC3000H (trade names, Nippon Kayaku) ), Epicron N695, Epicron HP-7200, Epicron HP-4032 (trade name, manufactured by DIC Corporation) and the like, but are not limited thereto. Two or more of these may be combined.
- the epoxy compound contains both a liquid epoxy compound and a solid epoxy compound.
- a preferable content of the liquid epoxy compound is 10 to 50% by weight, more preferably 20 to 50% by weight, based on the weight of the epoxy compound (a).
- the liquid epoxy compound indicates a viscosity of 150 Pa ⁇ s or less in an atmosphere of a temperature of 25 ° C. and a pressure of 1.013 ⁇ 10 5 N / m 2
- the solid epoxy compound is a temperature of 25 ° C. and a pressure of 1 It shows a viscosity exceeding 150 Pa ⁇ s in an atmosphere of 013 ⁇ 10 5 N / m 2
- the liquid epoxy compound include, but are not limited to, JER828, JER1750, JER152, JER630, YL980, and Epicron HP-4032 among the above-described epoxy compounds.
- the resin composition for semiconductors of the present invention contains (b) inorganic particles.
- the inorganic particle can adjust the melt viscosity of the resin composition for semiconductors to such an extent that it does not foam.
- Examples of the material of the inorganic particles include silica, alumina, titania, silicon nitride, boron nitride, aluminum nitride, iron oxide, glass and other metal oxides, metal nitrides, metal carbonates, barium sulfate and other metal sulfates Etc. can be used alone or in admixture of two or more.
- silica can be preferably used in terms of low thermal expansion, heat dissipation, low moisture absorption, and dispersion stability in the resin composition for semiconductors.
- the shape of the inorganic particles may be any of non-spherical shapes such as crushed, flaked, elliptical, flat, rod-like, and fibrous, in addition to the spherical shape. It can be preferably used because it is easily dispersed uniformly in the composition.
- the average particle size of the inorganic particles is preferably 10 nm or more and 5 ⁇ m or less. More preferably, the average particle size is 10 nm or more and 1 ⁇ m or less.
- the average particle diameter of the inorganic particles is 10 nm or more and 5 ⁇ m or less, it can be more sufficiently dispersed in the resin composition for semiconductors, and the melt viscosity can be adjusted more appropriately.
- the average particle diameter of (b) inorganic particles is preferably 100 nm or less, and more preferably 60 nm or less. For example, after forming a film of a semiconductor resin composition on a substrate, it is necessary to visually recognize a mark on the substrate surface through the semiconductor resin composition for purposes such as alignment.
- the average particle diameter of inorganic particles indicates the particle diameter when (b) inorganic particles exist alone.
- the particle diameter represents the diameter when the shape is spherical, and represents the maximum length of the shape when the shape is crushed, flaky, elliptical or flat. Further, when the shape is rod-like or fibrous, the particle diameter represents the maximum length in the longitudinal direction.
- a method of measuring the average particle diameter of (b) inorganic particles in the resin composition for semiconductor a method of directly observing the particles with an SEM (scanning electron microscope) and calculating the average particle diameter of 100 particles Can be measured.
- the added amount of (b) inorganic particles used in the present invention is 60% by weight or more and 92% by weight or less with respect to the weight of the total solid content excluding the weight of the solvent (d) from the total weight of the resin composition for semiconductor. Yes, it is preferably 65% by weight or more and 85% by weight or less. If the addition amount is less than 60% by weight, there is a difference in the coefficient of linear expansion from the chip to be joined, so that the connection reliability of a semiconductor device manufactured using this semiconductor resin composition is lowered. In particular, it is difficult to maintain connection reliability in the case where processing requiring higher durability such as moisture absorption reflow processing and thermal cycle processing is performed. When it exceeds 92% by weight, the following problems a and b occur.
- a Dispersibility of the inorganic particles is poor in the semiconductor resin composition, and the inorganic particles are aggregated.
- b When forming a resin composition for a semiconductor on a releasable plastic film to form a resin film for a semiconductor, when it is wound up in a roll shape, it breaks off from the resin resin film for a semiconductor or falls off the releasable plastic film.
- inorganic particles When preparing the resin composition for a semiconductor of the present invention, (b) inorganic particles may be added in a slurry state dispersed in a solvent, or may be added in a powder state without a solvent. Further, both inorganic particles in a slurry state and inorganic particles in a powder state may be added.
- the resin composition for semiconductors of the present invention further contains (e) rubber particles.
- rubber particles By containing rubber particles, a coating film in which (b) inorganic particles are distributed evenly in the film thickness direction when a semiconductor resin composition is formed can be obtained.
- the rubber particle here refers to a particle composed of a rubber-like substance having an elastic modulus of 10 6 to 10 8 Pa.
- materials constituting the rubber particles include silicone rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber (SBR), nitrile rubber (NBR), acrylic rubber, methyl methacrylate-styrene-butadiene copolymer (MBS). ), Acrylonitrile-butadiene-methacrylic acid copolymer, acrylonitrile-butadiene-acrylic acid copolymer, and the like, but are not limited thereto.
- rubber particles (e) rubber particles composed of these materials alone and core-shell rubber particles obtained by graft polymerization of a different polymer on the surface of the rubber particles composed of these materials alone can be used.
- Core-shell rubber particles are preferably used because they can be stably dispersed in the semiconductor resin composition.
- core-shell rubber particles are preferable from the viewpoint of handleability and the like.
- Rubber particles include FX501P (manufactured by JSR) made of a crosslinked product of carboxyl-modified butadiene-acrylonitrile copolymer, CX-MN series (manufactured by Nippon Shokubai Co., Ltd.) made of acrylic rubber fine particles, YR -500 series (manufactured by Nippon Steel Chemical Co., Ltd.) can be used.
- FX501P manufactured by JSR
- CX-MN series manufactured by Nippon Shokubai Co., Ltd.
- YR -500 series manufactured by Nippon Steel Chemical Co., Ltd.
- Examples of commercially available core-shell rubber particles include butadiene, alkyl methacrylate, “Paraloid (registered trademark)” EXL-2655 (manufactured by Kureha Chemical Industry Co., Ltd.) made of a styrene copolymer, “STAPHYLOID (registered trademark)” AC-3355 made of an acrylate ester / methacrylate ester copolymer, TR-2122 (manufactured by Takeda Pharmaceutical Co., Ltd.), “PARALOID (registered trademark)” EXL-2611, EXL-3387 (above, manufactured by Rohm & Haas), “Kane Ace (registered trademark)” MX113 (manufactured by Kaneka Corporation), etc., made of butyl acrylate / methyl methacrylate copolymer Can be used.
- the preferable range of the weight of the (e) rubber particles used is 2 to 50 parts by weight, more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the (a) epoxy compound.
- the preferred range of the weight of the rubber particles used is 2 to 100 parts by weight, more preferably 5 to 50 parts by weight with respect to 100 parts by weight of the liquid epoxy compound. Within the range of 2 to 100 parts by weight with respect to 100 parts by weight of the liquid epoxy compound, the distribution of inorganic particles in the film thickness direction when the resin composition for semiconductor is formed becomes more uniform, and chips and the like are bonded. The bonding strength at the time becomes more sufficient.
- the average particle diameter of rubber particles indicates the particle diameter when (e) rubber particles exist alone.
- the average particle diameter of (e) rubber particles in the resin composition for semiconductors is determined by observing the particles directly with a microscope such as TEM (transmission electron microscope) and calculating the average particle diameter of 100 particles. Can be measured.
- the average particle diameter of (e) rubber particles used in the present invention is not particularly limited, but 10 nm to 5 ⁇ m is preferably used. Within this range, it is relatively easy to obtain industrially, and the physical properties of the cured product of the semiconductor resin composition become more uniform.
- the average particle size of the rubber particles is preferably (b) less than the average particle size of the inorganic particles. In this case, the distribution of (b) inorganic particles in the film thickness direction when the semiconductor resin composition is formed becomes more uniform. (E) Although the effect can be obtained even when the average particle size of the rubber particles is larger than the average particle size of the (b) inorganic particles, the obtained effect may be reduced.
- the resin composition for semiconductors of the present invention contains (c) polyimide.
- C Since the polyimide has an imide ring, it has excellent heat resistance and chemical resistance.
- polyimide having at least one functional group capable of reacting with an epoxy group in the side chain promotes the ring opening of the epoxy compound and the addition reaction to the aromatic polyimide during heat treatment, and more A composition having a network structure with a higher density can be obtained.
- the functional group capable of reacting with the epoxy group include a phenolic hydroxyl group, a sulfonic acid group, and a thiol group.
- the method for synthesizing such a (c) polyimide is not limited to the following example.
- an acid dianhydride having a group capable of reacting with an epoxy group is reacted with a diamine to obtain a polyimide precursor.
- terminal modification of this polyimide precursor is performed using primary monoamine as a terminal blocking agent, followed by heat treatment at 150 ° C. or higher to perform polyimide ring closure.
- a diamine is added to synthesize a terminal precursor-modified polyimide precursor, and the polyimide ring closure is performed at a high temperature of 150 ° C. or higher.
- the method of performing is mentioned.
- a preferred example of the (c) polyimide used in the present invention has a structure represented by any one of the general formulas (2) and (3). And it has at least one functional group capable of reacting with an epoxy group in the side chain. And having a structure represented by the general formula (1) General formula (2), as R 4 in (3). And the structure represented by General formula (1) is 5 to 15 weight% with respect to (c) polyimide whole quantity.
- the total amount of polyimide means the weight of the polymer (polyimide) obtained by polymerization of the constituent components consisting of diamine, acid dianhydride and end-capping agent, and is excessive during synthesis.
- the charged diamine, acid dianhydride, and terminal blocking agent are not included in the weight of the polyimide.
- R 1 is a divalent hydrocarbon group
- R 2 is a monovalent hydrocarbon group
- n is an integer of 1 to 10
- R 1 is a divalent hydrocarbon group.
- R 1 is preferably an alkylene group having 1 to 5 carbon atoms or a phenylene group.
- R 2 is a monovalent hydrocarbon group.
- R 2 is preferably an alkyl group having 1 to 5 carbon atoms or a phenyl group.
- the polyimide may be a polyimide containing one type of R 1 and one type of R 2 , or may be a polyimide containing a plurality of types of R 1 and / or a plurality of types of R 2 .
- the polyimide may be a mixture of a plurality of types of polyimide containing R 1 having a different structure and / or R 2 having a different structure.
- the ratio and / or ratios of a plurality of types of R 2 of a plurality of types of R 1 may be a mixture of different kinds of polyimide .
- the structure represented by the general formula (1) is (c) 5% by weight to 15% by weight with respect to the total amount of polyimide.
- the structure represented by the general formula (1) may not be 5 wt% or more and 15 wt% or less with respect to the total amount of polyimide.
- the total structure represented by the general formula (1) included in each polyimide may be 5% by weight or more and 15% by weight or less of the total amount of each polyimide.
- N represents an integer of 1 to 10, preferably 1 to 2.
- R 3 is a 4 to 14 valent organic group
- R 4 is a 2 to 12 valent organic group
- at least one of R 3 and R 4 is 1,1,1,3,3.
- .R 5 and R 6 at least one contains a group selected from the group consisting of a thioether group and a SO 2 group, the phenolic hydroxyl group, sulfonic acid group and thiol
- X represents a monovalent organic group
- m represents 8 to 200
- ⁇ and ⁇ each represents an integer of 0 to 10 and ⁇ + ⁇ Is an integer of 0 to 10.
- R 3 is a 4 to 14 valent organic group
- R 4 is a 2 to 12 valent organic group
- at least one of R 3 and R 4 is 1,1,1,3,3, It contains at least one group selected from the group consisting of 3-hexafluoropropyl group, isopropyl group, ether group, thioether group and SO 2 group (hereinafter, the group selected from this group is referred to as “specific group”).
- R 3 and R 4 preferably contain an aromatic group.
- R 5 and R 6 represent an organic group having at least one group selected from the group consisting of a phenolic hydroxyl group, a sulfonic acid group, and a thiol group.
- the polyimide may be a polyimide containing one type of R 3, one type of R 4, one type of R 5 and one type of R 6 , or a plurality of types of R 3 and / or a plurality of types of R 4 and / or Alternatively, polyimide containing a plurality of types of R 5 and / or a plurality of types of R 6 may be used. In addition, (c) the polyimide may be a mixture of a plurality of types of polyimide containing R 3 having a different structure and / or R 4 having a different structure and / or R 5 having a different structure and / or R 6 having a different structure.
- the ratio of the types of R 3 and / or the types of R A plurality of types of polyimides having different ratios of 4 and / or a plurality of types of R 5 and / or a plurality of types of R 6 may be mixed.
- X represents a monovalent organic group.
- m is 8 to 200.
- ⁇ and ⁇ each represents an integer of 0 to 10, and ⁇ + ⁇ is an integer of 0 to 10.
- ⁇ + ⁇ is an integer of 1 to 10 in the structural unit having the repeating number m.
- polyimide used for this invention is organic solvent soluble. Even if it is a polyimide which is not soluble in an organic solvent, it can be used by being dispersed in (d) a solvent, but a uniform semiconductor resin layer may not be formed.
- soluble in an organic solvent means that 20% by weight or more dissolves in at least one solvent selected from the following at 23 ° C.
- Ketone solvents acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone.
- Glycol ether solvents methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol methyl ethyl ether.
- Other solvents benzyl alcohol, N-methylpyrrolidone, ⁇ -butyrolactone, ethyl acetate, N, N-dimethylformamide.
- R 3 represents a structural component of acid dianhydride, and among them, a C 4 to C 14 valent organic group is preferable.
- R 4 represents a structural component of diamine, and among them, a divalent to 12-valent organic group having 5 to 40 carbon atoms is preferable. Moreover, it is preferable that both R 3 and R 4 contain at least one specific group.
- R 5 is an acid dianhydride substituent, and is preferably a group selected from the group consisting of a phenolic hydroxyl group, a sulfonic acid group, and a thiol group.
- R 6 is a substituent of diamine, and is preferably a group selected from the group consisting of a phenolic hydroxyl group, a sulfonic acid group, and a thiol group.
- the acid dianhydride used will be described.
- Specific examples of the acid dianhydride having at least one specific group include 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride and 2,2-bis (2,3-dicarboxy).
- R 9 represents C (CF 3 ) 2 , C (CH 3 ) 2 , SO 2 , S or O.
- R 10 and R 11 represent a hydrogen atom, a hydroxyl group, a thiol group or a sulfonic acid group. However, R 10 and R 11 are not simultaneously hydrogen atoms.
- the acid dianhydride having no specific group and having at least one group selected from the group consisting of a phenolic hydroxyl group, a sulfonic acid group and a thiol group is specifically an aromatic acid diacid having the structure shown below. Mention may be made of anhydrides.
- R 7 and R 8 represent a hydrogen atom, a hydroxyl group, a thiol group or a sulfonic acid group. However, R 7 and R 8 are not simultaneously hydrogen atoms.
- acid dianhydride having no specific group and having no phenolic hydroxyl group, sulfonic acid group, and thiol group include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetra Carboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4 '-Benzophenone tetracarboxylic dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1 -Bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2
- these acid dianhydrides are used alone or in combination of two or more.
- diamine used will be described.
- Specific examples of the diamine having at least one specific group include 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl ether, and 4,4'-diamino.
- Diphenyl ether 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4- Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-a Nofenokishi) phenyl] propane, or compounds substituted with alkyl group or halogen atom in the aromatic ring.
- diamine having at least one specific group and at least one group selected from the group consisting of a phenolic hydroxyl group, a sulfonic acid group, and a thiol group include 2,2-bis (3- Amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2 -Bis (3-hydroxy-4-aminophenyl) propane, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 3,3'- Diamino-4,4'-dihydroxydiphenylsulfide or an aromatic ring thereof can be substituted with an alkyl group or a halogen atom.
- R 16 represents C (CF 3 ) 2 , C (CH 3 ) 2 , SO 2 , S or O.
- R 17 to R 18 represent a hydrogen atom, a hydroxyl group, a thiol group, or a sulfonic acid group. However, R 17 and R 18 are not simultaneously hydrogen atoms.
- diamine having no specific group and having at least one group selected from the group consisting of a phenolic hydroxyl group, a sulfonic acid group, and a thiol group include 3,3′-diamino-4,4′-dihydroxy.
- Biphenyl 2,4-diamino-phenol, 2,5-diaminophenol, 1,4-diamino-2,5-dihydroxybenzene, diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxydiaminopyrimidine, 9,9-bis (3- Amino-4-hydroxyphenyl) fluorene, a compound in which these aromatic rings are substituted with an alkyl group or a halogen atom, or a diamine having the structure shown below.
- R 12 to R 15 represent a hydrogen atom, a hydroxyl group, a thiol group, or a sulfonic acid group. However, R 12 and R 13 are not simultaneously hydrogen atoms.
- diamines that do not have a specific group and do not have a phenolic hydroxyl group, sulfonic acid group, or thiol group include 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, benzidine, and m-phenylenediamine.
- P-phenylenediamine 1,5-naphthalenediamine, 2,6-naphthalenediamine, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-diethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-diethyl-4,4′-diaminobiphenyl, 2,2 ′, 3,3′-tetramethyl-4,4′-diaminobiphenyl 3,3 ′, 4,4′-tetramethyl-4,4′-diaminobiphenyl, 2,2′-di (trifluoromethyl) -4,4′-di Minobiphenyl, or a compound in which these aromatic rings are substituted with an alkyl group or a halogen atom, terephthalic acid hydrazide, isophthalic acid hydrazide, phthalic acid hydrazide, 2,
- the structure represented by the general formula (1) is general formula (2), because it contains as R 4 in (3), a constituent of a diamine.
- Examples of the diamine having the structure represented by the general formula (1) include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-amino-phenyl) octamethylpentasiloxane.
- R 5 and R 6 in general formulas (2) and (3), the reaction rate between the polyimide and the epoxy compound during the heat treatment can be adjusted, and the crosslinking density of the resin composition for semiconductor can be adjusted. .
- ⁇ and ⁇ each represents an integer of 0 to 10
- ⁇ + ⁇ represents an integer of 0 to 10.
- the structural unit in which ⁇ + ⁇ is an integer of 1 to 10 is 20 to 90 mol%.
- 20 to 90% of the total of R 5 and R 6 is preferably a phenolic hydroxyl group, a sulfonic acid group or a thiol group.
- X which is a structural component of the general formulas (2) and (3) is a component derived from a primary monoamine which is a terminal blocking agent. These may be used alone or in combination of two or more with other end-capping groups.
- Specific examples of the primary monoamine include 5-aminoquinoline, 4-aminoquinoline, 3-aminonaphthalene, 2-aminonaphthalene, 1-aminonaphthalene, aniline and the like. Of these, aniline is preferably used.
- a primary monoamine that does not have any other substituent that can react with the epoxy compound.
- This makes it possible to obtain an organic solvent-soluble polyimide that does not have a substituent that reacts with the epoxy compound at the terminal portion of the polyimide having high molecular mobility. By using this, the reaction between the organic solvent-soluble polyimide and the epoxy compound hardly proceeds at room temperature, and the storability of the semiconductor resin composition can be further enhanced.
- the introduction ratio of the X component in the general formulas (2) and (3) is 0.1 to 60 mol% with respect to the total diamine component, when converted in terms of the primary monoamine component of the terminal blocker that is the original component.
- the range is preferable, and particularly preferably 5 to 50 mol%.
- m represents the number of polymer repetitions, and ranges from 8 to 200. The preferred range is 10 to 150.
- weight average molecular weight it is preferably from 4,000 to 80,000, particularly preferably from 8,000 to 60,000 in terms of polystyrene by gel filtration chromatography.
- the weight average molecular weight in terms of polystyrene is calculated by GPC apparatus Waters 2690 (manufactured by Waters Co., Ltd.).
- GPC measurement conditions are such that the moving bed is NMP in which LiCl and phosphoric acid are dissolved at a concentration of 0.05 mol / L, and the development rate is 0.4 ml / min.
- Detector Waters 996 System controller: Waters 2690 Column oven: Waters HTR-B Thermo Controller: Waters TCM Column: TOSOH grand comn Column: TOSOH TSK-GEL ⁇ -4000 Column: TOSOH TSK-GEL ⁇ -2500 and the like.
- the (c) polyimide used in the present invention may be only one having a structure represented by the general formulas (2) and (3), or a structure represented by the general formulas (2) and (3). It may be a copolymer having another structure as a copolymerization component, or a mixture thereof. Furthermore, the polyimide represented by another structure may be mixed with any of these. In that case, it is preferable to contain 50 mol% or more of the structures represented by the general formulas (2) and (3).
- the type and amount of the structure used for copolymerization or mixing are preferably selected within a range that does not impair the heat resistance of the heat resistant resin film obtained by heat treatment.
- the structure of the general formula (1) introduced into the polymer and the end capping agent used in the present invention can be easily detected and quantified by the following method.
- a polymer in which the structure of the general formula (1) and the end-capping agent are introduced is dissolved in an acidic solution or a basic solution, and decomposed into a diamine component and an acid anhydride component which are constituent units of the polymer.
- the structure of the general formula (1) and the end-capping agent used can be easily detected and quantified by gas chromatography (GC) or NMR measurement.
- the structure of the general formula (1) is also used by directly measuring the pyrolysis gas chromatograph (PGC), infrared spectrum and 13C NMR spectrum of the polyimide into which the end-capping agent is introduced.
- PPC pyrolysis gas chromatograph
- the end capping agent can be easily detected and quantified.
- the content of the polyimide (c) is preferably 15 to 90 parts by weight with respect to 100 parts by weight of the (a) epoxy compound, and more preferably 30 to 90% for reacting with the epoxy compound to form a dense network structure. 70 parts by weight.
- an organic solvent-soluble polyimide is preferably used, whereas a polymer having an amide bond such as polyurethane, polyamide, and polyamideimide has a lower heat resistance and more water absorption than an organic solvent-soluble polyimide. Since it becomes a factor which reliability falls, it is not preferable.
- the present invention further provides a resin composition for a semiconductor containing (d) a solvent.
- the solvent (d) that can be used in the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, Ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether (ethyl diglycol), diethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), diethylene glycol monoethyl ether acetate, propyl acetate, butyl acetate Acetates such as isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl
- the boiling point in the present invention is a boiling point under a pressure of 1 atm, that is, 1.013 ⁇ 10 5 N / m 2 .
- the boiling point can be measured using a known technique and is not particularly limited. For example, the boiling point can be measured using a boiling point meter of Switzerland.
- particularly preferable organic solvents having such boiling point include cyclopentanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether.
- examples include acetate, methyl lactate, ethyl lactate, diacetone alcohol, and 3-methyl-3-methoxybutanol.
- the preferred range of the weight of the solvent (d) contained in the semiconductor resin composition of the present invention is 10 to 50% by weight, more preferably 20 to 40% by weight, based on the total weight of the semiconductor resin composition. is there. If the total weight of the semiconductor resin composition is 10 to 50% by weight, (a) the epoxy compound and (c) the polyimide can be dissolved more sufficiently, and the film thickness is sufficient when the film is formed. Obtainable.
- the semiconductor resin composition of the present invention preferably further contains (f) an epoxy curing agent.
- an epoxy curing agent By containing an epoxy curing agent, curing in a short time becomes possible.
- an imidazole curing agent is preferable from the viewpoints of reactivity and storage stability.
- Examples of those preferably used as the epoxy curing agent include 2PZ, 2P4MZ, 2E4MZ, 2MA-OK, C11Z (trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.) and the like, but are not limited thereto. .
- an epoxy curing agent called a microcapsule curing agent such as NovaCure HX-3941HP, NovaCure HXA3922HP, NovaCure HXA3932HP, NovaCure HXA3042HP (trade name, manufactured by Asahi Kasei E-Materials Co., Ltd.) has excellent reactivity, but is an organic solvent. When it is used for a coating material containing, the storage stability is poor and the viscosity increases.
- the content of the epoxy curing agent is preferably 0.1 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the (a) epoxy compound.
- the resin composition for semiconductors of the present invention may contain a surfactant for the purpose of improving the affinity with the substrate.
- a surfactant is not particularly limited, and examples thereof include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surfactant.
- fluorosurfactant hereinafter referred to as “trade name”
- Megafac F171, F173, and R-30 DIC Corporation (formerly Dainippon Ink and Chemicals)
- Florard FC430 and FC431 Sumitomo 3M Co., Ltd.
- Asahi Guard AG710 Surflon S-382
- SC101, SC102, SC103, SC104, SC105, SC106 Asahi Glass Co., Ltd.
- silicon surfactants May include, but are not limited to, BYK-313, BYK-333, BYK-337, BYK-378, BYK-A506 (manufactured by Big Chemie Japan). These surfactants can be used alone or in combination of two or more.
- the resin composition for semiconductors of the present invention may contain (g) an adhesion promoter for the purpose of improving the adhesion to the substrate.
- an adhesion promoter for the purpose of improving the adhesion to the substrate.
- adhesion promoter include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane; trimethylmethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylvinylethoxy.
- Alkoxysilanes such as silane, diphenyldimethoxysilane, phenyltriethoxysilane; silazanes such as hexamethyldisilazane, N, N′-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, trimethylsilylimidazole; vinyltrichlorosilane, ⁇ -chloro Propyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -glycidoxy Silanes such as propyltrimethoxysilane and ⁇ - (N-piperidinyl) propyltrimethoxysilane; benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole
- the semiconductor resin composition obtained by mixing and dissolving the above materials may be filtered using a filter paper or a filter.
- the filtration method is not particularly limited, in order to pass the dispersed (b) inorganic particles, a method of filtering by pressure filtration using a filter having a retained particle diameter of 10 ⁇ m or more is preferable.
- the identification of the resin composition for semiconductors of the present invention and the confirmation of the amount of each component can be performed by the following method.
- the resin composition for semiconductor is subjected to HPLC measurement and GPC measurement using various eluent compositions, and the number of components blended in the resin composition for semiconductor is confirmed.
- the solvent is removed by a rotary evaporator or precision distillation, taking care not to denature each component. Thereafter, (isolation) purification of each component is performed by a technique such as preparative HPLC, preparative GPC, or column chromatography using various eluents. (Isolation) purification of each component may be performed by (isolation) purification without removing the solvent by techniques such as preparative HPLC, preparative GPC, column chromatography with various eluents, etc. it can.
- the solvent species can be identified by various two-dimensional NMR techniques such as GC-MASS, 1 HNMR, 13 CNMR, HMBC, and HMQC. When a plurality of high molecular weight components are contained, various good solvents and poor solvents can be selected and purified by reprecipitation using the difference in solubility of the high molecular components.
- the high molecular weight component it can be determined whether (c) polyimide is contained in the high molecular weight component by techniques such as 1 HNMR, 13 CNMR, various two-dimensional NMR such as HMBC and HMQC, and IR measurement. Next, the solubility of the purified polyimide can be evaluated to determine whether (c) the polyimide is an organic solvent-soluble polyimide. Regarding other components (a) epoxy compound, (d) solvent, (f) epoxy curing agent, etc., each isolated component was subjected to mass spectrometric confirmation of parent peak and fragment analysis, 1 HNMR and 13 It can be identified by techniques such as CNMR, DEPT measurement, various two-dimensional NMR such as HMBC and HMQC.
- the particle diameter of the inorganic particles is measured after the semiconductor resin composition is diluted with a solvent contained in the semiconductor resin composition. Thereafter, the semiconductor resin composition is filtered and collected using a filter having a size capable of capturing particles of the minimum size. The particle diameter of the collected inorganic particles is measured again to confirm that the inorganic particles are completely recovered. Next, the composition can be confirmed by performing elemental analysis of the recovered inorganic particles.
- the rubber particles can be identified by collecting the rubber particles from the filtrate after collecting the inorganic particles and performing analysis such as IR, TOF-SIMS, and elemental analysis. Recovery of the rubber particles from the filtrate can be performed by filtration using a filter having a size capable of capturing the rubber particles or by separation using an ultracentrifuge.
- the compounding amount of each component can be confirmed by, for example, isolating 100 g of a resin composition for semiconductors into each component and weighing the weight. It is also possible to determine the compounding amount by creating a calibration curve using HPLC or GC and quantifying each component using an internal standard substance such as biphenyl and an isolated purified product. By these methods, it is possible to confirm the ratio of the blending amounts of (c) polyimide and (a) epoxy compound, (f) epoxy curing agent, (b) inorganic particles, and the like.
- the weight of the total solid content obtained by removing the weight of the solvent (d) from the total weight of the resin composition for semiconductors can be known. That is, the residue after thermogravimetric analysis under a nitrogen stream corresponds to (B) total solid content, and the difference between the weight of (B) total solid content and the weight of the sample used in (A) analysis is (d) the solvent content. It hits the weight. That is, when the (a) epoxy compound contains a liquid epoxy compound, the liquid epoxy compound is also regarded as a solid content.
- thermogravimetric analysis a temperature and a time sufficient to volatilize the solvent are sufficient. For example, if a semiconductor resin composition using PGMEA as a solvent is used for thermogravimetric analysis of about 10 mg, the temperature is increased to 250 ° C. at a temperature increase rate of 10 ° C./min, and then held at 250 ° C. for 30 minutes. Etc. Furthermore, by performing thermogravimetric analysis of (B) total solid content under an air (or oxygen-containing gas) stream, the proportion of (b) inorganic particles in the weight of (B) total solid content can be known.
- thermogravimetric analysis under an air stream a temperature and a time at which the nonvolatile organic component in the resin composition for semiconductors is sufficiently burned are sufficient. For example, the temperature is increased to 550 ° C. at a temperature increase rate of 10 ° C./min and then held at 550 ° C. for 60 minutes.
- thermogravimetric analysis a differential thermothermogravimetric simultaneous measurement device (TG / DTA6200, manufactured by SII Nanotechnology Co., Ltd.) can be used.
- the polyimide monomer unit structure can be identified by the following method. After dissolving the polyimide in an acidic solution and decomposing it into an amine component and a carboxylic anhydride component, which are constituent units of the polyimide, each method can be performed by means of preparative HPLC, preparative GPC, column chromatography with various eluents, etc. Isolate and purify components. Each component can be identified by techniques such as 1 HNMR, 13 CNMR, DEPT measurement, various two-dimensional NMR such as HMBC and HMQC.
- the resin composition for semiconductors of the present invention can be suitably used as a resin adhesive for semiconductors or a coating material for bonding, fixing or sealing semiconductor elements, semiconductor devices, circuit boards and metal wiring materials.
- the resin film for semiconductor of the present invention is a resin film for semiconductor having a semiconductor resin layer containing (a) an epoxy compound, (b) inorganic particles, and (c) polyimide on a support, and the resin for semiconductor
- the proportion of the inorganic particles (b) is 60 wt% or more and 92 wt% or less of the weight of the layer, and (e) contains rubber particles.
- the components (a) to (c) and (e) are the same as described above. There is no restriction
- the material for the support include, but are not limited to, resin, copper, stainless steel, aluminum and the like. Although there is no restriction
- a resin film (hereinafter referred to as a support film) is most preferably used as the support.
- the resin film for semiconductor of the present invention can be obtained by applying the above-mentioned resin composition for semiconductor on a support, and then drying it to form a resin layer for semiconductor on the support.
- the resin layer for semiconductor is formed on a support film that is a support.
- a support film that is a support.
- various commercially available films such as a polyethylene terephthalate (PET) film, a polyphenylene sulfide film, and a polyimide film can be used.
- PET polyethylene terephthalate
- the bonding surface between the support film and the semiconductor resin layer may be subjected to a surface treatment such as silicone, a silane coupling agent, or an aluminum chelating agent in order to improve adhesion and peelability.
- the thickness of the support film is not particularly limited, but is preferably in the range of 10 to 75 ⁇ m from the viewpoint of workability.
- a protective film may be provided on the resin layer for semiconductor in order to protect the resin layer for semiconductor.
- the semiconductor resin layer surface of the semiconductor resin film can be protected from contaminants such as dust and dust in the atmosphere.
- the protective film examples include a polyethylene film, a polypropylene (PP) film, and a polyester film.
- the protective film is preferably one having a small adhesive force with the semiconductor resin layer.
- the resin composition for semiconductor of the present invention As a method for applying the resin composition for semiconductor of the present invention to a support film, spray coating, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater, comma roll coater, gravure Examples of the method include a coater, a screen coater, and a slit die coater.
- a coating film thickness changes with application methods, solid content concentration of composition, viscosity, etc., it is preferable that the film thickness after drying is usually 0.5 ⁇ m or more and 100 ⁇ m or less.
- Oven, hot plate, infrared, etc. can be used for drying.
- the drying temperature and the drying time may be in a range where the solvent can be volatilized, and it is preferable to appropriately set a range in which the resin film for a semiconductor is in an uncured or semi-cured state. Specifically, it is preferable to carry out from 1 minute to several tens of minutes in the range of 40 ° C to 120 ° C. Moreover, you may heat up in steps combining these temperatures, for example, you may heat-process at 50 degreeC, 60 degreeC, and 70 degreeC for 1 minute each.
- the semiconductor device of the present invention comprises (d) a cured product obtained by removing the solvent from the semiconductor resin composition of the present invention or a cured product of the semiconductor resin layer obtained by removing the support from the semiconductor resin film of the present invention. Have.
- the semiconductor device in the present invention refers to all devices that can function by utilizing the characteristics of semiconductor elements, and electro-optical devices, semiconductor circuits, and electronic devices are all included in the semiconductor devices.
- An example of a method for producing a semiconductor device having (d) a cured product obtained by removing the solvent from the semiconductor resin composition of the present invention or a cured product of the semiconductor resin layer of the present invention is as follows.
- a first circuit member having a first connection terminal and a second circuit member having a second connection terminal are arranged so that the first connection terminal and the second connection terminal face each other.
- the support is made from the composition obtained by removing (d) the solvent from the semiconductor resin composition of the present invention or the semiconductor resin film of the present invention between the first connection terminal and the second connection terminal arranged opposite to each other.
- the resin layer for semiconductor from which is removed is interposed. And it heat-presses and the 1st connection terminal and 2nd connection terminal which were arrange
- the composition obtained by removing the solvent (d) from the semiconductor resin composition of the present invention or the semiconductor resin layer of the present invention becomes a cured product.
- the composition obtained by removing the solvent from the above resin composition for semiconductor or the resin layer for semiconductor of the present invention is formed only on the surface on the connection terminal side of any circuit member first. It may be performed after forming on both surfaces of the connection terminals of the first and second circuit members.
- the penetration electrode may be formed in the first circuit member and / or the second circuit member, and the connection terminal may be formed on one side and / or both sides of the member.
- Such circuit members include semiconductor chips on which bumps such as plating bumps and stud bumps are formed, chip components such as resistor chips and capacitor chips, semiconductor chips and silicon interposers having TSV (through silicon via) electrodes, A substrate such as a glass epoxy circuit board or a film circuit board is used.
- an adhesive resin material for producing a die attach film, a dicing die attach film, a lead frame fixing tape, a heat sink, a reinforcing plate, an adhesive for a shielding material, a solder resist, and the like.
- composition obtained by removing (d) the solvent from the semiconductor resin composition of the present invention or the semiconductor resin of the present invention when electrically connecting the semiconductor chip having bumps and the circuit board or semiconductor chip having the wiring pattern A composition obtained by removing the solvent (d) from the semiconductor resin composition of the present invention, or a gap between a semiconductor chip having bumps and a circuit board or a semiconductor chip having a wiring pattern connected through layers, or the present invention A method for manufacturing a semiconductor device by sealing with a semiconductor resin layer will be described.
- the semiconductor chip having bumps and the circuit board or semiconductor chip having a wiring pattern are connected via the composition obtained by removing the solvent (d) from the semiconductor resin composition of the present invention or the semiconductor resin layer of the present invention. .
- the composition obtained by removing the solvent (d) from the semiconductor resin composition of the present invention or the semiconductor resin layer of the present invention is a bump formation of a semiconductor chip having a wiring pattern surface of a circuit board having a wiring pattern or a bump. It may be formed on any of the surfaces.
- the semiconductor wafer is diced into individual pieces. By doing so, you may produce the semiconductor chip which the composition layer which removed the (d) solvent from the resin composition for semiconductors of this invention, or the resin layer for semiconductors of this invention stuck.
- the semiconductor resin composition is directly applied to a semiconductor chip, a circuit board, or a semiconductor wafer, and then dried. And a method of removing the support after the resin film for semiconductor of the present invention is attached to a semiconductor chip, a circuit board, or a semiconductor wafer.
- An oven, a hot plate, infrared rays, or the like can be used for drying.
- the drying temperature and drying time need only be within a range in which the solvent can be volatilized, and (d) the composition obtained by removing the solvent from the semiconductor resin composition of the present invention or the semiconductor resin layer of the present invention is uncured.
- the range which becomes a semi-hardened state suitably. Specifically, it is preferable to carry out from 1 minute to several tens of minutes in the range of 40 ° C to 120 ° C. Moreover, you may heat up in steps combining these temperatures, for example, you may heat-process at 50 degreeC, 60 degreeC, and 70 degreeC for 1 minute each. Further, after forming the composition obtained by removing the solvent (d) or the semiconductor resin layer of the present invention from the semiconductor resin composition of the present invention, the bumps are exposed by a mechanical method before mounting with a bonding apparatus. There may be a process of making it. That is, the method described in (2012 IEEE 62nd ELECTRONIC COMPONENTS AND TECHNOLOGY CONFERENCE (ECTC), pages 444 to 449, 2012).
- a composition obtained by removing the solvent from the semiconductor resin composition of the present invention or a semiconductor resin layer of the present invention is formed on a circuit board or a semiconductor chip on which a wiring pattern is formed, and then mounted on a bonding apparatus. It can be carried out.
- the mounting conditions are not particularly limited as long as the electrical connection is satisfactorily obtained, but (d) the composition obtained by removing the solvent from the semiconductor resin composition of the present invention or the semiconductor resin layer of the present invention.
- the temperature is 120 ° C.
- the bonding is preferably performed under a bonding condition of 1 second to 60 seconds, more preferably 2 seconds to 30 seconds. Also, after bonding, the bump on the semiconductor chip and the wiring pattern on the circuit board are brought into contact with each other by heating and pressing at a temperature of 50 ° C. or more, a pressure of 1 mN / bump or more, and a time of 0.1 second or more. Bonding is performed under the above conditions. After performing bonding as necessary, the circuit board with a semiconductor chip may be heated at a temperature of 50 ° C. to 200 ° C. for 10 seconds to 24 hours.
- a part of the wafer on which the coating film was formed was put into this mixture and allowed to stand for about 1 hour to cure the resin. Polishing was performed so that a cross-section of the resin-embedded wafer appeared, and an evaluation sample was obtained.
- TegraPol-21 manufactured by Struers was used as the polishing apparatus.
- DP-Nap was used for the abrasive paper
- DP-suspension P (1 ⁇ m) was used for the abrasive
- DP-lubricant was used for the lubricant.
- the obtained evaluation sample was observed with a scanning electron microscope (SEM, JSM-6510A manufactured by JEOL Ltd.).
- the ratio of the cross-sectional area of the inorganic particles in the area of a square surrounded by a square in which one side is adjacent to the wafer surface and the length of each side is 1/10 of the film thickness
- the wafer The ratio of the cross-sectional area of the inorganic particles in the area of the area surrounded by a square that is adjacent to the upper surface of the film on the opposite side and the length of each side is 1/10 of the film thickness is compared. If it is within 5 times, the distribution of inorganic particles is uniform, and if it is more than 5 times, it can be judged that the distribution of inorganic particles is non-uniform.
- arbitrary measurement points can be set in the SEM image in the direction parallel to the wafer, in the case of FIG. 1 in the left-right direction of the photograph.
- the above observation was performed at the right end and the central portion of the left end and the right end, and when the distribution of the inorganic particles could be judged to be uniform at all of the left end, the right end, and the central portion, it was evaluated as good, and otherwise it was evaluated as defective.
- FIG. 1 is an example of an SEM image of a semiconductor resin layer in which inorganic particles are uniformly distributed to the upper part of the film
- FIG. 2 is a semiconductor resin layer having a region where the inorganic particles are insufficient in the upper part of the film. It is an example of SEM image of.
- YK57, single-sided corona discharge treated product having a thickness of 8 ⁇ m as a peelable substrate for surface protection on the obtained resin film for semiconductor is heated at a heating roll temperature of 35 ° C. And roll up on a paper tube with an outer diameter of 9.6 cm so that the peelable substrate is inside, and a raw fabric having a peelable substrate on both sides of the resin film for semiconductor (a peelable substrate, A three-layer structure of a resin film for semiconductor and a peelable substrate for surface protection) was obtained.
- the obtained original fabric was observed with a microscope, and the presence or absence of cracks in the resin film for semiconductors and the removal of the peelable substrate from the polypropylene film was evaluated. Those that were not cracked or dropped out were judged good, and those that were seen were judged bad.
- the heat-treated laminate was cut using a dicing apparatus DAD3350 (manufactured by Disco Corporation) to produce a rectangular parallelepiped having a width of 2 mm, a length of 15 mm, and a height of 2.5 mm.
- Evaluation of the linear expansion coefficient of the rectangular parallelepiped was performed using a heat / stress / strain measuring apparatus (TMA / SS6100, manufactured by SII Nano Technologies, Inc.).
- TMA / stress / strain measuring apparatus TMA / SS6100, manufactured by SII Nano Technologies, Inc.
- the measurement temperature range was ⁇ 50 to 300 ° C., and the heating rate was 10 ° C./min.
- the linear expansion coefficient was calculated in the temperature range below the glass transition temperature (Tg).
- Synthesis Example 1 (c) Synthesis of Polyimide 4.82 g (0.0165 mol) of 1,3-bis (3-aminophenoxy) benzene (hereinafter referred to as APB-N) under a dry nitrogen stream, 3,3′- Diamino-4,4′-dihydroxydiphenylsulfone (hereinafter referred to as ABPS) 3.08 g (0.011 mol), bis (3-aminopropyl) tetramethyldisiloxane (hereinafter referred to as SiDA) 4.97 g (0 0.02 mol), 0.47 g (0.005 mol) of aniline as a terminal blocking agent was dissolved in 130 g of NMP.
- APB-N 1,3-bis (3-aminophenoxy) benzene
- ABPS 3,3′- Diamino-4,4′-dihydroxydiphenylsulfone
- SiDA bis (3-aminopropyl) tetramethyldisiloxane
- BSAA 2,2-bis ⁇ 4- (3,4-dicarboxyphenoxy) phenyl ⁇ propane dianhydride
- SE5100 sica particles manufactured by Admatechs Co., Ltd., average particle size 1.5 ⁇ m
- YA100C-SP3 sica particles manufactured by Admatechs Co., Ltd., average particle size 0.1 ⁇ m
- FB-5LDX Electrochemical Industry Co., Ltd.
- Example 1 NC3000-H (manufactured by Nippon Kayaku Co., Ltd.), 11.35 g, SE2050 (silica particles manufactured by Admatechs Co., Ltd., average particle size 0.5 micron), 54.60 g, Kaneace MX-113 (Kaneka Corporation) 4.68 g of epoxy resin containing 30% by weight of core-shell rubber particles), 6.90 g of polyimide A obtained in Synthesis Example 1 and 22.00 g of PGMEA (manufactured by KH Neochem) were added to a 250 mL plastic container. The mixture was stirred for 96 hours on a ball mill base at room temperature.
- Example 2 Resin composition 2 for semiconductor was obtained in the same manner as in Example 1 except that 4.34 g of Kaneace MX-113 was used and 2.34 g of Kaneace MX-113 and 2.34 g of YL980 were used.
- Example 3 Resin composition 3 for semiconductor was obtained in the same manner as in Example 1 except that 1.17 g of Kaneace MX-113 and 3.51 g of YL980 were used instead of 4.68 g of Kaneace MX-113.
- Example 4 Resin composition 4 for semiconductors was obtained in the same manner as in Example 1 except that all of PGMEA was replaced with ethyl diglycol (manufactured by Daicel Corporation).
- Example 5 Resin composition 5 for semiconductors was obtained in the same manner as in Example 1 except that SE2050 was entirely replaced with SE5100 (silica particles manufactured by Admatechs Co., Ltd., average particle size 1.5 ⁇ m).
- Example 6 Resin composition 6 for semiconductor was obtained in the same manner as in Example 1 except that SE2050 was entirely replaced with YA100C-SP3 (silica particles manufactured by Admatechs Co., Ltd., average particle size 0.1 ⁇ m).
- Example 7 Resin composition 7 for semiconductor was obtained in the same manner as in Example 1 except that SE2050 was entirely replaced with FB-5LDX (silica particles manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 4.2 ⁇ m).
- SE2050 was entirely replaced with FB-5LDX (silica particles manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 4.2 ⁇ m).
- Example 8 Resin composition for semiconductor 8 is obtained in the same manner as in Example 1 except that the blending amounts of the respective components are as shown in Table 2 and that the proportion of SE2050 is 60% by weight in the total solid weight. It was.
- Example 9 Resin composition for semiconductor 9 is obtained in the same manner as in Example 1 except that the blending amount of each component is as shown in Table 2 and that the proportion of SE2050 is 90% by weight of the total solid weight. It was.
- Comparative Example 1 Comparative resin composition 1 was obtained in the same manner as in Example 1 except that Kaneace MX-113 was entirely replaced with YL980.
- Comparative Example 2 Comparative resin composition 2 was obtained in the same manner as in Example 1, except that Kaneace MX-113 was replaced with all YL980 and PGMEA with all ethyl diglycol.
- Comparative Example 3 Comparative resin composition 3 was obtained in the same manner as in Example 1 except that the blending amounts of the respective components were as shown in Table 2 and that the proportion of SE2050 was 50% by weight of the total solid content. It was.
- Comparative Example 4 Comparative resin composition 4 was obtained in the same manner as in Example 1 except that the blending amounts of each component were as shown in Table 2 and that the proportion of SE2050 was 95% by weight of the total solid weight. It was.
- Tables 1 and 2 show the evaluation results of each example and comparative example.
- the comparative resin composition 4 and the comparative resin composition 5 were cracked and dropped off in the semiconductor resin film. When the film was cut, cracks occurred more severely, so a sample for evaluating the linear expansion coefficient could not be produced. For this reason, the linear expansion coefficient of the comparative resin composition 4 could not be evaluated.
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Abstract
Description
a:半導体用樹脂組成物中で無機粒子の分散性が悪く、無機粒子同士が凝集する。
b:半導体用樹脂組成物を離型性プラスチックフィルム上に形成して半導体用樹脂フィルムとする場合に、ロール状に巻き取ると、半導体用樹脂フィルムの割れや離型性プラスチックフィルムから脱落する。
スチレン共重合物からなる“パラロイド(登録商標)”EXL-2655(呉羽化学工業
(株)製)、アクリル酸エステル・メタクリル酸エステル共重合体からなる“スタフィロ
イド(登録商標)”AC-3355、TR-2122(以上、武田薬品工業(株)製)、
アクリル酸ブチル・メタクリル酸メチル共重合物からなる“PARALOID(登録商標
)”EXL-2611、EXL-3387(以上、Rohm&Haas社製)、“カネエ
ース(登録商標)”MX113(カネカ(株)製)等を使用することができる。
式中、R1は2価の炭化水素基である。R1は、好ましくは炭素数1~5のアルキレン基、またはフェニレン基である。R2は1価の炭化水素基である。R2は、好ましくは炭素数1~5のアルキル基、またはフェニル基である。(c)ポリイミドは1種類のR1および1種類のR2を含むポリイミドでも良いし、複数種類のR1および/または複数種類のR2を含むポリイミドでも良い。また、(c)ポリイミドは異なる構造のR1および/または異なる構造のR2を含む複数種類のポリイミドを混合していても良い。また、複数種類のR1および/または複数種類のR2を含むポリイミドにおいて、複数種類のR1の比および/または複数種類のR2の比が異なる複数種類のポリイミドを混合していても良い。
式中、R3は4~14価の有機基であり、R4は2~12価の有機基であって、R3、R4の少なくとも一つは1,1,1,3,3,3-ヘキサフルオロプロピル基、イソプロピル基、エーテル基、チオエーテル基およびSO2基からなる群より選ばれる基(以下、この群より選ばれる基を「特定基」という)を少なくとも一つ含有する。またR3、R4は芳香族基を含有することが好ましい。R5およびR6は、フェノール性水酸基、スルホン酸基およびチオール基からなる群より選ばれる基を少なくとも一つ有する有機基を示す。
ケトン系溶剤のアセトン、メチルエチルケトン、メチルイソブチルケトン、シクロペンタノン、シクロヘキサノン。
エーテル系溶剤の1,4-ジオキサン、テトラヒドロフラン、ジグライム。
グリコールエーテル系溶剤のメチルセロソルブ、エチルセロソルブ、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノブチルエーテル、ジエチレングリコールメチルエチルエーテル。
その他の溶剤のベンジルアルコール、N-メチルピロリドン、γ-ブチロラクトン、酢酸エチル、N,N-ジメチルホルムアミド。
検出器:Waters996
システムコントローラー:Waters2690
カラムオーブン:Waters HTR-B
サーモコントローラー:Waters TCM
カラム:TOSOH grard comn
カラム:TOSOH TSK-GEL α-4000
カラム:TOSOH TSK-GEL α-2500などが挙げられる。
実施例1~9で得られた半導体用樹脂組成物1~9および比較例1~4で得られた比較用樹脂組成物1~4を、4インチのシリコンウエハ上にアプリケータで塗工し、100℃のホットプレート上で10分間乾燥させ、膜厚およそ40μmの半導体用樹脂層をシリコンウエハ上に形成した。半導体用樹脂層を形成したウエハの一部をエポキシ樹脂に包埋、研磨することで評価サンプルを作製した。包埋樹脂にはストルアス社製Claro Cit PowderおよびClaro Cit Liquidの5:3混合物を用いた。この混合物に塗膜を形成したウエハの一部を入れ、約1時間静置して樹脂を硬化させた。樹脂包埋したウエハの断面が出るように研磨を行い評価サンプルとした。研磨装置はストルアス社製TegraPol-21を用いた。研磨紙にはDP-Nap、研磨剤にはDP-懸濁液P(1μm)、潤滑剤にはDP-ルーブリカントを用いた。得られた評価サンプルを走査型電子顕微鏡(SEM、日本電子株式会社製JSM-6510A)で観察した。得られたSEM像において、一辺がウエハ面と隣接しており各辺の長さが膜厚の10分の1である正方形で囲まれたエリアの面積における無機粒子の断面積の割合と、ウエハと反対側の膜上部面と隣接しており各辺の長さが膜厚の10分の1である正方形で囲まれたエリアの面積における無機粒子の断面積の割合を比較し、その差が5倍以内である場合は無機粒子の分布が均一、5倍より大きい場合には無機粒子の分布が不均一と判断できる。
実施例1~9で得られた半導体用樹脂組成物1~9および比較例1~4で得られた比較用樹脂組成物1~4を、スリットダイコーター(塗工機)を用いて、剥離性基材として厚さ37.5μmのポリイミドフィルム(商品名、カプトン150EN-C)に乾燥後の厚みが25μmとなるように塗布し、80℃で10分間乾燥を行った。得られた半導体用樹脂フィルム上に表面保護用剥離性基材として厚さ8μmのポリプロピレンフィルム(商品名、トレファンBO型番YK57、片面コロナ放電処理品)の未処理面を、加熱ロール温度35℃でラミネートし、外径9.6cmの紙管上に剥離性基材が内側になるようロール状に巻き取り、半導体用樹脂フィルムの両面に剥離性基材を有する原反(剥離性基材、半導体用樹脂フィルム、表面保護用剥離性基材の3層構造)を得た。
前記評価で得られた原反を8cm角サイズに切断し、真空ラミネート装置MVLP-500/600((株)名機製作所製)を用いて厚さ2mmになるまで繰り返し積層した。積層条件は、上熱盤と下熱盤の温度を90℃、真空時間を20秒、加圧力を0.3MPa、加圧時間を30秒とした。得られた積層物を200℃で15分加熱処理を行った。加熱処理した積層物をダイシング装置DAD3350((株)ディスコ製)を用いて切断し、幅2mm、長さ15mm、高さ2.5mmの直方体を作製した。直方体の線膨張係数の評価を熱・応力・歪測定装置(TMA/SS6100、エスアイアイ・ナノテクノロジーズ(株)製)を用いて行った。測定温度範囲は-50~300℃、昇温速度は10℃/分で行った。線膨張係数はガラス転移温度(Tg)以下の温度範囲で算出した。
乾燥窒素気流下、1,3-ビス(3-アミノフェノキシ)ベンゼン(以下、APB-Nとする)4.82g(0.0165モル)、3,3’-ジアミノ-4,4’-ジヒドロキシジフェニルスルホン(以下、ABPSとする)3.08g(0.011モル)、ビス(3-アミノプロピル)テトラメチルジシロキサン(以下、SiDAとする)4.97g(0.02モル)、末端封止剤としてアニリン0.47g(0.005モル)をNMP130gに溶解した。ここに2,2-ビス{4-(3,4-ジカルボキシフェノキシ)フェニル}プロパン二無水物(以下、BSAAとする)26.02g(0.05モル)をNMP20gとともに加えて、25℃で1時間反応させ、次いで50℃で4時間撹拌した。その後、180℃で5時間撹拌した。撹拌終了後、溶液を水3Lに投入し、ろ過して沈殿を回収し、水で3回洗浄した後、真空乾燥機を用いて80℃20時間乾燥した。得られたポリマー固体の赤外吸収スペクトルを測定したところ、1780cm-1付近、1377cm-1付近にポリイミドに起因するイミド構造の吸収ピークが検出された。このようにしてエポキシ基と反応可能な官能基を有し、一般式(1)で表される構造がポリイミド全量に対し11.6重量%含まれるポリイミドAを得た。4gのポリイミドAにテトラヒドロフラン6gを加え、23℃で撹拌したところ溶解した。すなわち有機溶剤可溶性であった。
固形エポキシ化合物:NC3000-H(日本化薬(株)製)
液状エポキシ化合物:YL980(三菱化学(株)製)
(b)無機粒子
SE2050((株)アドマテックス製シリカ粒子、平均粒子径0.5μm)
SE5100((株)アドマテックス製シリカ粒子、平均粒径1.5μm)
YA100C-SP3((株)アドマテックス製シリカ粒子、平均粒径0.1μm)
FB-5LDX(電気化学工業(株)製シリカ粒子、平均粒径4.2μm)
(d)溶剤
PGMEA(KHネオケム(株)製)
エチルジグリコール((株)ダイセル製)
(e)ゴム粒子
カネエースMX-113((株)カネカ製、コアシェルゴム粒子30重量%含有液状エポキシ樹脂(液状エポキシ樹脂70重量%)、コアシェルゴム粒子の平均粒子径0.1μm)
(f)エポキシ硬化剤
2PZ(四国化成工業(株)製)。
NC3000-H(日本化薬(株)製)を11.35g、SE2050((株)アドマテックス製シリカ粒子、平均粒子径0.5ミクロン)を54.60g、カネエースMX-113((株)カネカ製、コアシェルゴム粒子30重量%含有エポキシ樹脂)を4.68g、合成例1で得られたポリイミドAを6.90gおよびPGMEA(KHネオケム(株)製)を22.00g、250mLポリ容器に添加し、室温下、ボールミル架台上で96時間攪拌した。その後、2PZ(四国化成工業(株)製)を0.47gを加えさらに24時間攪拌した。保留粒子径10μmのフィルターを用いて、得られた混合液の加圧ろ過を行い、半導体用樹脂組成物1を得た。全固形分の重量(ポリイミドA、カネエースMX-113、NC3000-H、SE2050、2PZの合計の重量)のうち、SE2050の割合は70重量%である。
カネエースMX-113を4.68g用いる代わりに、カネエースMX-113を2.34gおよびYL980を2.34g用いた以外は実施例1と同様にして、半導体用樹脂組成物2を得た。
カネエースMX-113を4.68g用いる代わりに、カネエースMX-113を1.17gおよびYL980を3.51g用いた以外は実施例1と同様にして、半導体用樹脂組成物3を得た。
PGMEAをすべてエチルジグリコール((株)ダイセル製)に置き換えた以外は実施例1と同様にして、半導体用樹脂組成物4を得た。
SE2050をすべてSE5100((株)アドマテックス製シリカ粒子、平均粒径1.5μm)に置き換えた以外は実施例1と同様にして、半導体用樹脂組成物5を得た。
SE2050をすべてYA100C-SP3((株)アドマテックス製シリカ粒子、平均粒径0.1μm)に置き換えた以外は実施例1と同様にして、半導体用樹脂組成物6を得た。
SE2050をすべてFB-5LDX(電気化学工業(株)製シリカ粒子、平均粒径4.2μm)に置き換えた以外は実施例1と同様にして、半導体用樹脂組成物7を得た。
各成分の配合量を表2のとおりとして、全固形分の重量のうち、SE2050の割合が60重量%になるようにした以外は実施例1と同様にして、半導体用樹脂組成物8を得た。
各成分の配合量を表2のとおりとして、全固形分の重量のうち、SE2050の割合が90重量%になるようにした以外は実施例1と同様にして、半導体用樹脂組成物9を得た。
カネエースMX-113をすべてYL980に置き換えた以外は実施例1と同様にして、比較用樹脂組成物1を得た。
カネエースMX-113をすべてYL980に、PGMEAをすべてエチルジグリコールに置き換えた以外は実施例1と同様にして、比較用樹脂組成物2を得た。
各成分の配合量を表2のとおりとして、全固形分の重量のうち、SE2050の割合が50重量%になるようにした以外は実施例1と同様にして、比較用樹脂組成物3を得た。
各成分の配合量を表2のとおりとして、全固形分の重量のうち、SE2050の割合が95重量%になるようにした以外は実施例1と同様にして、比較用樹脂組成物4を得た。
2 半導体用樹脂層
3 比較用樹脂層
4 無機粒子が不足している領域
Claims (17)
- (a)エポキシ化合物、(b)無機粒子、(c)ポリイミドおよび(d)溶剤を含有する半導体用樹脂組成物であって、前記半導体用樹脂組成物の全重量から前記(d)溶剤の重量を除いた全固形分の重量のうち、前記(b)無機粒子の割合が60重量%以上92重量%以下であり、さらに(e)ゴム粒子を含有することを特徴とする半導体用樹脂組成物。
- 前記(c)ポリイミドが、一般式(2)または一般式(3)で表される構造を有し、かつエポキシ基と反応可能な官能基を側鎖に少なくとも一つ有し、かつ一般式(1)で表される構造を一般式(2)および一般式(3)中のR4として有し、一般式(1)で表される構造は(c)ポリイミド全量に対し5~15重量%であることを特徴とする請求項1に記載の半導体用樹脂組成物。
- 前記(c)ポリイミドが、有機溶剤可溶性であることを特徴とする請求項1または2に記載の半導体用樹脂組成物。
- 前記(b)無機粒子の平均粒子径が10nm以上、5μm以下であることを特徴とする請求項1~3のいずれかに記載の半導体用樹脂組成物。
- 前記(e)ゴム粒子の平均粒子径が、前記(b)無機粒子の平均粒子径以下であることを特徴とする請求項1~4のいずれかに記載の半導体用樹脂組成物。
- 前記(a)エポキシ化合物が、液状エポキシ化合物および固形エポキシ化合物を含有し、(a)エポキシ化合物の重量のうち、液状エポキシ化合物の割合が10~50重量%であることを特徴とする請求項1~5のいずれかに記載の半導体用樹脂組成物。
- 前記液状エポキシ化合物100重量部に対して、前記(e)ゴム粒子が2~100重量部であることを特徴とする請求項6に記載の半導体用樹脂組成物。
- 前記(e)ゴム粒子がコアシェルゴム粒子であることを特徴とする請求項1~7のいずれかに記載の半導体用樹脂組成物。
- 支持体上に(a)エポキシ化合物、(b)無機粒子、(c)ポリイミドを含有する半導体用樹脂層を有する半導体用樹脂フィルムであって、前記半導体用樹脂層の重量のうち、前記(b)無機粒子の割合が60重量%以上92重量%以下であり、さらに前記半導体用樹脂層が(e)ゴム粒子を含有することを特徴とする半導体用樹脂フィルム。
- 前記(c)ポリイミドが、一般式(2)または一般式(3)で表される構造を有し、かつエポキシ基と反応可能な官能基を側鎖に少なくとも一つ有し、かつ一般式(1)で表される構造を一般式(2)および一般式(3)中のR4として有し、一般式(1)で表される構造は前記(c)ポリイミド全量に対し5~15重量%であることを特徴とする請求項9に記載の半導体用樹脂フィルム。
- 前記(c)ポリイミドが、有機溶剤可溶性であることを特徴とする請求項9または10に記載の半導体用樹脂フィルム。
- 前記(b)無機粒子の平均粒子径が10nm以上、5μm以下であることを特徴とする請求項9~11のいずれかに記載の半導体用樹脂フィルム。
- 前記(e)ゴム粒子の平均粒子径が、前記(b)無機粒子の平均粒子径以下であることを特徴とする請求項9~12のいずれかに記載の半導体用樹脂フィルム。
- 前記(a)エポキシ化合物が、液状エポキシ化合物および固形エポキシ化合物を含有し、前記(a)エポキシ化合物の重量のうち、液状エポキシ化合物の割合が10~50重量%であることを特徴とする請求項9~13のいずれかに記載の半導体用樹脂フィルム。
- 前記液状エポキシ化合物100重量部に対して、前記(e)ゴム粒子が2~100重量部であることを特徴とする請求項14に記載の半導体用樹脂フィルム。
- 前記(e)ゴム粒子がコアシェルゴム粒子であることを特徴とする請求項9~15のいずれかに記載の半導体用樹脂フィルム。
- 請求項1~8のいずれかに記載の半導体用樹脂組成物から(d)溶剤を除去した組成物の硬化物または請求項9~16のいずれかに記載の半導体用樹脂層の硬化物を有する半導体装置。
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KR20160091925A (ko) | 2016-08-03 |
TWI648342B (zh) | 2019-01-21 |
US10050005B2 (en) | 2018-08-14 |
TW201527430A (zh) | 2015-07-16 |
CN105745274A (zh) | 2016-07-06 |
US20160300810A1 (en) | 2016-10-13 |
KR102256525B1 (ko) | 2021-05-26 |
CN105745274B (zh) | 2018-06-29 |
JPWO2015080098A1 (ja) | 2017-03-16 |
JP6528404B2 (ja) | 2019-06-12 |
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