JP4483270B2 - Adhesive composition for semiconductor device, adhesive sheet for semiconductor device using the same, substrate for semiconductor connection, semiconductor device - Google Patents

Description

  The present invention relates to an adhesive composition constituting a semiconductor connection substrate (interposer) used when a semiconductor integrated circuit (IC) is mounted and packaged, an adhesive sheet for a semiconductor device using the same, and a semiconductor connection The present invention relates to a manufacturing substrate and a semiconductor device.

  Conventionally, package forms such as a dual inline package (DIP), a small outline package (SOP), and a quad flat package (QFP) have been used as semiconductor integrated circuit (IC) packages. However, with the increase in the number of pins of ICs and the downsizing of packages, the QFP package that can increase the number of pins is approaching the limit. Therefore, in recent years, the BGA method, the LGA method, the PGA method and the like have been put into practical use as means for increasing the number of pins and reducing the size. Among them, the BGA method has been attracting attention because of the possibility of cost reduction, weight reduction and thinning by using plastic materials.

  FIG. 1 shows an example of the BGA method. The BGA method is characterized by having solder balls on the grid (grid array) corresponding to the number of pins of the IC as an external connection portion of the semiconductor connection substrate to which the IC is connected. Connection to the printed circuit board (mother board) is performed by placing the solder balls so as to coincide with the conductor pattern of the printed circuit board on which the solder has already been printed, and melting the solder by reflow. The biggest feature is that since the bottom surface of the interposer can be used, many terminals can be arranged in a small space compared to a package such as QFP that can only be used at the periphery. For this reason, on the mounting surface, it is possible to reduce the mounting area and increase the mounting efficiency. As a further advancement of this miniaturization function, there is a chip scale package (CSP), a micro BGA (μ-BGA), a fine pitch BGA (FP-BGA), a memory BGA (m-BGA), a board on chip (BOC). ) Etc. have been proposed.

   On the other hand, in the BGA method, a method of laminating a metal plate or the like on a semiconductor connection substrate is generally used for the purpose of reinforcement, heat dissipation, and electromagnetic shielding. In particular, it is effective when a TAB tape, a flexible printed circuit board, or a rigid board is used for a wiring board made of an insulating layer and a conductor pattern for connecting an IC. For this reason, the substrate for semiconductor connection is a wiring board layer composed of an insulator layer and a conductor pattern for connecting an IC, a layer in which a conductor pattern such as a reinforcing plate (stiffener) or a heat sink (heat spreader) is not formed, And it has the structure which has at least 1 layer of the adhesive bond layer for laminating these, respectively. An IC chip is mounted on these semiconductor connection substrates, and the semiconductor element and metal wiring are connected by wire bonding or inner leads. Thereafter, resin sealing is performed, and the semiconductor device sealed with resin is coated with a solder paste and mounted with solder balls.

  Eventually, the adhesive layer remains in the package. Therefore, the properties required for the adhesive layer are (a) reflow heat resistance, (b) absorbability of stress generated during temperature cycle and reflow between different materials such as wiring board layer and reinforcing plate (stress (Relaxability), (c) easy processability, (d) insulation when laminated on the wiring.

From this point of view, various systems have been developed as adhesive layers for semiconductor connection substrates. As what improved reflow heat resistance, the adhesive composition containing a carboxy modified acrylonitrile butadiene rubber, an epoxy resin, a hardening | curing agent, and a silica powder is mentioned (for example, refer patent document 1). Moreover, the adhesive composition containing epoxy modified acrylic rubber, an epoxy resin, and a hardening | curing agent is mentioned as what improved thermal cycling resistance (for example, refer patent document 2). Moreover, as what improved insulation, the adhesive composition containing a polyamide resin, an epoxy resin, and a silicone compound is mentioned (refer patent documents 3-4). Furthermore, silicone compounds typified by silicone oil are used in sealing resins for semiconductor devices (Patent Document 5, etc.).
Japanese Patent Laid-Open No. 10-178067 (P4-7) Japanese Patent Laid-Open No. 57-210695 JP-A-6-256732 Japanese Patent Laid-Open No. 3-11464 JP 2002-237554 A

  However, the adhesives improved by various methods have also been effective in reflow heat resistance, thermal cycle resistance and insulation, but have not fully satisfied all the properties.

  In addition, the adhesive sheet for semiconductor is bonded to the wiring board layer composed of the insulating layer and the conductor pattern constituting the substrate for semiconductor connection, and the layer where the conductor pattern is not formed, using a laminating method or a vacuum pressure bonding method. ing. However, in this process, the conventional adhesive has a strong tack force, and it is difficult to perform alignment by temporary bonding, and in some cases, bubbles are involved at the bonding interface. As a result, there arises a problem that peeling or cracking occurs during reflow. In addition, when the semiconductor device adhesive sheet is appropriately punched in accordance with the package shape using a mold, there is a problem in the process that the adhesive adheres to the punching mold and the conveyance path due to high tackiness. There is a method to control the tack force of the adhesive sheet for semiconductors by pre-curing reaction (aging treatment), but since the reaction of the whole system proceeds, such as deterioration of adhesiveness in the uncured state and life of the adhesive Problems arise.

  An object of the present invention is to eliminate the problems that occur in such processing steps, and to have excellent reflow heat resistance and thermal cycle resistance, an adhesive composition for semiconductor devices, an adhesive sheet for semiconductor devices using the same, and a semiconductor connection It is to provide a substrate and a semiconductor device industrially.

That is, this invention is the adhesive composition for semiconductor devices which forms the adhesive bond layer of a board | substrate for semiconductor connection, Comprising: An adhesive composition has a thermosetting resin (A) and a C1-C8 side chain. At least one selected from a copolymer (B), an inorganic filler (C), an alkyl modification, an alkylaralkyl modification, a fatty acid ester modification, a fluoroalkyl modification, and a methylstyryl modification. type of adhesive der thermosetting containing a silicone oil (D) is, the amount of the silicone oil (D) is 0.1 to 5 parts by weight der against the adhesive composition 100 parts by weight A semiconductor device adhesive composition, a semiconductor device substrate, and a semiconductor device using the same.

  The adhesive composition of the present invention has excellent reflow heat resistance and thermal cycle resistance, and is excellent in easy processability.

  The present invention, as a result of intensive studies on the tack force and the initial adhesive force expression mechanism at the time of lamination and vacuum pressure bonding of the adhesive composition for semiconductor devices, by adding a specific silicone oil, excellent reflow heat resistance and It has excellent processability while maintaining thermal cycle resistance.

  The adhesive sheet for semiconductor devices in the present invention is produced from the adhesive composition for semiconductor devices (hereinafter referred to as adhesive composition) of the present invention, and the adhesive composition is curable. Usually, the adhesive is provided in an uncured state or a semi-cured state, and forms an adhesive layer of the substrate for semiconductor connection.

  The adhesive composition of the present invention is selected from a thermosetting resin (A), a thermoplastic resin (B), an inorganic filler (C), and an alkyl modification, an alkylaralkyl modification, a fatty acid ester modification, a fluoroalkyl modification, and a methylstyryl modification. At least one kind of silicone oil (D) contained as an essential component. The thermoplastic resin has functions such as adhesion, flexibility, and relaxation of thermal stress, and the thermosetting resin has functions of heat resistance, high temperature insulation, chemical resistance, and improvement of the strength of the adhesive layer. The inorganic filler is necessary for further improving the reflow heat resistance and the thermal cycle resistance. Further, at least one silicone oil selected from alkyl modification, alkyl aralkyl modification, fatty acid ester modification, fluoroalkyl modification, and methylstyryl modification is necessary for reducing the tackiness of the adhesive layer while maintaining reflow heat resistance. .

  Examples of the thermosetting resin used in the present invention include known resins such as epoxy resins, phenol resins, melamine resins, xylene resins, furan resins, and cyanate ester resins. In particular, an epoxy resin and a phenol resin are preferable because of excellent insulation. The epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule, but diglycidyl ether such as bisphenol A, bisphenol F, bisphenol S, resorcinol, dihydroxynaphthalene, dicyclopentadiene diphenol, epoxy Aliphatic rings such as epoxidized phenol novolac (phenol novolac type epoxy resin), epoxidized cresol novolak (cresol novolac type epoxy resin), epoxidized trisphenylol methane, epoxidized tetraphenylol ethane, epoxidized metaxylene diamine, cyclohexane diepoxide And formula epoxies. Further, for imparting flame retardancy, a halogenated epoxy resin, particularly a brominated epoxy resin may be used.

  Examples of brominated epoxy resins include copolymerized epoxy resins of tetrabromobisphenol A and bisphenol A, or brominated phenol novolac type epoxy resins such as “BREN” -S (manufactured by Nippon Kayaku Co., Ltd.). It is done. These brominated epoxy resins may be used in combination of two or more in consideration of bromine content and epoxy equivalent.

  As the phenol resin, any known phenol resin such as novolac type phenol resin and resol type phenol resin can be used. For example, alkyl-substituted phenols such as phenol, cresol, p-t-butylphenol, nonylphenol, p-phenylphenol, cyclic alkyl-modified phenols such as terpene and dicyclopentadiene, hetero groups such as nitro groups, halogen groups, cyano groups, and amino groups Examples thereof include those having functional groups containing atoms, those having a skeleton such as naphthalene and anthracene, and resins composed of polyfunctional phenols such as bisphenol A, bisphenol F, bisphenol S, resorcinol, and pyrogallol. The addition amount of the thermosetting resin is 5 to 400 parts by weight, preferably 100 to 200 parts by weight with respect to 100 parts by weight of the thermoplastic resin. When the addition amount of the thermosetting resin is less than 5 parts by weight, the adhesiveness after heat curing and the breaking strength of the adhesive layer are remarkably lowered, and the reflow heat resistance is lowered. Moreover, when the addition amount of a thermosetting resin exceeds 400 weight part, since the relaxation effect of a thermal stress falls by the fall of coating property or high elastic modulus of a hardening body, it is unpreferable.

  The thermoplastic resin used in the present invention includes acrylonitrile-butadiene copolymer (NBR), acrylonitrile-butadiene rubber-styrene resin (ABS), polybutadiene, polyethylene, ethylene-butadiene-ethylene resin (SEBS), acrylic ester and methacrylic ester. Examples thereof include a copolymer (acrylic resin) having an acid ester as an essential copolymerization component, polyvinyl butyral, polyamide, polyester, polyimide, polyamideimide, and polyurethane. Moreover, these thermoplastic resins may have a functional group capable of reacting with the functional group of the above-mentioned thermosetting resin. Specific examples include an amino group, a carboxyl group, an epoxy group, a hydroxyl group, a methylol group, an isocyanate group, a vinyl group, and a silanol group. These functional groups are preferable because the bond with the thermosetting resin becomes strong and the film strength and reflow heat resistance are improved.

  Among these thermoplastic resins, butadiene is an essential co-polymer from the viewpoint of adhesiveness between the adhesive layer and the material that forms the layer without the conductor pattern such as a heat sink, flexibility, and thermal stress relaxation effect. Copolymers to be combined are particularly preferred, and various types can be used. In particular, acrylonitrile-butadiene copolymer (NBR), styrene-butadiene-ethylene resin (SEBS), styrene-butadiene resin (SBS) and the like are preferable from the viewpoints of adhesion to metal, chemical resistance, and the like. Further, a copolymer having butadiene as an essential copolymer component and having a carboxyl group is more preferable from the viewpoint of adhesion and heat resistance. For example, carboxyl group-containing NBR (NBR-C), carboxyl group-containing SEBS (SEBS-C), Examples thereof include carboxyl group-containing SBS (SBS-C). Examples of NBR-C include those obtained by carboxylating terminal groups of a copolymer rubber obtained by copolymerizing acrylonitrile and butadiene at a molar ratio of about 10/90 to 50/50, or acrylonitrile, butadiene and acrylic acid, maleic acid, etc. And a terpolymer rubber of a carboxyl group-containing copolymerizable monomer. Specifically, PNR-1H (manufactured by JSR Corporation), "Nipol" 1072J, "Nipol" DN612, "Nipol" DN631 (manufactured by Nippon Zeon Co., Ltd.), "Hiker" 'CTBN (manufactured by BF Goodrich Co., Ltd.) and the like. Moreover, MX-073 (Asahi Kasei Co., Ltd.) can be illustrated as SEBS-C, and D1300 (Shell Japan Co., Ltd.) can be illustrated as SBS-C.

  Moreover, the copolymer which uses acrylic acid ester and methacrylic acid ester which have a C1-C8 side chain as an essential copolymerization component from the point of adhesiveness and thermal cycle resistance is also preferable. Furthermore, a copolymer having an acrylic acid ester and a methacrylic acid ester as a copolymer component and having an epoxy group or a carboxyl group is more preferable from the viewpoints of adhesiveness and reflow heat resistance. For example, epoxy group-containing acrylic rubber HTR-860 (manufactured by Teikoku Chemical Industry Co., Ltd.) and carboxyl group-containing acrylic rubber SG-280DR (manufactured by Teikoku Chemical Industry Co., Ltd.) can be exemplified.

  Examples of the inorganic filler contained in the adhesive composition of the present invention include crystalline silica powder, fused silica powder, alumina, aluminum hydroxide, silicon nitride, magnesium hydroxide, calcium aluminate hydrate, zirconium oxide, and zinc oxide. , Antimony trioxide, antimony pentoxide, titanium oxide, iron oxide, cobalt oxide, chromium oxide, talc, aluminum, gold, silver, nickel, iron, clay, mica and the like. Among these, from the viewpoint of dispersibility, aluminum hydroxide, alumina and silica are preferable, and the average particle size (the particle size showing the maximum value in the particle size distribution measurement of the primary particles dispersed in the organic solvent) is 0.2 to 15 μm. Is preferred. From the viewpoint of reflow heat resistance, silica having a 5% weight loss temperature (thermal decomposition temperature) of 350 ° C. or higher by TGA (heating weight loss measurement), preferably spherical silica powder, more preferably fused spherical silica. The blending amount of these inorganic fillers is preferably 10 to 50 parts by weight with respect to 100 parts by weight of the adhesive composition. More preferably, it is 20-40 weight part. If the blending amount is less than 10 parts by weight, reflow heat resistance and film strength cannot be improved, such being undesirable. Moreover, when a compounding quantity exceeds 50 weight part, since the deterioration of coating property, the adhesive fall after hardening, etc. are seen, it is unpreferable.

  It is important that the silicone oil contained in the adhesive composition of the present invention is at least one silicone oil selected from alkyl modification, alkyl aralkyl modification, fatty acid ester modification, fluoroalkyl modification, and methylstyryl modification. The structure of these silicone oils is a side chain modified type in which an organic group is introduced into the side chain of polysiloxane, a both end modified type in which an organic group is introduced into both ends, a one end modified type in which an organic group is introduced into one end, Either a side chain or a side chain modified with both ends introduced with an organic group may be used, but the side chain modified type and the side chain modified with both ends are particularly preferred from the viewpoint of tack reduction effect. By adding a silicone oil having these specific organic groups, it is possible to reduce the tack force of the adhesive layer while maintaining reflow heat resistance and thermal cycle resistance. These specific silicone oils are thought to contribute to the improvement of mold release and lubricity on the resin surface. Moreover, you may use these individually or in mixture of 2 or more types. The compounding quantity of silicone oil is 0.1-5 weight part with respect to 100 weight part of adhesive compositions, More preferably, it is 1-3 weight part. If it is less than 0.1 parts by weight, the effect of reducing tack is low, which is not preferable, and if the amount exceeds 5 parts by weight, it is not preferable because adhesiveness after heat curing and reflow heat resistance are reduced. . Furthermore, silicone oils other than those described above, such as epoxy-modified silicone oil, amino-modified silicone oil, carboxyl-modified silicone oil, and alcohol-modified silicone oil, are not limited to the position where the organic group is introduced, and the tack reduction effect is small and the reflow heat resistance is small. Also, dimethyl silicone oil and phenyl silicone oil have poor compatibility with the resin.

  Moreover, you may add the hardening | curing agent and hardening accelerator of thermosetting resins, such as an epoxy resin, to the adhesive bond layer of this invention. For example, 3,3′5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 3,3′5,5′-tetraethyl-4,4′-diaminodiphenylmethane, 3,3′-dimethyl-5, 5'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,2'3,3'-tetrachloro-4,4'-diaminodiphenylmethane, 4, 4'-diaminodiphenyl sulfide, 3,3'-diaminobenzophenone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminobenzophenone, Aromatic polyamines such as 3,4,4'-triaminodiphenylsulfone, boron trifluoride triethylamine complexes and the like Known amine complexes, imidazole derivatives such as 2-alkyl-4-methylimidazole and 2-phenyl-4-alkylimidazole, organic acids such as phthalic anhydride and trimellitic anhydride, dicyandiamide, and triphenylphosphine Can be used. You may use these individually or in mixture of 2 or more types. The addition amount is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the adhesive composition constituting the adhesive layer. If the addition amount is less than 1 part by weight, the curing reaction does not proceed efficiently, and the adhesiveness after heat curing, the Tg and the reflow heat resistance are decreased. Moreover, since the fall of the thermal stress relaxation effect of hardened | cured material and the lifetime of an adhesive bond layer is seen when the addition amount exceeds 30 weight part, it is unpreferable.

  In addition to the above components, the addition of organic / inorganic components such as antioxidants and ion scavengers is not limited as long as the properties of the adhesive are not impaired. Examples of the organic component include crosslinked polymers such as styrene, NBR rubber, acrylic rubber, and polyamide. Examples of the antioxidant include hindered phenol-based and amine-based primary antioxidants, and sulfur-based and phosphorus-based secondary antioxidants. Examples of the ion scavenger include antimony trioxide and antimony pentoxide. These may be used alone or in combination of two or more. The average particle size of the fine particle component is preferably 0.02 to 15 μm, more preferably 0.2 to 5 μm. Moreover, 2-30 weight part of the whole adhesive composition is suitable for a compounding quantity.

Further, the uncured probe tack force of the semiconductor device adhesive sheet formed from the semiconductor adhesive composition of the present invention is preferably ² N / cm ² (40 gf / 5 mmφ) or less at 25 ° C. The tack force of the adhesive sheet for semiconductor devices has a great influence on the laminate pressure bonding property and press pressure bonding property of the adhesive sheet. The probe tack test method described in JISZ0237 was used as an index for tackiness. The probe tack test method is a method in which the tack force is defined by the force required to peel the probe vertically from the adhesive sheet after the probe is brought into contact with the adhesive sheet for a certain period of time while applying a certain load. The void value generated when the adhesive sheet for semiconductor is bonded to the wiring board layer composed of the insulator layer and the conductor pattern or the layer where the conductor pattern is not formed, and the adhesion to the punching die has a tack value of 2 N / cm ^2. (40 gf / 5 mmφ) or less is not confirmed, and the workability is excellent.

  Furthermore, it is preferable that the adhesive force P in the uncured state of the adhesive sheet for a semiconductor device formed from the adhesive composition of the present invention is 0.5 N / cm ≦ P ≦ 10 N / cm. If the adhesive force P in the uncured state is smaller than 0.5 N / cm, it is not preferable because a position shift or a substrate or a metal plate is dropped in the process from bonding to heat curing. On the other hand, if it is larger than 10N, the adhesive force P is too strong, which hinders the laminating process. Furthermore, the adhesive composition has an adhesive strength after heat curing of preferably 5 N / cm or more, and more preferably 10 N / cm or more. When the adhesive strength after heat curing is less than 5 N / cm, it is not preferable because peeling occurs during handling of the package, or a decrease in reflow heat resistance and a decrease in reliability are observed. Moreover, what is necessary is just to be able to ensure the adhesive force of 50 N / cm or less. In addition, the uncured state of the adhesive layer in the present invention is a state in which the heat generation of less than 10% of the total curing heat generation amount measured using a normal DSC (differential scanning calorimetry) is finished.

  The thickness of the adhesive layer can be appropriately selected in relation to tack force, adhesive force, elastic modulus, etc., but is preferably 5 μm to 300 μm, more preferably 10 μm to 150 μm. Adhesion in the adhesive sheet for semiconductor devices of the present invention The agent layer is not particularly limited as long as it is a sheet having a thickness of 10 to 300 μm. The shape of the adhesive sheet is preferably such that the adhesive composition for semiconductor devices of the present invention is used as an adhesive layer and has at least one peelable protective film layer. For example, a two-layer structure of protective film layer / adhesive layer, or a three-layer structure of protective film layer / adhesive layer / protective film layer as shown in FIG. In addition to a single film of the adhesive composition, the adhesive sheet includes a composite structure in which an insulating film such as polyimide is laminated as in an adhesive layer / insulating film / adhesive layer. The degree of cure of the adhesive sheet may be adjusted by heat treatment (aging treatment). Adjustment of the degree of cure has the effect of preventing excessive flow of the adhesive when adhering the adhesive sheet to the wiring board or IC and preventing foaming (curing foaming) due to moisture during heat curing. The degree of cure can be defined by, for example, the minimum viscosity (flow tester method) at the bonding processing temperature specified in JIS-K7210. Under conditions of a temperature of 120 ° C., a die size of 2 × 5 mm, and a test pressure of 9.8 MPa, 3000 to 60000 Pa · s, preferably 6000 to 30000 Pa · s is preferable.

  The protective film layer as used herein refers to an adhesive before bonding an adhesive layer to a wiring board layer (TAB tape or the like) composed of an insulator layer and a conductor pattern or a layer (stiffener or the like) where no conductor pattern is formed. Although it will not specifically limit if it can peel without impairing the form and function of a layer, For example, polyester, polyolefin, polyphenylene sulfide, polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polyvinyl butyral, polyvinyl acetate, polyvinyl alcohol , Polycarbonate, polyamide, polyimide, polymethylmethacrylate, and other plastic films, films coated with a release agent such as silicone or fluorine compound, and these films are laminated. Sorted paper, paper or the like impregnated or coated with a releasing property of a certain resin.

When there are protective film layers on both sides of the adhesive layer, F ₁ -F ₂ is preferably when the peel strength of each protective film layer to the adhesive layer is F ₁ , F ₂ (F ₁ > F ₂ ). 5 Nm ⁻¹ or more, more preferably 15 Nm ⁻¹ or more is required. When F ₁ -F ₂ is smaller than 5 Nm ⁻¹ , which protective film layer side the release surface is on is not stable, which is a serious problem in use. The peeling forces F ₁ and F ₂ are preferably ¹ to 200 Nm ⁻¹ , more preferably 3 to 100 Nm ⁻¹ . If it is lower than ¹ Nm ⁻¹ , the protective film layer will drop off, and if it exceeds 200 Nm ⁻¹ , peeling is unstable and the adhesive layer may be damaged.

  The board | substrate for semiconductor connection of this invention means what used the adhesive composition of this invention. This substrate has a structure having at least one wiring substrate layer composed of an insulator layer and a conductor pattern and / or a layer where no conductor pattern is formed and an adhesive layer. For example, a flexible printed circuit board, a rigid board, or a TAB tape is used as a wiring board layer made of an insulator layer and a conductor pattern, and an adhesive layer and a conductor pattern made of the adhesive composition for a semiconductor device of the present invention are formed. A semiconductor connection substrate using a metal plate such as copper, stainless steel, 42 alloy or the like can be exemplified as the layer that is not formed.

  The semiconductor device of the present invention refers to a device using the semiconductor connection substrate of the present invention, and the shape and structure are not particularly limited as long as it is a BGA type or LGA type package, for example. The method for connecting the semiconductor connection substrate and the IC may be any of gang bonding, inner lead bonding, single point bonding, wire bonding, and the like. A package called CSP is also included in the semiconductor device of the present invention.

  Next, the example of the manufacturing method of the adhesive sheet for semiconductor devices using the adhesive composition of this invention, the board | substrate for semiconductor connection, and a semiconductor device is demonstrated.

(1) Adhesive sheet (a) A paint obtained by dissolving the adhesive composition of the present invention in a solvent is applied on a polyester film having releasability and dried. It is preferable to apply so that the thickness of the adhesive layer is 10 to 100 μm. Drying conditions are 100 to 200 ° C. and 1 to 5 minutes. Solvents are not particularly limited, but aromatics such as toluene, xylene and chlorobenzene, ketones such as methylethylketone and methylisobutylketone, and aprotic polar solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone alone or a mixture are preferred. It is. The preferable amount of the solvent in the paint is 50 to 80 parts by weight, more preferably 70 to 80 parts by weight, assuming that the whole paint is 100 parts by weight. When the amount of the solvent is less than 50 parts by weight, the stirring efficiency of the paint is lowered and the life of the paint is shortened, which is not desirable. On the other hand, if it exceeds 80 parts by weight, the coatability deteriorates, which is not preferable.

  (B) The adhesive sheet of the present invention is obtained by laminating a polyester or polyolefin-based protective film layer having a releasability with a lower peel strength than the above to the film of (a). In order to further increase the adhesive thickness, the adhesive layer on the adhesive sheet may be laminated a plurality of times.

(2) Semiconductor device (a) Creation of wiring board comprising insulator layer and conductor pattern Conditions of 130-170 ° C., 0.1-0.5 MPa with 12-35 μm electrolytic copper foil on tape with adhesive for TAB Then, the film is sequentially heated and cured at 80 to 170 ° C. in an air oven to prepare a TAB tape with copper foil. Photoresist film formation, etching, resist stripping, electrolytic nickel plating, electrolytic gold plating, and solder resist film creation are respectively performed on the copper foil surface of the obtained TAB tape with copper foil by a conventional method to prepare a wiring board.

(B) Creation of a layer in which no conductor pattern is formed A metal plate such as a pure copper plate, nickel-plated copper plate, blackened copper plate or stainless steel plate having a thickness of 0.05 to 0.5 mm is degreased with acetone.

(C) Preparation of a component for a semiconductor connection board (wiring board with adhesive) The one-side protective film of the adhesive sheet created in (1) above is formed on the wiring board layer composed of the insulator layer and conductor pattern in (a). Laminate after peeling. The laminate surface may be a surface with or without a conductor pattern. The laminating temperature is 60 ° C. to 200 ° C., and the pressure is 0.1 to 5 MPa. Finally, depending on the shape of the semiconductor device, it is appropriately punched and cut.

(D) Creation of parts for semiconductor connection substrate (stiffener with adhesive) After peeling off the one-side protective film of the adhesive sheet created in (1) above on the layer where the conductor pattern of (b) is not formed Laminate. The laminating temperature is 60 ° C. to 200 ° C., and the pressure is 0.1 to 5 MPa. Finally, depending on the shape of the semiconductor device, it is appropriately punched and cut.

(E) Creation of a substrate for semiconductor connection (e-1) When using a wiring board with adhesive (c) The protective film of the adhesive layer was peeled off from the component (wiring board with adhesive) and punched into an appropriate shape. Affix to a metal plate. For example, the metal plate can be exemplified by a rectangular outer shape, in which a square hole is punched in the center in accordance with the device hole of the wiring board. The bonding conditions are a temperature of 60 ° C. to 200 ° C. and a pressure of 0.1 to 5 MPa. Finally, post-curing is performed at 80 ° C. to 200 ° C. for about 15 to 180 minutes in order to heat and cure the adhesive in a hot air oven.

(E-2) When using a stiffener with an adhesive The part (d) (stiffener with an adhesive) in (d) is punched out with a die, for example, with an adhesive having a square outer shape and a square hole at the center. Stiffener. Remove the protective film from the stiffener with adhesive, and match the hole in the center of the stiffener with adhesive to the conductor film surface or backside polyimide film surface of the wiring board layer in (a) above, Paste together. The bonding conditions are a temperature of 60 ° C. to 200 ° C. and a pressure of 0.1 to 5 MPa. Finally, post-curing is performed at 80 ° C. to 200 ° C. for about 15 to 180 minutes in order to heat and cure the adhesive in a hot air oven.

  An example of the semiconductor connection substrate described above is shown in FIG.

(3) Production of Semiconductor Device The inner lead portion of the semiconductor connection substrate of (2) is thermocompression-bonded (inner lead bonding) to the IC gold bump, and the IC is mounted. Next, a semiconductor device is manufactured through resin sealing. The obtained semiconductor device is connected to a printed circuit board or the like on which other components are mounted via solder balls, and mounted on an electronic component.

  The adhesive composition of the present invention constitutes a substrate for semiconductor connection used in a ball grid array (BGA), a chip scale package (CSP) having a BGA structure, a land grid array (LGA), and a pin grid array (PGA) system. It can be used as an adhesive for a semiconductor device for bonding between a wiring board layer composed of an insulating layer and a conductor pattern and a layer where a conductor pattern such as a metal plate (stiffener or heat spreader) is not formed. . Moreover, the obtained composition can be used for the adhesive sheet for semiconductor devices, the board | substrate for semiconductor connection, and a semiconductor device.

  EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. First, the evaluation method is described.

Evaluation Method (1) Adhesive strength in an uncured state: An adhesive layer having a thickness of 100 μm was laminated on the surface of a pure copper plate having a thickness of 0.5 mm under conditions of 130 ° C. and 0.5 MPa. A polyimide film ("UPILEX" 75S, manufactured by Ube Industries, Ltd.) was bonded to the pure copper plate with the adhesive on the adhesive layer side at 130 ° C and 0.5 MPa. The polyimide film and adhesive layer of the obtained sample were cut with a cutter so as to have a width of 5 mm, and at the speed of 50 mm / min in the 90 ° direction at the interface between the adhesive layer and the polyimide film or at the interface between the adhesive layer and the pure copper plate. The force applied at that time was taken as the adhesive force. The adhesive force in an uncured state is preferably 0.5 N / cm or more and 10 N / cm or less from the viewpoint of workability. The peeling force was measured with TENSILON / UTM-4-100 manufactured by TOYOBALDWIN.

  (2) Adhesive strength after curing: An adhesive layer having a thickness of 100 μm was laminated on the surface of a pure copper plate having a thickness of 0.5 mm under the conditions of 130 ° C. and 0.5 MPa. A polyimide film ("UPILEX" 75S, manufactured by Ube Industries, Ltd.) was bonded to the pure copper plate with the adhesive on the adhesive layer side at 130 ° C and 0.5 MPa. The prepared sample was heated and cured in an air oven at 150 ° C. for 2 hours. Cut the polyimide film and adhesive layer of the obtained sample with a cutter so that the width is 5 mm, and at the interface of the adhesive layer and the polyimide film or the interface between the adhesive layer and the pure copper plate at a speed of 50 mm / min in the 90 ° direction. The force applied at that time was taken as the adhesive force. From the viewpoint of processability, handling properties, moldability, and reliability of the semiconductor device, the adhesive strength in the cured state is desirably 5 N / cm or more. The peeling force was measured with TENSILON / UTM-4-100 manufactured by TOYOBALDWIN.

  (3) Reflow heat resistance: An adhesive layer having a thickness of 100 μm was laminated on the surface of a pure copper plate having a thickness of 0.5 mm under the conditions of 130 ° C. and 0.5 MPa. A polyimide film ("UPILEX" 75S, manufactured by Ube Industries, Ltd.) was bonded to the pure copper plate with the adhesive on the adhesive layer side at 130 ° C and 0.5 MPa. The prepared sample was heated and cured in an air oven at 150 ° C. for 2 hours. The obtained sample was cut into 30 mm squares, conditioned for 168 hours in an atmosphere of 30 ° C. and 70% RH, and then immediately subjected to IR reflow at a maximum temperature of 220 to 280 ° C. for 10 seconds, and the peeled state was subjected to ultrasonic flaw detection. Observation was performed using an apparatus (MISCOPE, manufactured by Hitachi Construction Machinery Finetech Co., Ltd.). The maximum temperature at which peeling was not observed in this test was defined as the reflow heat resistance temperature. A reflow heat-resistant temperature lower than 260 ° C. is not preferable because it does not correspond to lead-free.

(4) Probe tack force: It was applied on a polyester film having releasability and dried to obtain an adhesive layer having a thickness of 100 μm. Next, the polyester film was peeled off, and the tack force at 25 ° C. was measured with a probe tack tester (TAC-II, manufactured by Resuka Co., Ltd.) with only the adhesive layer. In this test, when the tack value is 2 N / cm ² (40 gf / 5 mmφ) or less, the tack is low and the easy processability is satisfied.

  (5) Bonded surface void observation: Using the ultrasonic flaw detector (MISSCOPE, manufactured by Hitachi Construction Machinery Finetech Co., Ltd.), the sample created by the method of (1) above was used to check for voids on the bonded surface. Was confirmed (visual confirmation from a photographed image of an ultrasonic flaw detector). In addition, after confirming that the void in the adhesive bond layer before bonding a polyimide film did not generate | occur | produce, this evaluation is performed.

  (6) Thermal cycle resistance: Twenty levels of evaluation samples cut into 30 mm squares prepared by the method of (3) above were prepared for each level, and a thermal cycle tester (PL-3 type, manufactured by Tabay Espec Co., Ltd.) Among them, the treatment was carried out under the condition of holding at -65 ° C to 150 ° C at the minimum and maximum temperatures for 30 minutes each, and the occurrence of peeling was evaluated. Samples were taken out at the end of each of 100 cycles, 300 cycles, 500 cycles, and 800 cycles, and the occurrence of peeling was evaluated. If one of the 20 pieces was peeled off, it was judged as defective.

Example 1 and Comparative Examples 1 to 4
(Creation of adhesive sheet)
The following thermoplastic resin, epoxy resin and other additives are blended so as to have the composition ratio shown in Table 1, respectively, and dimethylformaldehyde (DMF) / monochlorobenzene (CB) / methyl so as to have a solid content concentration of 28 parts by weight. The mixture was stirred and dissolved in isobutyl ketone (MIBK) mixed solvent at 40 ° C. to prepare an adhesive solution.

A. Epoxy resin Bisphenol A type epoxy resin (epoxy equivalent: 186) (Epicoat 828, manufactured by Japan Epoxy Resin Co., Ltd.)
B. Thermoplastic resin SEBS-C (Asahi Kasei Co., Ltd., MX-073)
Carboxyl-modified acrylic rubber (Teikoku Chemical Industry Co., Ltd., SG-280DR)
C. Silicone oil alkyl-modified (KF-412 manufactured by Shin-Etsu Silicone Co., Ltd.)
Alkyl aralkyl modification (TSF-4427 made by GE Toshiba Silicones)
Fatty acid ester modification (X22-715, manufactured by Shin-Etsu Silicone Co., Ltd.)
Fluoroalkyl modified (FS1265 made by Toray Dow Corning Silicone)
Methyl styryl modified (Shin-Etsu Silicone KF-410)
Amino modification (KF-8005 made by Shin-Etsu Silicone Co., Ltd.)
Epoxy modification (Shin-Etsu Silicone KF101)
D. Inorganic filler Spherical silica powder (manufactured by Admatechs, SO-C2)
E. Curing agent 4,4′-DDS: 4,4′-diaminodiphenylsulfone (Sumitomo Chemical Co., Ltd., Sumicure S)
Dicyandiamide (Japan Epoxy Resin Co., Ltd., DICY7).

  The obtained adhesive solution was applied to a 25 μm thick polyethylene terephthalate film I which had been treated with a bar coater to a dry thickness of about 50 μm, dried at 100 ° C. for 1 minute and then at 150 ° C. for 5 minutes for adhesion. An agent sheet was prepared. On the other hand, an adhesive solution is applied to a polyethylene terephthalate film II having a lower peel strength than that of the polyethylene terephthalate film I so that the adhesive solution becomes 50 μm, and dried under the same conditions as those used for the polyethylene terephthalate film I. And the adhesive surfaces were laminated together to produce an adhesive sheet having a thickness of 100 μm. This sheet was measured for uncured and post-cured adhesive strength, tack strength, reflow heat resistance and thermal cycle resistance. The results are shown in Table 1.

  From the examples, the adhesive composition of the present invention achieved easy processability by reducing the tack force, and was excellent in adhesive force, reflow heat resistance, and thermal cycle resistance. On the other hand, the comparative example was inferior in easy workability and reflow heat resistance.

Sectional drawing of the one aspect | mode of the BGA type semiconductor device using the adhesive composition for semiconductor devices of this invention, and the adhesive agent sheet for semiconductor devices. Sectional drawing of the one aspect | mode of the adhesive agent sheet for semiconductor devices of this invention. 1 is a diagram illustrating one embodiment of a semiconductor connection substrate of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Semiconductor integrated circuit 2 Gold bump 3, 11 Flexible insulating film 4, 12 Adhesive layer 5, 13 which comprises wiring board layer Semiconductor connection conductor 6, 14, 18 Adhesive composition of this invention Adhesive layers 7 and 15 composed of layers 8 and 16 in which no conductor pattern is formed Solder resist 9 Solder ball 10 Sealing resin 18 Protective film layer

Claims (5)

An adhesive composition for a semiconductor device for forming an adhesive layer of a substrate for semiconductor connection, wherein the adhesive composition is a thermosetting resin (A), an acrylate ester having a side chain having 1 to 8 carbon atoms, and Copolymer (B) having methacrylic acid ester as copolymerization component , inorganic filler (C), alkyl modification, alkylaralkyl modification, fatty acid ester modification, fluoroalkyl modification, methylstyryl modification, at least one silicone oil ( D) Ri adhesive der thermosetting containing, amount of the silicone oil (D) is a feature of 0.1-5 parts by weight der Rukoto against the adhesive composition 100 parts by weight An adhesive composition for a semiconductor device. The uncured probe tack is ² N / cm ² or less at 25 ° C., and the uncured adhesive force P is 0.5 N / cm ≦ P ≦ 10 N / cm at 25 ° C. The adhesive composition for semiconductor devices according to 1. The adhesive sheet for semiconductor devices which uses the adhesive composition for semiconductor devices of Claim 1 as an adhesive layer, and has a protective film layer which can peel on at least one surface of an adhesive bond layer. 2. A semiconductor connection substrate having at least one insulating layer, a wiring substrate comprising a conductor pattern, a layer in which no conductor pattern is formed, and an adhesive layer, respectively, wherein the adhesive layer is bonded to the adhesive layer. A substrate for semiconductor connection using an agent composition. A semiconductor device using the semiconductor connection substrate according to claim 4.

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