TWI791672B - Semiconductor adhesive film and semiconductor adhesive sheet - Google Patents

Abstract

The present invention provides a semiconductor adhesive film (1) including a heat-curable adhesive agent and 15% by mass or more and 70% by mass or less of a titanium oxide filer, and a semiconductor adhesive sheet (2) in which the semiconductor adhesive film (1) is provided on a removable sheet (21).

Description

Adhesive film for semiconductor and adhesive sheet for semiconductor

The present invention relates to an adhesive film for semiconductors and an adhesive sheet for semiconductors. This application claims priority based on Japanese Patent Application No. 2017-229522 for which it applied to Japan on November 29, 2017, and uses the content here.

Adhesive films for semiconductors are used to fix semiconductor wafers to substrates and electrode members. The lower the dielectric tangent of the adhesive film for semiconductors, the more it can suppress interference with other chips and devices, and it can reduce noise and can be used as a shield for electromagnetic waves.

Patent Document 1 discloses an adhesive film for embedding a first semiconductor element that has been fixed on an adherend and fixing a second semiconductor element different from the aforementioned first semiconductor element to the adherend. After thermosetting The adhesive film, which has a dielectric constant of 4.00 or less at 1 MHz, can suppress corrosion of connection structures and conduction between wirings to manufacture highly reliable semiconductor devices. prior art literature patent documents

[Patent Document 1] Japanese Patent Laid-Open No. 2015-122433

The problem to be solved by the invention

However, Patent Document 1 does not disclose at all an adhesive film for semiconductors that lowers the dielectric tangent and improves electromagnetic wave shielding properties by adding an inorganic filler.

Therefore, the object of the present invention is to provide an adhesive film for semiconductors with a low dielectric tangent and excellent electromagnetic wave shielding properties. means to solve problems

The inventors of the present invention found that by adding 15% by mass to 70% by mass of titanium oxide to a thermosetting resin, an adhesive film for semiconductors with a low dielectric tangent after thermosetting and excellent electromagnetic shielding properties can be obtained, And the present invention has been accomplished. That is, the present invention provides an adhesive film for a semiconductor and an adhesive sheet for a semiconductor having the following characteristics. [1] An adhesive film for semiconductors containing a thermosetting adhesive and a titanium oxide filler of 15% by mass to 70% by mass. [2] The adhesive film for semiconductors according to [1], wherein the dielectric tangent at 1 MHz after thermosetting is 0.01 or less. [3] An adhesive sheet for semiconductors in which the adhesive film for semiconductors according to [1] or [2] is provided on a release sheet. Invention effect

According to the present invention, it is possible to provide an adhesive film for semiconductors that has a low dielectric tangent after thermosetting and has excellent electromagnetic wave shielding properties.

The adhesive film for semiconductors of the present invention contains a thermosetting adhesive and a titanium oxide filler in an amount of not less than 15% by mass and not more than 70% by mass. In addition, unless otherwise mentioned, mass % in this specification means the ratio of each component when the adhesive film for semiconductors is taken as 100 mass %.

The adhesive film for semiconductors of the present invention can reduce the dielectric tangent and has excellent electromagnetic wave shielding properties by containing the titanium oxide filler in an amount of 15% by mass to 70% by mass.

The thermosetting adhesive constituting the adhesive film for semiconductors of the present invention preferably contains a thermosetting component and an adhesive polymer component.

Examples of the thermosetting component include epoxy resins, phenol resins, melamine resins, urea resins, polyimide resins, benzoxazine resins, and mixtures thereof. Among these, epoxy resins, phenol resins, and mixtures thereof can be suitably used.

Epoxy resins are three-dimensionally networked when heated and have the property of forming a strong film. As this epoxy resin, conventionally known various epoxy resins have been used, usually those with a molecular weight of 200-2000 are preferred, and those with a molecular weight of 300-500 are particularly preferred. Furthermore, it is preferable to use in the form which mix|blends the epoxy resin whose molecular weight is 310-400 and is normally liquid, and the epoxy resin whose molecular weight is 400-2500, especially 500-2000 and which is solid at normal temperature. Also, the epoxy equivalent of the epoxy resin is preferably 50~5000g/eq. In this specification, "epoxy equivalent" means the number of grams (g/eq) of an epoxy compound containing 1 gram equivalent of an epoxy group, and can be measured in accordance with the method of JIS K 7236:2001.

As such epoxy resins, specifically, glycidyl ethers of phenols such as bisphenol A, bisphenol F, resorcinol (resorcinol), phenyl novolac, and cresol novolak; Glycidyl ethers of alcohols such as glycol, polyethylene glycol, and polypropylene glycol; glycidyl ethers of carboxylic acids such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; isotrimerization of aniline Epoxy resins such as cyanate esters, which use epoxypropyl or alkylepoxypropyl to replace the active hydrogen bonded to the nitrogen atom; such as vinyl rings Hexane diepoxide, 3,4-epoxycyclohexylmethyl-3,4-dicyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3 , 4-epoxy)cyclohexane-m-dioxane, etc., are so-called alicyclic epoxides formed by introducing the carbon-carbon double bond in the molecule into epoxy, for example, by oxidation. In addition, it is also possible to use Epoxy resins with biphenyl skeleton, dicyclopentadiene skeleton, dicyclohexadiene skeleton, naphthalene skeleton, etc.

Among them, a bisphenol-based glycidyl epoxy resin, an o-cresol novolac epoxy resin, a phenol novolac epoxy resin, and an epoxy resin having a dicyclopentadiene skeleton can be suitably used. These epoxy resins can be used individually by 1 type or in combination of 2 or more types.

When epoxy resin is used, it is better to use a thermoactive latent epoxy resin hardener together as a thermosetting adhesive. The so-called thermally active latent epoxy resin hardener refers to a type of hardener that does not react with epoxy resin at room temperature, but is activated by heating above a certain temperature and reacts with epoxy resin. The activation methods of thermally active latent epoxy resin hardeners include the following methods: a method of chemically reacting and generating active species (anions, cations) by heating; stable dispersion in epoxy resin around room temperature In addition, it is compatible with epoxy resin at high temperature, dissolves and starts the hardening reaction; the molecular sieve-encapsulated hardener is dissolved at high temperature to start the hardening reaction; and the method of using microcapsules, etc.

Specific examples of thermally active latent epoxy resin hardeners include various onium salts, dibasic acid dihydrazide compounds, dicyanodiamide, amine adduct hardeners, imidazole compounds, etc. Hydrogen compounds etc. These heat active type latent epoxy resin hardeners can be used individually by 1 type or in combination of 2 or more types. The thermally active latent epoxy resin hardener described above can be used in a ratio of 0.1 to 20 parts by mass, preferably 0.2 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, relative to 100 parts by mass of epoxy resin. ratio is used.

The phenolic resin is not particularly limited, and condensation products of phenols such as alkylphenols, polyhydric alcohols, and naphthols with aldehydes can be used. Specifically, phenol novolak resins, o-cresol novolak resins, p-cresol novolac resins, tert-butylphenol novolac resins, dicyclopentadiene cresol resins, poly-p-vinylphenol resins, etc. , bisphenol A novolac resin, or modified products thereof.

The phenolic hydroxyl group contained in these phenolic resins can easily perform addition reaction with the epoxy group of the said epoxy resin by heating, and can form the cured product with high impact resistance. Therefore, an epoxy resin and a phenol resin can also be used together.

The adhesive polymer component is capable of providing appropriate viscosity to the adhesive film for semiconductors and improving the handling of the adhesive sheet for semiconductors. The mass average molecular weight of the binder polymer is usually in the range of 20,000 to 2 million, preferably 50,000 to 1.5 million, and most preferably 100,000 to 1 million. When the molecular weight is too low, film formation of the adhesive film for semiconductors becomes insufficient. When it is too high, compatibility with other components deteriorates, and as a result, formation of a uniform thin film is hindered. When the mass average molecular weight is in the range of 20,000 to 2 million, preferably in the range of 50,000 to 1.5 million, and most preferably in the range of 100,000 to 1 million, the thin film system of the adhesive film for semiconductors can be fully formed, and it is compatible with other components. Compatibility is also good and a uniform film can be formed. As such a binder polymer, for example, acrylic polymers, polyester resins, phenoxy resins, urethane resins, silicone resins, rubber-based polymers, and the like can be used. In particular, acrylic polymers can be suitably used. In addition, in this specification, "mass average molecular weight" is the polystyrene conversion value measured by the gel permeation chromatography (GPC) method, unless notified previously.

As an acrylic polymer, the (meth)acrylate copolymer which consists of an alkyl (meth)acrylate monomer, and the structural unit derived from another (meth)acrylic acid derivative is mentioned, for example. Here, as the alkyl (meth)acrylate monomer, preferably an alkyl (meth)acrylate having an alkyl group having 1 to 18 carbon atoms, for example, methyl (meth)acrylate, (meth) Ethyl acrylate, propyl (meth)acrylate, butyl (meth)acrylate, etc. Moreover, as a (meth)acrylic acid derivative, (meth)acrylic acid, glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate, etc. are mentioned, for example.

Among the above, when a glycidyl group is introduced into an acrylic polymer, the compatibility with the epoxy resin as the aforementioned thermosetting component is improved, and the glass transition temperature (Tg) after curing of the adhesive film for semiconductors becomes high and heat-resistant sexual enhancement. In addition, among the above, when a hydroxyl group is introduced into an acrylic polymer by using hydroxyethyl acrylate or the like as a structural unit, it is possible to control the adhesion and adhesive properties to a semiconductor.

When an acrylic polymer is used as the binder polymer, the mass average molecular weight of the polymer is preferably more than 100,000, particularly preferably 150,000 to 1 million. The glass transition temperature (Tg) of the acrylic polymer is generally below 40°C, preferably around -70 to 20°C. In this specification, the term "glass transition temperature (Tg)" means that the DSC curve of a sample is measured using a differential scanning calorimeter, and is represented by the inflection point temperature of the obtained DSC curve.

The blending ratio of the thermosetting component and the binder polymer component is relative to 100 parts by mass of the binder polymer component, and the thermosetting component is preferably 50-1500 parts by mass, and particularly preferably 70-1200 parts by mass. , it is better to mix 80~1000 parts by mass. When the thermosetting component and the binder polymer component are blended in such a ratio, the system exhibits appropriate viscosity before curing and can be stably attached, and after curing, a film with excellent film strength can be obtained.

The content of the thermosetting adhesive in the adhesive film for semiconductors of the present invention is preferably 20 to 75% by mass, more preferably 20 to 50% by mass, and 20 to 40% relative to the total mass of the adhesive film for semiconductors. Quality % is especially good. With respect to the total content of the thermosetting adhesive, the content of the thermosetting component is preferably 30-95% by mass, more preferably 40-95% by mass, and most preferably 40-92% by mass. Furthermore, the content of the binder polymer component relative to the total content of the thermosetting adhesive is preferably 5 to 70% by mass, more preferably 5 to 60% by mass, and most preferably 8 to 60% by mass. . However, the sum of the content of the thermosetting component and the content of the binder polymer component is not more than 100% by mass.

The adhesive film for semiconductors of the present invention may also contain a coupling agent. By using, as a coupling agent, a substance having a functional group reactive with an inorganic compound and a functional group reactive with an organic functional group, the adhesiveness and adhesion of the adhesive film for a semiconductor to an adherend can be improved. Moreover, by using the coupling agent, the water resistance can be improved without impairing the heat resistance of the cured product obtained by curing the adhesive film for semiconductors.

The coupling agent is preferably a compound having a functional group that reacts with a functional group of an acrylic polymer, epoxy resin, phenol resin, etc., and a silane coupling agent is preferred. As a preferable aforementioned silane coupling agent, γ-glycidoxypropyltrimethoxysilane (also known as 3-glycidoxypropyltrimethoxysilane), γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, Triethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-(methacryl Oxypropyl)trimethoxysilane, γ-aminopropyltrimethoxysilane, N-6-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-6-(aminoethyl)- γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-ureapropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane , γ-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyl Silane compounds such as trimethoxysilane, vinyltriacetyloxysilane, and imidazole silane, and hydrolyzed condensates of these silane compounds. A coupling agent may be used individually by 1 type, and may use 2 or more types together.

When using a coupling agent, the content of the coupling agent in the adhesive film for semiconductors is preferably 0.03-20 parts by mass, more preferably 0.05-10 parts by mass, based on 100 parts by mass of the total content of the thermosetting component and the binder polymer. , preferably 0.1 to 5 parts by mass. When the content of the coupling agent is too small, the above-mentioned effect by using the coupling agent may not be obtained, and when the content of the coupling agent is too large, there is a possibility of outgassing. By setting the content of the coupling agent within the above range, the adhesiveness and adhesion of the adhesive film for semiconductors to the adherend can be improved without generating outgassing, and the cured product obtained by curing the adhesive film for semiconductors will not be affected. Heat resistance does damage and enables water resistance.

(titanium oxide filler) The adhesive film for semiconductors of the present invention contains, with respect to the total mass of the adhesive film for semiconductors, 15% by mass to 70% by mass of titanium oxide filler, preferably 20% by mass to 70% by mass, preferably 20% by mass. More than 60 mass % is more preferable, and 30 mass % or more and 60 mass % are especially preferable. By making content of a titanium oxide filler more than the said minimum, the dielectric tangent of the adhesive film for semiconductors can be further reduced, and electromagnetic wave shielding property can be further improved.

The titanium oxide filler used in the adhesive film for semiconductor of the present invention can be anatase type, rutile type, or a mixture of anatase type and rutile type. In addition, in order to impart hydrophilicity or water repellency to titanium oxide particles, a surface-modified titanium oxide filler can also be used. The surface treatment can be either an inorganic surface treatment or an organic surface treatment.

The titanium oxide filler preferably has a granular shape. The average particle diameter of the titanium oxide filler is preferably not less than 10 nm and not more than 500 nm, more preferably not less than 30 nm and not more than 400 nm. By making the average particle diameter of the titanium oxide filler into the above-mentioned range, it becomes easier to adjust the dielectric tangent of the adhesive film for semiconductors.

The adhesive film for semiconductors of the present invention may contain general-purpose additives within the range that does not impair the effect of the present invention. General-purpose additives can be conventional ones, can be arbitrarily selected according to the purpose, and are not particularly limited. Examples of preferred ones include fillers other than titanium oxide, plasticizers, antioxidants, colorants (dyes, pigments), Degasser, etc.

Any of organic fillers and inorganic fillers (except titanium oxide) may be used as fillers other than titanium oxide. Inorganic fillers (except titanium oxide) are preferred. As preferred inorganic fillers, for example, powders of silicon oxide, aluminum oxide, talc, calcium carbonate, red iron oxide, silicon carbide, boron nitride, etc.; beads obtained by spheroidizing these inorganic fillers; Surface-modified products of inorganic fillers; single crystal fibers of such inorganic fillers; glass fibers, etc. Among them, the inorganic filler is preferably silicon oxide or aluminum oxide. The powder of silicon oxide (silica filler) may have a surface modifying group such as an organic group on its surface.

The filler other than titanium oxide preferably has a granular shape. The average particle size of fillers other than titanium oxide may be 1 nm to 25 μm, or 20 nm to 1000 nm, or 30 nm to 200 nm. The average particle diameter is a volume average diameter measured by a dynamic light scattering method using a particle size distribution measuring device.

The filler other than titanium oxide that can be contained in the adhesive film for a semiconductor may be only one type, or may be two or more types. When there are two or more types, the combination and ratio of these can be selected arbitrarily.

The dielectric tangent at 1 MHz of the adhesive film for semiconductors of the present invention after thermosetting is preferably 0.01 or less. When the dielectric constant at 1 MHz after thermal curing of the adhesive film for a semiconductor is not more than the aforementioned upper limit, the electromagnetic wave shielding properties can be further improved. Furthermore, the above-mentioned dielectric tangent system is preferably 0.0001 or more. The dielectric tangent at 1 MHz after thermosetting of the adhesive film for semiconductors of the present invention can be measured by the method described below.

The adhesive film for semiconductors may be composed of one layer (single layer), or may be composed of multiple layers of two or more layers. When the adhesive film for semiconductors is composed of multiple layers, the multiple layers may be the same as or different from each other. The combination of these plural layers will not be specifically limited unless the effect of this invention is impaired.

The thickness of the adhesive film for semiconductors is not particularly limited, but is preferably 1-100 μm, more preferably 3-40 μm. When the thickness of the adhesive film for semiconductors is more than the said lower limit, high adhesive force can be acquired with respect to the to-be-adhered objects, such as a semiconductor wafer. Moreover, when the thickness of the adhesive film for semiconductors is below the said upper limit, it can manufacture with a stable thickness. Here, the "thickness of the adhesive film for semiconductors" means the thickness of the entire adhesive film for semiconductors. For example, the thickness of an adhesive film for a semiconductor composed of a plurality of layers means the total thickness of all layers constituting the adhesive film for a semiconductor.

In this specification, "thickness" is the value indicated by the average of the thickness measured at five arbitrary places, which can be measured under the conditions of a sub-diameter of 5mm and a pressurized load of 1.22N using a constant pressure thickness measuring device in accordance with JIS K 6783:1994. Measured below.

The adhesive force (N/25mm) of the adhesive film for semiconductors before hardening to a semiconductor wafer can be measured using the following method. That is to manufacture a laminated sheet of adhesive film and adhesive tape for semiconductors with a width of 25 mm and an arbitrary length. This laminated sheet is what laminated|stacked the adhesive film for semiconductors on the adhesive surface of an adhesive tape. Next, use the adhesive film for semiconductors heated to 40~70°C, attach the laminated sheet to the semiconductor wafer, and laminate the adhesive tape, the adhesive film for semiconductors, and the semiconductor wafer sequentially. . Immediately after the manufactured laminate was left to stand in an environment of 23°C for 30 minutes, the laminated sheet of the adhesive film for semiconductors and the adhesive tape was separated from the semiconductor wafer, and the adhesive film for semiconductors and the semiconductor wafer were not in contact with each other. The so-called 180° peeling is performed at a peeling speed of 300mm/min in such a way that the angle between the faces is 180°. The peeling force at this time was measured, and the measured value was made into the adhesive force (N/25mm) of the adhesive film for semiconductors before hardening with respect to a semiconductor wafer. The length of the aforementioned laminated sheet for measurement is not particularly limited as long as the peeling force can be measured stably, but is preferably 100 to 300 mm.

The adhesive force of the adhesive film for semiconductor before hardening to the semiconductor wafer is preferably 100mN/25mm or more, for example, can be set to any one of 200mN/25mm or more, 300mN/25mm or more, but it is not limited thereto. Moreover, the upper limit of the said adhesive force is not specifically limited, For example, it can be selected from 10N/25mm, 800mN/25mm, 600mN/25mm etc., These are an example. For example, the above-mentioned adhesive force can be 100 mN/25 mm to 10 N/25 mm, 200 mN/25 mm to 800 mN/25 mm, 300 mN/25 mm to 600 mN/25 mm.

The adhesive force of the adhesive film for a semiconductor before curing to a semiconductor wafer can be appropriately adjusted by, for example, adjusting the type and amount of components contained in the adhesive film for a semiconductor. For example, the molecular weight of the binder polymer can be easily adjusted by adjusting the ratio of each monomer component constituting the binder polymer, the softening point of the thermosetting component, and the content of each component contained in the adhesive film for semiconductors. The aforementioned adhesion of adhesive films for semiconductors. But such adjustment method is only an example.

The shear strength of the adhesive film for semiconductors can be measured by the following method. Stick the adhesive film for semiconductor on the back of the silicon wafer with a thickness of 350μm and #2000 grinding and cut it into 2mm×2mm, pick up the silicon wafer with the adhesive film for semiconductor and stick it on the 30mm×2mm A copper plate with a thickness of 30 mm and a thickness of 300 μm was cured at 160° C. for 60 minutes to be a sample. The shear adhesion strength (N/2 mm×2 mm) of the sample was measured using a bond tester (Series 4000, manufactured by Dage). In addition, at the time of measurement, it held on the 250 degreeC hotplate for 30 seconds, and it measured at the load velocity of 0.2 mm/sec in this state.

The shear strength of the adhesive film for semiconductor is preferably 2N/(2mm×2mm) or more. When the shear strength of the adhesive film for semiconductors is 2N/(2mm×2mm) or more, the adhesiveness as the adhesive film for semiconductors is further excellent.

The adhesive film for semiconductors of the present invention can prepare a coating agent for adhesive films for semiconductors by mixing a thermosetting adhesive, a titanium oxide filler, and other above-mentioned additives and diluting them with an organic solvent such as ethyl acetate as necessary. , and it is manufactured by applying it to an adherend such as a release sheet and drying it.

The adhesive film for semiconductors of the present invention can be used as an adhesive film between a substrate and a semiconductor. Since the dielectric tangent of the adhesive film system for semiconductors of the present invention is low, interference with other semiconductor chips and devices can be suppressed, noise can be reduced, and electromagnetic wave shielding can be used.

The adhesive film for semiconductors of this embodiment is an adhesive film for semiconductors containing a thermosetting adhesive and a titanium oxide filler of 15% by mass to 70% by mass. Composition and binder polymer composition is preferred. As a thermosetting component, epoxy resin, phenolic resin and their mixtures are preferred, such as bisphenol-based glycidyl epoxy resin, o-cresol novolak epoxy resin, phenol novolak epoxy resin, etc. Resins and epoxy resins having a dicyclopentadiene skeleton are preferred. As the binder polymer component, an acrylic polymer is preferred. In addition, in the adhesive film for semiconductors according to this embodiment, it is preferable that the content of the thermosetting adhesive is 20% by mass to 75% by mass and the content of the titanium oxide filler is 20% by mass to 70% by mass. Preferably, the thermosetting adhesive content is more than 20% by mass and less than 75% by mass, and the titanium oxide filler content is more than 20% by mass and 60% by mass. The average particle diameter of the titanium oxide filler is preferably not less than 10 nm and not more than 500 nm.

[Adhesive sheets for semiconductors] The present invention provides an adhesive sheet for semiconductors in which the adhesive film for semiconductors of the present invention is provided on a release sheet. Fig. 1 is a cross-sectional view of an adhesive sheet for semiconductors according to an embodiment of the present invention. As shown in FIG. 1 , the adhesive sheet 2 for a semiconductor of this embodiment is constituted by including an adhesive film 1 for a semiconductor and a release sheet 21 . However, the peeling sheet 21 is peeled when the adhesive film 1 for semiconductors is used.

The release sheet 21 protects the adhesive film for a semiconductor until the adhesive film 1 for a semiconductor is used, and is not necessarily necessary. The structure of the peeling sheet 21 is optional, and examples include plastic films that are peelable from the adhesive film 1 for semiconductors, and plastic films that have been peeled using a release agent or the like. Specific examples of plastic films include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyester films such as polypropylene and polyethylene. Olefin film. As the release agent, polysiloxane-based, fluorine-based, long-chain alkyl-based, etc. can be used, and among them, polysiloxane-based, which is inexpensive and can provide stable performance, is preferable. The thickness of the release sheet 21 is not particularly limited, and is usually about 20 to 250 μm.

The release sheet 21 described above may be laminated on the surface opposite to the release sheet 21 of the adhesive film 1 for a semiconductor (the upper surface in FIG. 1 ). In this case, it is preferable to increase the peeling force of one release sheet 21 to be a heavy release die release sheet, and to reduce the release force of the other release sheet 21 to be a light release die release sheet.

To manufacture the adhesive sheet 2 for semiconductors of this embodiment, the adhesive film 1 for semiconductors is formed on the peeling surface of the peeling sheet 21 (the peeling surface; usually the peeling-treated surface, but not limited thereto). Specifically, a coating agent for an adhesive film for a semiconductor containing a thermosetting adhesive constituting the adhesive film for a semiconductor 1 is prepared, and a roll coater, a blade coater, a roll blade coater, an air blade coater, or a die coater is used. Coater, rod coater, gravure coater, curtain coater, etc., is applied to the release surface of the release sheet 21 and dried to form the adhesive film 1 for semiconductors.

The drying conditions of the coating agent for the adhesive film for semiconductors are not particularly limited. When the coating agent for the adhesive film for semiconductors contains an organic solvent such as ethyl acetate, it is better to make it dry by heating. It is better to dry it at 130°C for 10 seconds to 5 minutes.

(How to use adhesive sheets for semiconductors) The method of using the adhesive sheet 2 for semiconductors according to this embodiment will be described below with reference to FIG. 2 . The surface of the adhesive film 1 for semiconductors (the surface opposite to the release sheet 21) is used as the adhesive surface, and the adhesive sheet 2 for semiconductors is attached to the substrate 32. Next, after the release sheet 21 is peeled off from the adhesive sheet 2 for semiconductors, The semiconductor wafer 31 is attached to the surface of the semiconductor adhesive film 1 and the semiconductor adhesive film 1 is cured. [Example]

Hereinafter, the present invention will be described in more detail by specific examples. However, the present invention is not limited at all by the Examples shown below.

[Example 1] The following components were mixed at the compounding ratio (solid content conversion) shown in Table 1, and diluted with methyl ethyl ketone so that the solid content concentration became 60 mass %, and the coating agent for adhesive films for semiconductors was prepared. (a): Acrylic copolymer ("Teisanresin SG-P3" manufactured by NAGASE CHEMTEX) (b)-1: Bisphenol F-type epoxy resin ("jERY L983U" manufactured by Mitsubishi Chemical Corporation) (b)-2: Dicyclopentadiene skeleton epoxy resin ("XD-1000" manufactured by Nippon Kayaku Co., Ltd.) (c): o-cresol type novolak resin ("PHENOLITE KA-1160" manufactured by DIC Corporation) (d): Imidazole-based thermally active latent epoxy resin hardener ("CUREZOLE 2PHZ-PW" manufactured by Shikoku Chemical Industry Co., Ltd.) (e): Silane coupling agent ("X-41-1056" manufactured by Shin-Etsu Chemical Co., Ltd.) (f): Titanium oxide-containing filler ("DIMIC SZ 7030 WHITE" manufactured by Dainichi Seika Kogyo Co., Ltd., average particle diameter: 300 nm) (approximately 60% by mass of the total amount of titanium oxide-containing filler is titanium oxide) (g): Silica filler ("SC2050MA" manufactured by ADMATECHS, average particle size 0.5 μm)

After coating the above-mentioned coating agent for an adhesive film for semiconductors on a polyethylene terephthalate-based film release sheet (SP-PET381031, manufactured by Lintec Co., Ltd.) that has been subjected to release treatment on one side, dry it in an oven at 100°C for 1 minute. , to obtain an adhesive sheet for a semiconductor provided with a release sheet on an adhesive film for a semiconductor with a thickness of 30 μm.

[Example 2] An adhesive sheet for a semiconductor was manufactured in the same manner as in Example 1, except that the compounding amount of each component constituting the adhesive film for a semiconductor was changed as shown in Table 1.

[Comparative example 1, 2] An adhesive sheet for a semiconductor was manufactured in the same manner as in Example 1, except that the compounding amount of each component constituting the adhesive film for a semiconductor was changed as shown in Table 1.

[Comparative example 3, 4] In addition to using silicon oxide filler (g) [Admatechs Co., Ltd. "SC2050MA"; average particle size 0.5μm] instead of titanium oxide filler, and changing the compounding amount of each component constituting the semiconductor adhesive film as shown in Table 1, the same The adhesive sheet for semiconductors was manufactured in the same manner as in Example 1.

[Test example 1] <Dielectric tangent evaluation> After peeling off the release sheet from each of the adhesive sheets for semiconductors obtained in Examples 1, 2, and Comparative Examples 1 to 4, and laminating a plurality of adhesive films for semiconductors, the laminate was die-cut to obtain a test piece with a diameter of 10 mm and a thickness of 1 mm. piece. The test piece was hardened by heating in an oven at 160° C. for 1 hour. The dielectric tangent at 1 MHz was calculated in accordance with JIS C 2138 using 4194A manufactured by Hewlett-Packard. The results are shown in Table 1.

[Test Example 2] <Evaluation of Shear Strength> Adhesive film for semiconductors is attached to the back of silicon wafer with a thickness of 350 μm and #2000 grinding, and cut into 2mm×2mm. It was picked up together with the adhesive film for semiconductors, and the obtained silicon wafer with adhesive film for semiconductors was attached to a copper plate of 30mm×30mm and thickness 300μm and cured at 160°C for 60 minutes as a sample. The shear adhesive strength (N/(2mm×2mm)) of the sample was measured using an adhesive strength tester (Series 4000, manufactured by Dage Corporation). In addition, during the measurement, it was held on a hot plate at 250°C for 30 seconds, and in this state, it was measured at a load speed of 0.2 mm/sec. A shear strength of 2N/(2mm×2mm) or more was rated as ◯, and a shear strength of less than 2N/(2mm×2mm) was rated as ×. The results are shown in Table 1.

[Table 1]

As can be clearly seen from Table 1, the dielectric tangent of the adhesive films for semiconductors of Comparative Examples 1 and 2 of Comparative Examples 1 and 2 with a titanium oxide filler content of less than 15% by mass is greater than 0.01, and the examples with a titanium oxide filler content of 15% by mass or more The adhesive films for semiconductors of 1 and 2 have a dielectric tangent of 0.01 or less. Furthermore, both of the adhesive films for semiconductors of Examples 1 and 2 had good shear strength. In addition, the dielectric tangent of the adhesive films for semiconductors of Comparative Examples 3 and 4 in which silicon oxide fillers were used instead of titanium oxide fillers was greater than 0.01. Industrial availability

The adhesive film for semiconductors of the present invention has a low dielectric tangent at 1 MHz and has excellent electromagnetic wave shielding properties.

1‧‧‧Adhesive film for semiconductor 2‧‧‧Adhesive sheets for semiconductors 21‧‧‧Peeling sheet 3‧‧‧semiconductor device 31‧‧‧semiconductor chip 32‧‧‧substrate

Fig. 1 is a cross-sectional view of an adhesive sheet for a semiconductor according to an embodiment of the present invention. Fig. 2 is a cross-sectional view of a semiconductor device using an adhesive film for a semiconductor according to an embodiment of the present invention.

1‧‧‧Adhesive film for semiconductor

2‧‧‧Adhesive sheet for semiconductor

21‧‧‧Peeling sheet

Claims (2)

An adhesive film for semiconductors, which contains a thermosetting adhesive and 15% by mass to 70% by mass of titanium oxide filler, and has a dielectric tangent of 0.01 or less at 1 MHz after thermosetting. An adhesive sheet for semiconductors is provided with the adhesive film for semiconductors as described in item 1 of the scope of the patent application on the release sheet.

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