TW201925395A - 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 a semiconductor and an adhesive sheet for a semiconductor.
The present application claims priority based on Japanese Patent Application No. 2017-229522, filed on Jan.

An adhesive film for a semiconductor is used to fix a semiconductor wafer to a substrate and an electrode member. The lower the dielectric tangent of the adhesive film for a semiconductor, the more it is possible to suppress interference with other wafers and devices, and it is possible to reduce noise and to use shielding as 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 first semiconductor element to an adherend, and after heat curing The adhesive film having a dielectric constant of 1.40 or less at 1 MHz is capable of suppressing connection structure corrosion and conduction between wirings to manufacture a highly reliable semiconductor device.
Prior art document patent document

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

Problem to be solved by the invention

However, Patent Document 1 does not disclose at all the adhesive film for a semiconductor which reduces dielectric tangent and improves electromagnetic shielding properties by adding an inorganic filler.

Accordingly, an object of the present invention is to provide an adhesive film for a semiconductor which has a low dielectric tangent and excellent electromagnetic shielding properties.
Means to solve the problem

The present inventors have found that by adding 15% by mass or more and 70% by mass or less of titanium oxide to the thermosetting resin, it is possible to obtain an adhesive film for a semiconductor having low dielectric tangent after thermal curing and having excellent electromagnetic shielding properties. The present invention has been completed.
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 a semiconductor comprising a thermosetting adhesive and a titanium oxide filler in an amount of 15% by mass or more and 70% by mass or less.
[2] The adhesive film for a semiconductor according to [1], wherein a dielectric tangent at 1 MHz after heat curing is 0.01 or less.
[3] An adhesive sheet for a semiconductor, comprising the adhesive film for a semiconductor according to [1] or [2], which is provided on the release sheet.
Effect of the invention

According to the present invention, it is possible to provide an adhesive film for a semiconductor which has a low dielectric tangent after thermal curing and which has excellent electromagnetic shielding properties.

The adhesive film for a semiconductor of the present invention contains a thermosetting adhesive and a titanium oxide filler of 15% by mass or more and 70% by mass or less. In addition, the term "% by mass" as used herein means the ratio of the respective components when the adhesive film for a semiconductor is 100% by mass.

The adhesive film for a semiconductor of the present invention contains a titanium oxide filler of 15% by mass or more and 70% by mass or less, and can have a dielectric tangent and excellent electromagnetic wave shielding properties.

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

Examples of the thermosetting component include an epoxy resin, a phenol resin, a melamine resin, a urea resin, a polyimide resin, a benzoxazine resin, and the like, and a mixture thereof. Among these, an epoxy resin, a phenol resin, and the like can be suitably used.

The epoxy resin is three-dimensionally networked when heated, and has a property of forming a strong film. As such an epoxy resin, various conventional epoxy resins are conventionally used, and those having a molecular weight of about 200 to 2,000 are preferable, and those having a molecular weight of 300 to 500 are particularly preferable. Further, it is preferred to use an epoxy resin having a molecular weight of 310 to 400 and a normal state in a form of an epoxy resin having a molecular weight of 400 to 2,500, particularly 500 to 2,000, and a solid at room temperature. Further, the epoxy resin has an epoxy equivalent of from 50 to 5,000 g/eq.
In the present specification, the term "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.

Specific examples of such an epoxy resin include phenolic propyl ethers such as bisphenol A, bisphenol F, resorcinol, phenyl novolac, and cresol novolac; Epoxy propyl ether of alcohols such as diol, polyethylene glycol, polypropylene glycol; epoxidized propyl ether of carboxylic acid such as phthalic acid, isophthalic acid or tetrahydrophthalic acid; aniline heterotrimerization An epoxy resin such as a cyanide ester or the like which is substituted with an epoxy group or an alkyl epoxy group to bond an active hydrogen bonded to a nitrogen atom to an epoxy group or an alkyl epoxy group; for example, a vinyl ring Hexane diepoxide, 3,4-epoxycyclohexylmethyl-3,4-dicyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,5-spiro (3 a 4-cyclohexane) cyclohexane-m-dioxane or the like, which is obtained by, for example, oxidizing a carbon-carbon double bond in a molecule, and is introduced into an epoxy resin, and can also be used as an alicyclic epoxide. An epoxy resin such as a biphenyl skeleton, a dicyclopentadiene skeleton, a dicyclohexadiene skeleton, or a naphthalene skeleton.

Among these, a bisphenol-based epoxy propyl epoxy resin, an o-cresol novolac epoxy resin, a phenol novolak epoxy resin, and an epoxy resin having a dicyclopentadiene skeleton can be suitably used. These epoxy resins can be used alone or in combination of two or more.

When an epoxy resin is used, as the thermosetting adhesive, a thermally active latent epoxy resin hardener is preferably used in combination. The thermally active latent epoxy resin hardener is a type of hardener which does not react with an epoxy resin at room temperature and is activated by heating at a temperature or higher and reacts with an epoxy resin. A method for activating a heat-active latent epoxy resin hardener is a method in which a chemical reaction is carried out by heating and an active species (anion, a cation) is formed; and the epoxy resin is stably dispersed in the vicinity of room temperature. In addition, a method of dissolving at a high temperature and epoxy resin, a method of dissolving and starting a hardening reaction, a method of encapsulating a hardening agent of a molecular sieve and melting at a high temperature to start a hardening reaction, and a method using a microcapsule.

Specific examples of the thermally active latent epoxy resin hardener include high melting point activities of various onium salts, dibasic acid diterpenoids, dicyanodiamides, amine adduct hardeners, and imidazole compounds. Hydrogen compounds, etc. These thermally active latent epoxy resin hardeners can be used alone or in combination of two or more. The heat-activatable latent epoxy resin curing agent can be used in an amount of 0.1 to 20 parts by mass, particularly preferably 0.2 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, per 100 parts by mass of the epoxy resin. The ratio is used instead.

The phenol resin is not particularly limited, and a condensate of a phenol such as an alkylphenol, a polyhydric alcohol or a naphthol, and an aldehyde can be used. Specifically, a phenol novolak resin, an o-cresol novolak resin, a p-cresol novolak resin, a third butyl phenol novolak resin, a dicyclopentadiene cresol resin, a poly-p-vinylphenol resin can be used. A bisphenol A type novolak resin, or a modified product thereof.

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

The binder polymer component is capable of providing appropriate adhesion to the adhesive film for a semiconductor and improving the operability of the adhesive sheet for a semiconductor. The mass average molecular weight of the binder polymer is usually in the range of 20,000 to 2,000,000, preferably 50,000 to 1.5 million, and particularly preferably 100,000 to 1,000,000. When the molecular weight is too low, the film formation of the adhesive film for a semiconductor becomes insufficient. When it is too high, compatibility with other components is deteriorated, and as a result, formation of a uniform film is hindered. When the mass average molecular weight is in the range of 20,000 to 2,000,000, preferably 50,000 to 1.5 million, and particularly preferably in the range of 100,000 to 1,000,000, the film of the adhesive film for semiconductor can be sufficiently formed, and other components are used. The compatibility is also good and a uniform film can be formed. As such a binder polymer, for example, an acrylic polymer, a polyester resin, a phenoxy resin, a urethane resin, a polyoxyxylene resin, a rubber-based polymer or the like can be used. In particular, an acrylic polymer can be suitably used.
In addition, in the present specification, the "mass average molecular weight" is a polystyrene-converted value measured by a gel permeation chromatography (GPC) method unless otherwise notified.

Examples of the acrylic polymer include a (meth) acrylate copolymer composed of a (meth)acrylic acid alkyl ester monomer and a structural unit guided from another (meth)acrylic acid derivative. Here, as the alkyl (meth)acrylate monomer, an alkyl (meth)acrylate having an alkyl group having 1 to 18 carbon atoms is preferable, and for example, methyl (meth)acrylate or (methyl) can be used. Ethyl acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and the like. Further, examples of the (meth)acrylic acid derivative include (meth)acrylic acid, glycidyl (meth)acrylate, and hydroxyethyl (meth)acrylate.

In the above, when the epoxy propyl group is introduced into the acrylic polymer, the compatibility with the epoxy resin as the thermosetting component is improved, and the glass transition temperature (Tg) after curing of the adhesive film for a semiconductor is high and heat resistant. Sexual improvement. In addition, when hydroxyethyl acrylate or the like is used as a structural unit and a hydroxyl group is introduced into the acrylic polymer, the adhesion to the semiconductor and the adhesive property can be controlled.

When an acrylic polymer is used as the binder polymer, the mass average molecular weight of the polymer is preferably 100,000 or more, particularly preferably 150,000 to 1,000,000. The glass transition temperature (Tg) of the acrylic polymer is usually 40 ° C or lower, preferably about -70 to 20 ° C.
In the present specification, the "glass transition temperature (Tg)" is a DSC curve of a sample measured by a differential scanning calorimeter and expressed by the inflection point temperature of the obtained DSC curve.

The blending ratio of the thermosetting component to the binder polymer component is formulated to be a thermosetting component, preferably 50 to 1500 parts by mass, particularly preferably 70 to 1200 parts by mass, based on 100 parts by mass of the binder polymer component. It is better to mix 80 to 1000 parts by mass. When the thermosetting component and the binder polymer component are blended in such a ratio, an appropriate viscosity is obtained before curing, and the bonding operation can be stably performed, and a film having excellent film strength can be obtained after curing.

The content of the thermosetting adhesive for the adhesive film for a semiconductor of the present invention is preferably 20 to 75% by mass, more preferably 20 to 50% by mass, and 20 to 40% by mass based on the total mass of the adhesive film for a semiconductor. The mass % is particularly good.
The content of the thermosetting component is preferably from 30 to 95% by mass, preferably from 40 to 95% by mass, particularly preferably from 40 to 92% by mass, based on the total amount of the thermosetting adhesive. Further, the content of the binder polymer component relative to the total content of the thermosetting adhesive is preferably 5 to 70% by mass, preferably 5 to 60% by mass, and particularly 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 a semiconductor of the present invention may further contain a coupling agent. By using a functional group having a reaction with an inorganic compound and a functional group reactive with an organic functional group as a coupling agent, the adhesion and adhesion of the adhesive film for a semiconductor to an adherend can be improved. Further, by using a coupling agent, the heat resistance of the cured product obtained by curing the adhesive film for a semiconductor is not impaired, and the water resistance can be improved.

The coupling agent is preferably a compound having a functional group reactive with a functional group possessed by an acrylic polymer, an epoxy resin, a phenol resin or the like, and preferably a decane coupling agent.
As the preferred decane coupling agent, γ-glycidoxypropyltrimethoxydecane (also referred to as 3-glycidoxypropyltrimethoxydecane) and γ-glycidoxypropane can be exemplified. Triethoxy decane, γ-glycidoxypropylmethyldiethoxy decane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-(methacryl oxime Oxypropyl)trimethoxydecane, γ-aminopropyltrimethoxydecane, N-6-(aminoethyl)-γ-aminopropyltrimethoxydecane, N-6-(aminoethyl)- γ-Aminopropylmethyldiethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane, γ-ureidopropyltriethoxydecane, γ-Hydroxypropyltrimethoxydecane , γ-hydrothiopropylmethyldimethoxydecane, bis(3-triethoxydecylpropyl)tetrasulfane, methyltrimethoxydecane, methyltriethoxydecane, vinyl a decane compound such as trimethoxy decane, vinyl triethoxy decane or imidazolium, or a hydrolysis condensate of the decane compound.
The coupling agent may be used alone or in combination of two or more.

When a coupling agent is used, the coupling agent content of the adhesive film for a semiconductor is preferably from 0.03 to 20 parts by mass, preferably from 0.05 to 10 parts by mass, based on 100 parts by mass of the total of the thermosetting component and the binder polymer. It is particularly good at 0.1 to 5 parts by mass. When the content of the coupling agent is too small, there is a case where the above effect by using a coupling agent cannot be obtained, and when the amount of the coupling agent is too large, there is a possibility that exhaust gas is generated. When the content of the coupling agent is in the above range, the exhaust gas is not generated, and the adhesion and adhesion of the adhesive film for a semiconductor to the adherend can be improved, and the cured product obtained by curing the adhesive film for a semiconductor is not obtained. Heat resistance causes damage and can improve water resistance.

(titanium oxide filler)
The adhesive film for a semiconductor of the present invention contains a titanium oxide filler in an amount of 15% by mass or more and 70% by mass or less based on the total mass of the adhesive film for a semiconductor, preferably 20% by mass or more and 70% by mass or less, and preferably 20% by mass or less. The above is preferably 60% by mass or less, and particularly preferably 30% by mass or more and 60% by mass. By setting the content of the titanium oxide filler to the above lower limit or more, the dielectric tangent of the adhesive film for a semiconductor can be further lowered, and the electromagnetic wave shielding property can be further improved.

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

The titanium oxide filler is preferably a granular shape. The average particle diameter of the titanium oxide filler is preferably 10 nm or more and 500 nm or less, and more preferably 30 nm or more and 400 nm or less. By setting the average particle diameter of the titanium oxide filler to the above range, the adjustment of the dielectric tangent of the adhesive film for a semiconductor becomes easier.

The adhesive film for a semiconductor of the present invention may contain a general-purpose additive insofar as the effects of the present invention are not impaired.
The general-purpose additive can be arbitrarily selected according to the purpose, and is not particularly limited. Examples of the preferred product include a filler other than titanium oxide, a plasticizer, an antioxidant, a colorant (dye, pigment), and Degassing agent, etc.

The filler other than titanium oxide may be any of an organic filler and an inorganic filler (except for titanium oxide). It is preferred to use an inorganic filler (except for titanium oxide). Examples of preferred inorganic fillers include powders of cerium oxide, aluminum oxide, talc, calcium carbonate, iron oxide red, cerium carbide, and boron nitride; and beads obtained by spheroidizing the inorganic fillers; A surface modification of an inorganic filler; a single crystal fiber of the inorganic filler; a glass fiber or the like. Among these, the inorganic filler is preferably cerium oxide or aluminum oxide. The powder of cerium oxide (cerium oxide filler) may have a surface-modified group such as an organic group on the surface thereof.

The filler other than titanium oxide is preferably a granular shape. The filler other than titanium oxide may have an average particle diameter of 1 nm to 25 μm, may be 20 nm to 1000 nm, or may be 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 the titanium oxide which can be contained in the adhesive film for semiconductors may be used alone or in combination of two or more. When two or more types are used, the combinations and ratios can be arbitrarily selected.

The adhesive film for a semiconductor of the present invention is preferably cured at a dielectric tangential of 1 MHz or less after thermal curing. When the dielectric constant at 1 MHz is thermally hardened by the adhesive film for a semiconductor, the electromagnetic wave shielding property can be further improved. Further, the dielectric tangent system is preferably 0.0001 or more. The dielectric tangent system at 1 MHz after the adhesive film for a semiconductor of the present invention is thermally cured can be measured by the method described later.

The adhesive film for a semiconductor may be composed of one layer (single layer) or a plurality of layers of two or more layers. When the adhesive film for a semiconductor is composed of a plurality of layers, the plurality of layers may be the same or different. The combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.

The thickness of the adhesive film for a semiconductor is not particularly limited, and is preferably 1 to 100 μm, more preferably 3 to 40 μm. When the thickness of the adhesive film for a semiconductor is at least the above lower limit value, a high adhesive force can be obtained for an adherend such as a semiconductor wafer. Moreover, the thickness of the adhesive film for a semiconductor is less than or equal to the above upper limit value, and it can be manufactured with a stable thickness.
Here, the "thickness of the adhesive film for a semiconductor" means the thickness of the entire adhesive film for a semiconductor. For example, the thickness of the adhesive film for a semiconductor formed of a plurality of layers means the total thickness of all the layers constituting the adhesive film for a semiconductor.

In the present specification, the "thickness" is a value obtained by measuring the average thickness at any five points, and it is possible to use a constant pressure thickness measuring device according to JIS K 6783:1994, and to measure a sub-diameter of 5 mm and a press load of 1.22 N. The measurement was carried out.

The adhesion (N/25 mm) of the adhesive film for semiconductor before curing to the semiconductor wafer can be measured by the following method.
That is, a laminated sheet of an adhesive film for a semiconductor and an adhesive tape having a width of 25 mm and a length is prepared. This laminated sheet is formed by laminating an adhesive film for a semiconductor on the adhesive surface of the adhesive tape. Next, a laminate for a semiconductor adhesive film which is heated to 40 to 70 ° C is used for production, and the laminate is attached to a semiconductor wafer to laminate the adhesive tape, the semiconductor adhesive film, and the semiconductor wafer in this order. . After the manufactured laminate was allowed to stand in an environment of 23 ° C for 30 minutes, the laminated film for the adhesive film for the semiconductor and the adhesive tape were not brought into contact with each other from the semiconductor wafer, the adhesive film for the semiconductor, and the semiconductor wafer. The surface was formed to have an angle of 180° and peeled off at a peeling speed of 300 mm/min to perform so-called 180° peeling. The peeling force at this time was measured, and the measured value was made into the adhesive force (N/25 mm) of the semiconductor adhesive film before hardening to the semiconductor wafer. The length of the laminated sheet to be measured is not particularly limited as long as the range of the peeling force can be stably measured, and is preferably 100 to 300 mm.

The adhesion of the adhesive film for a semiconductor to the semiconductor wafer before curing is preferably 100 mN/25 mm or more, and may be, for example, 200 mN/25 mm or more and 300 mN/25 mm or more, but is not limited thereto.
Further, the upper limit of the adhesive force is not particularly limited, and for example, it can be selected from 10N/25 mm, 800 mN/25 mm, 600 mN/25 mm, etc., but these are examples.
For example, the adhesive force can be 100 mN/25 mm or more and 10 N/25 mm or less, 200 mN/25 mm or more, 800 mN/25 mm or less, 300 mN/25 mm or more, and 600 mN/25 mm or less.

The adhesion of the adhesive film for a semiconductor before the hardening to the semiconductor wafer can be appropriately adjusted by, for example, adjusting the type and amount of the component 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 of the adhesive film for a semiconductor. The aforementioned adhesion of the adhesive film for semiconductors. But these adjustment methods are just an example.

The shear strength of the adhesive film for a semiconductor can be measured by the following method. The adhesive film for semiconductor was attached to the back surface of a ruthenium wafer having a thickness of 350 μm and #2000, and cut into 2 mm × 2 mm, and the ruthenium wafer with the adhesive film for semiconductor obtained by picking up the adhesive film for semiconductor was attached at 30 mm × A copper plate of 30 mm and a thickness of 300 μm was allowed to harden at 160 ° C for 60 minutes as 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 Co., Ltd.). Further, the measurement was carried out on a hot plate at 250 ° C for 30 seconds, and in this state, the measurement was carried out at a load rate of 0.2 mm / sec.

The shear strength of the adhesive film for a semiconductor is preferably 2 N/(2 mm × 2 mm) or more. The adhesive strength of the adhesive film for a semiconductor is 2 N/(2 mm × 2 mm) or more, and the adhesion to the adhesive film for a semiconductor is more excellent.

The adhesive film for a semiconductor of the present invention can be prepared by mixing a thermosetting adhesive, a titanium oxide filler, and other additives, and diluting with an organic solvent such as ethyl acetate as necessary to prepare a coating agent for an adhesive film for a semiconductor. Further, it is applied to an adherend such as a release sheet, and then dried to be produced.

In the adhesive film for a semiconductor of the present invention, an adhesive film which is a substrate and a semiconductor can be used. Since the adhesive film for a semiconductor of the present invention has a low dielectric tangent, it is possible to suppress interference with other semiconductor wafers and devices, and it is possible to reduce noise and to use shielding as electromagnetic waves.

The adhesive film for a semiconductor of the present embodiment contains a thermosetting adhesive and a titanium oxide filler having a titanium oxide filler of 15% by mass or more and 70% by mass or less, and contains a thermosetting adhesive as a thermosetting adhesive. The composition and the binder polymer component are preferred. As the thermosetting component, an epoxy resin, a phenol resin, and the like are preferable, and a bisphenol-based epoxy propyl epoxy resin, an o-cresol novolac epoxy resin, and a phenol novolak epoxy resin are preferable. A resin and an epoxy resin having a dicyclopentadiene skeleton are preferred. As the binder polymer component, an acrylic polymer is preferred.
In the adhesive film for a semiconductor of the present embodiment, the content of the thermosetting adhesive is 20% by mass or more and 75% by mass or less, and the content of the titanium oxide filler is preferably 20% by mass or more and 70% by mass or less. The content of the thermosetting adhesive is 20% by mass or more and 75% by mass or less, and the content of the titanium oxide filler is preferably 20% by mass or more and 60% by mass. The average particle diameter of the titanium oxide filler is preferably 10 nm or more and 500 nm or less.

[Semiconductor Adhesive Sheet]
The present invention provides an adhesive sheet for a semiconductor provided with an adhesive film for a semiconductor of the present invention on a release sheet. Fig. 1 is a cross-sectional view showing an adhesive sheet for a semiconductor according to an embodiment of the present invention. As shown in FIG. 1, the adhesive sheet 2 for a semiconductor of the present embodiment is provided with an adhesive film 1 for a semiconductor and a release sheet 21. However, the release sheet 21 is peeled off when the adhesive film for semiconductor 1 is used.

The release sheet 21 is used to protect the semiconductor adhesive film during the period from the use of the adhesive film for semiconductor 1 , and is not necessarily required. The structure of the release sheet 21 is arbitrarily exemplified, and a plastic film having a peeling property to the adhesive film 1 for a semiconductor itself and a plastic film obtained by peeling off a plastic film using a release agent can be exemplified. Specific examples of the plastic film include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polycondensation of polypropylene, polyethylene, and the like. Olefin film. As the release agent, a polyfluorene-based, a fluorine-based or a long-chain alkyl group can be used, and among these, a polyoxyl system which is inexpensive and can provide stable performance is preferable. The thickness of the release sheet 21 is not particularly limited, but is usually about 20 to 250 μm.

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

In the adhesive sheet 2 for a semiconductor of the present embodiment, the adhesive film 1 for a semiconductor is formed on the peeling surface of the release sheet 21 (the surface having the releasability; the surface to be subjected to the peeling treatment is usually not limited thereto). Specifically, a coating agent for a semiconductor adhesive film containing a thermosetting adhesive constituting the adhesive film for a semiconductor 1 is prepared, and a roll coater, a knife coater, a roll coater, a pneumatic blade coater, and a die coat are used. A coating machine such as a machine, a bar coater, a gravure coater, or a curtain coater is applied to the peeling surface of the release sheet 21 and dried to form an adhesive film 1 for a semiconductor.

The drying condition of the coating agent for an adhesive film for a semiconductor is not particularly limited, and when the coating agent for an adhesive film for a semiconductor contains an organic solvent such as ethyl acetate, it is preferably heated and dried, and in this case, for example, at 70~ It is preferably dried at 130 ° C for 10 seconds to 5 minutes.

(How to use the adhesive sheet for semiconductors)
A method of using the semiconductor adhesive sheet 2 of the present embodiment will be described below with reference to Fig. 2 . The surface of the adhesive film for semiconductor 1 (the surface opposite to the peeling sheet 21) is used as an adhesive surface, and the adhesive sheet 2 for semiconductor is attached to the substrate 32. Next, after the release sheet 21 is peeled off from the adhesive sheet 2 for a semiconductor, The semiconductor wafer 31 is attached to the surface of the semiconductor-adhesive film 1 and the semiconductor adhesive film 1 is cured.
[Examples]

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

[Example 1]
Each of the following components was mixed in the mixing ratio (solid content) shown in Table 1, and diluted with methyl ethyl ketone so that the solid content became 60% by mass to prepare a coating agent for an adhesive film for a semiconductor.
(a): Acrylic copolymer ("Teisanresin SG-P3" by NAGASE CHEMTEX"
(b)-1: bisphenol F type epoxy resin ("jERY L983U" manufactured by Mitsubishi Chemical Co., Ltd.)
(b)-2: Dicyclopentadiene skeleton epoxy resin ("XD-1000" manufactured by Nippon Kayaku Co., Ltd.)
(c): o-cresol novolac resin ("PHENOLITE KA-1160" manufactured by DIC Corporation)
(d): Imidazole-based thermal active latent epoxy resin hardener (CUREZOLE 2PHZ-PW, manufactured by Shikoku Chemicals Co., Ltd.)
(e): decane coupling agent ("X-41-1056" manufactured by Shin-Etsu Chemical Co., Ltd.)
(f): a filler containing titanium oxide ("DIMIC SZ 7030 WHITE" manufactured by Daisei Seiki Co., Ltd., average particle diameter: 300 nm) (about 60% by mass of the total amount of the filler containing titanium oxide is titanium oxide)
(g): cerium oxide filler ("SC2050MA" manufactured by ADMATECHS Co., Ltd., average particle size 0.5 μm)

The coating film for a semiconductor adhesive film was applied onto a release sheet (SP-PET381031, manufactured by LINTEC Co., Ltd.) of a polyethylene terephthalate film which was subjected to a release treatment, and then dried in an oven at 100 ° C for 1 minute. In the adhesive film for a semiconductor having a thickness of 30 μm, a semiconductor adhesive sheet on a release sheet was obtained.

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

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

[Comparative Examples 3 and 4]
In addition to using a cerium oxide filler (g) [SC2050MA" manufactured by ADMATECHS Co., Ltd.; an average particle diameter of 0.5 μm) instead of the titanium oxide filler, the amount of each component constituting the adhesive film for a semiconductor is changed as shown in Table 1. An adhesive sheet for a semiconductor was produced in the same manner as in Example 1.

[Test Example 1] <Dielectric Tangent Evaluation>
The release sheet was peeled off from each of the semiconductor adhesive sheets obtained in Examples 1 and 2 and Comparative Examples 1 to 4, and a plurality of adhesive films for a semiconductor were laminated, and then the laminate was die-cut to obtain a test having a diameter of 10 mm and a thickness of 1 mm. sheet. The test piece was heat-hardened in an oven at 160 ° C for 1 hour. A dielectric tangent of 1 MHz was calculated in accordance with JIS C 2138 using 4194A manufactured by Hewlett-Packard Co., Ltd. The results are shown in Table 1.

[Test Example 2] <Evaluation of Shear Strength>
The adhesive film for semiconductor was attached to the back surface of a ruthenium wafer having a thickness of 350 μm and #2000 and cut into 2 mm × 2 mm. The film was picked up together with an adhesive film for a semiconductor, and the obtained semiconductor wafer with an adhesive film for semiconductor was attached to a copper plate of 30 mm × 30 mm and a thickness of 300 μm, and cured at 160 ° C for 60 minutes as a sample. The shear adhesion strength (N/(2 mm × 2 mm)) of the sample was measured using a bonding strength tester (Series 4000, manufactured by Dage Co., Ltd.). Further, the measurement was carried out on a hot plate at 250 ° C for 30 seconds, and in this state, the load rate was measured at 0.2 mm / sec. Those having a shear strength of 2 N/(2 mm × 2 mm) or more were evaluated as ○, and those having a shear strength of less than 2 N/(2 mm × 2 mm) were evaluated as ×. The results are shown in Table 1.

[Table 1]

As can be seen from Table 1, the adhesive films for semiconductors of Comparative Examples 1 and 2 having a titanium oxide filler content of less than 15% by mass have an dielectric tangent of more than 0.01 and 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. Further, any of the adhesive films for semiconductors of Examples 1 and 2 had good shear strength.
Further, the adhesive films for semiconductors of Comparative Examples 3 and 4 in which the cerium oxide filler was used instead of the titanium oxide filler had a dielectric tangent of more than 0.01.
Industrial availability

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

1‧‧‧Adhesive film for semiconductors

2‧‧‧Semiconductor adhesive sheets

21‧‧‧ peeling film

3‧‧‧Semiconductor device

31‧‧‧Semiconductor wafer

32‧‧‧Substrate

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

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

Claims (3)

An adhesive film for a semiconductor comprising a thermosetting adhesive and a titanium oxide filler in an amount of 15% by mass or more and 70% by mass or less. The adhesive film for a semiconductor according to claim 1, wherein the dielectric tangent at 1 MHz after heat curing is 0.01 or less. An adhesive sheet for a semiconductor, comprising the adhesive film for a semiconductor according to claim 1 or 2, which is provided on the release sheet.