TW201723119A - Adhesive sheet - Google Patents

Abstract

Disclosed is an adhesive sheet (10) that is used at the time of sealing a semiconductor element on the adhesive sheet, the adhesive sheet (10) comprising: a substrate (11); an adhesive agent layer (12) including an adhesive agent; and an oligomer sealing layer (13) provided between the substrate (11) and the adhesive agent layer (12).

Description

Adhesive sheet

The present invention relates to adhesive sheets.

Various characteristics are required for the adhesive sheet used in the manufacturing steps of the semiconductor device. In recent years, it has been required for the adhesive sheet to not contaminate the device, the member, and the adherend used in the manufacturing step even after the step of applying the high temperature condition. Further, when the adhesive sheet is peeled off at room temperature after the step of high-temperature conditions, it is required that the residual adhesive (such as residual glue) of the adherend or the like is small and the peeling force is small.

For example, JP-A-2002-275435 discloses a mask sheet for a semiconductor package in which a QFN (Quad Flat Non-lead) is stably produced to suppress the adhesive of the adhesive. In Document 1, it is described that a mask sheet can be produced by using a specific heat-resistant film and a polyoxygen-based adhesive, and can withstand the die bonding step and the resin sealing step at 150 ° C to 180 ° C for 1 hour to 6 hours. surroundings.

In recent years, an adhesive sheet has been used even in the step of applying a high temperature condition of, for example, 180 ° C or more and 200 ° C or less. In such a high temperature step, for example, a film having a low heat resistance and a low price such as a polyimide film is used (for example) When a film such as polyethylene terephthalate or the like is used as a substrate, it is understood that the surface of the adherend is contaminated when the adhesive sheet is peeled off by the adherend after the end of the step. The reason for such contamination is that the low molecular weight component (oligomer) contained in the resin film as the substrate is deposited on the surface of the adherend. For example, when a high temperature condition is applied to a step of resin sealing a semiconductor element attached to an adhesive layer of an adhesive sheet, the surface of the semiconductor element is contaminated, which may cause a defect in the semiconductor device.

SUMMARY OF THE INVENTION An object of the present invention is to provide an adhesive sheet which can be prevented from being contaminated by the surface of an adherend even after a step of applying a high temperature condition.

According to an aspect of the present invention, there is provided an adhesive sheet which is used for sealing a semiconductor element on an adhesive sheet, comprising a substrate, an adhesive layer containing an adhesive, and a substrate disposed on the substrate An oligomer sealing layer between the aforementioned adhesive layers.

In the adhesive sheet according to an aspect of the invention, the oligomer sealing layer is preferably obtained by curing an epoxy compound, a polyester compound, and a composition for an oligomer sealing layer of a polyfunctional amine-based compound. Harden the film.

In the adhesive sheet according to one aspect of the invention, the composition for an oligomer sealing layer preferably contains (A) 50% by mass or more and 80% by mass or less of a bisphenol A type epoxy compound, and (B) 5 mass. A polyester compound having a % or more and 30% by mass or less and (C) a polyfunctional amino compound of 10% by mass or more and 40% by mass or less.

In the adhesive sheet of one aspect of the invention, the storage modulus of the substrate at 100 ° C is preferably 1 × 10 ⁷ Pa or more.

In the adhesive sheet according to one aspect of the invention, the pressure-sensitive adhesive layer preferably contains an acrylic pressure-sensitive adhesive composition or a polyoxygen-based pressure-sensitive adhesive composition.

In the adhesive sheet according to one aspect of the invention, the acrylic pressure-sensitive adhesive composition preferably contains an acrylic copolymer containing 2-ethylhexyl acrylate as a main monomer.

In the adhesive sheet according to an aspect of the invention, the polyfluorene-based pressure-sensitive adhesive composition preferably contains an addition polymerization type polyoxynoxy resin.

In an adhesive sheet according to an aspect of the invention, it is preferred that the oligomer sealing layer is provided on both sides of the substrate.

In the adhesive sheet according to an aspect of the invention, the substrate preferably contains a polyester resin.

According to the present invention, it is possible to provide an adhesive sheet which can be prevented from being contaminated by the surface of the adherend even after the step of applying a high temperature condition.

10, 10A‧‧‧ adhesive sheet

11‧‧‧Substrate

11a‧‧‧First substrate surface

11b‧‧‧Second substrate surface

12‧‧‧Adhesive layer

13‧‧‧ oligomer sealing layer

20‧‧‧Box components

21‧‧‧ openings

30‧‧‧ Sealing resin

30A‧‧‧ sealing resin layer

40‧‧‧Reinforcing components

41‧‧‧ reinforcing plate

42‧‧‧Next layer

50‧‧‧ Sealing body

CP‧‧‧Semiconductor wafer

Fig. 1 is a schematic cross-sectional view showing an adhesive sheet of the first embodiment.

Fig. 2A is a view for explaining a part of a manufacturing process of a semiconductor device using the adhesive sheet of the first embodiment.

Fig. 2B is a view for explaining a part of a manufacturing procedure of a semiconductor device using the adhesive sheet of the first embodiment.

Fig. 2C is a view for explaining a part of a manufacturing process of the semiconductor device using the adhesive sheet of the first embodiment.

Fig. 2D is a view showing a part of a manufacturing procedure of a semiconductor device using the adhesive sheet of the first embodiment.

Fig. 2E is a view showing a part of a manufacturing procedure of a semiconductor device using the adhesive sheet of the first embodiment.

Fig. 3 is a schematic cross-sectional view showing an adhesive sheet of a second embodiment.

[First Embodiment] (adhesive sheet)

Fig. 1 is a schematic cross-sectional view showing an adhesive sheet 10 of the present embodiment.

The adhesive sheet 10 has a substrate 11, an adhesive layer 12, and an oligomer sealing layer 13.

The base material 11 has a first base material surface 11a and a second base material surface 11b on the side opposite to the first base material surface 11a. An oligomer sealing layer 13 is provided between the substrate 11 and the adhesive layer 12. In the adhesive sheet 10, it is preferable that the oligomer sealing layer 13 is laminated on the first substrate surface 11a, and the first substrate surface 11a is covered with the oligomer sealing layer 13.

The shape of the adhesive sheet 10 can be any shape such as a sheet shape, a belt shape, or a label shape.

(substrate)

The substrate 11 is a member that supports the adhesive layer 12 and the oligomer sealing layer 13.

As the substrate 11, for example, a sheet material such as a synthetic resin film can be used. Wait. Examples of the synthetic resin film include a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, and polyethylene terephthalate. Ester film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate copolymer film, ionic polymer resin film, ethylene / (methyl) An acrylic copolymer film, an ethylene/(meth)acrylate copolymer film, a polystyrene film, a polycarbonate film, and a polyimide film. Other examples of the substrate 11 include a crosslinked film and a laminated film.

The base material 11 preferably contains a polyester resin, and more preferably is made of a material containing a polyester resin as a main component. In the present specification, the material containing the polyester resin as a main component means that the ratio of the mass of the polyester resin in the entire mass of the material constituting the substrate is 50% by mass or more.

The polyester resin is preferably selected, for example, from polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, and Any resin of the group of the copolymerized resins of these resins; more preferably a polyethylene terephthalate resin.

The substrate 11 is preferably a polyethylene terephthalate film or a polyethylene naphthalate film; more preferably a polyethylene terephthalate film. The oligomer contained in the polyester film is derived from a polyester-forming monomer, a dimer, a trimer or the like.

The lower limit of the storage modulus of the substrate 11 at 100 ° C is preferably 1 × 10 ⁷ Pa or more, and more preferably 1 × 10 ⁸ Pa or more from the viewpoint of dimensional stability during processing. The upper limit of the storage modulus of the substrate 11 at 100 ° C is preferably 1 × 10 ¹² Pa or less from the viewpoint of process suitability. Further, in the present specification, the storage modulus is a value measured by a torsional shear method at a frequency of 1 Hz using a dynamic viscoelasticity measuring device. The substrate to be measured was cut into a width of 5 mm and a length of 20 mm, and a storage viscoelasticity at 100 ° C was measured using a viscoelasticity measuring apparatus (manufactured by TA Instruments, DMAQ800) at a frequency of 1 Hz and a stretching mode.

The first base material surface 11a may be subjected to at least one surface treatment such as a primer treatment, a corona treatment, and a plasma treatment in order to improve the adhesion to the oligomer sealing layer 13. The adhesive treatment may be applied to the first substrate surface 11a of the substrate 11 by applying an adhesive. Examples of the adhesive used for the adhesion treatment of the substrate include an adhesive such as an acrylic, a rubber, a polyoxygen, or an urethane.

The thickness of the substrate 11 is preferably 10 μm or more and 500 μm or less, more preferably 15 μm or more and 300 μm or less, and still more preferably 20 μm or more and 250 μm or less.

(adhesive layer)

The adhesive layer 12 of the present embodiment contains an adhesive composition. The adhesive contained in the adhesive composition is not particularly limited, and various types of adhesives can be applied to the adhesive layer 12. Examples of the adhesive contained in the pressure-sensitive adhesive layer 12 include a rubber-based, acrylic-based, polyoxy-oxygen-based, polyester-based, and urethane-based adhesive. Further, the type of the adhesive is selected in consideration of the use and the type of the adherend to be attached. The adhesive layer 12 preferably contains an acrylic adhesive composition or a polyoxynitride adhesive composition.

. Acrylic adhesive composition

When the adhesive layer 12 contains an acrylic pressure-sensitive adhesive composition, the acrylic pressure-sensitive adhesive composition preferably contains an acrylic copolymer containing 2-ethylhexyl acrylate as a main monomer.

Further, when the adhesive layer 12 contains an acrylic adhesive composition, it preferably contains an acrylic copolymer and an adhesion aid. The acrylic copolymer is preferably a copolymer containing 2-ethylhexyl acrylate as a main monomer. The adhesion aid preferably contains a rubber-based material having a reactive group as a main component.

In the present specification, 2-ethylhexyl acrylate as a main monomer means that the mass ratio of the copolymer component derived from 2-ethylhexyl acrylate in the entire mass of the acrylic copolymer is 50% by mass or more. In the present embodiment, the ratio of the copolymer component derived from 2-ethylhexyl acrylate in the acrylic copolymer is preferably 50% by mass or more and 95% by mass or less, more preferably 60% by mass or more and 95% by mass or less. More preferably, it is 80% by mass or more and 95% by mass or less, and more preferably 85% by mass or more and 93% by mass or less. When the ratio of the copolymer component derived from 2-ethylhexyl acrylate is 50% by mass or more, the adhesive force after heating does not become excessively high, and the adhesive sheet is more likely to be peeled off by the adherend, and is 80% by mass or more. It is easier to peel off. When the ratio of the copolymer component derived from 2-ethylhexyl acrylate is 95% by mass or less, it is possible to prevent the base material from being deformed at the time of heating due to insufficient initial adhesion, or to peel off the adhesive sheet from the adherend due to the deformation.

The type and number of the copolymer components other than 2-ethylhexyl acrylate in the acrylic copolymer are not particularly limited. For example, as the second copolymer component, a functional group-containing monomer having a reactive functional group is preferred. Make When the reactive functional group of the second copolymer component is used, when a crosslinking agent described later is used, a functional group reactive with the crosslinking agent is preferred. The reactive functional group is preferably at least any one selected from the group consisting of a carboxyl group, a hydroxyl group, an amine group, a substituted amine group, and an epoxy group; more preferably at least one of a carboxyl group and a hydroxyl group. More preferably, it is a carboxyl group.

The monomer having a carboxyl group (monomer containing a carboxyl group) may, for example, be an ethylenically unsaturated carboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, isaconic acid or citraconic acid. Among the carboxyl group-containing monomers, acrylic acid is preferred from the viewpoint of reactivity and copolymerizability. The monomer having a carboxyl group may be used singly or in combination of two or more.

Examples of the monomer having a hydroxyl group (a monomer having a hydroxyl group) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate. Methyl)2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate, and hydroxyalkyl (meth)acrylate such as 4-hydroxybutyl (meth)acrylate. Among the hydroxyl group-containing monomers, 2-hydroxyethyl (meth)acrylate is preferred from the viewpoint of reactivity of the hydroxyl group and copolymerization property. The hydroxyl group-containing monomer may be used singly or in combination of two or more. In the present specification, "(meth)acrylic acid" means the expression used in the case of "acrylic acid" and "methacrylic acid", and the other similar terms are also the same.

Examples of the acrylate having an epoxy group include glycidyl acrylate and glycidyl methacrylate.

The other copolymer component in the acrylic copolymer may, for example, be an alkyl (meth)acrylate having an alkyl group having 2 to 20 carbon atoms. (meth)acrylic acid alkyl ester, For example, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, methyl 2-ethylhexyl acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, myristyl (meth)acrylate, (A) Base) acrylate palmitate, and stearyl (meth) acrylate. Among these alkyl (meth)acrylates, in view of further improving the adhesion, a (meth) acrylate having an alkyl group having 2 to 4 carbon atoms is preferred, and more preferably (meth) acrylate. N-butyl ester. The alkyl (meth)acrylate may be used singly or in combination of two or more.

The other copolymer component in the acrylic copolymer may, for example, be derived from a (meth) acrylate selected from an alkoxyalkyl group, a (meth) acrylate having an aliphatic ring, and an aromatic ring (A). At least one of a group of acrylate, non-crosslinkable acrylamide, (meth) acrylate having a non-crosslinkable tertiary amino group, vinyl acetate, and styrene Copolymer component.

Examples of the (meth) acrylate containing an alkoxyalkyl group include methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, and ethoxymethyl (meth)acrylate. And ethoxyethyl (meth)acrylate.

The (meth) acrylate having an aliphatic ring may, for example, be cyclohexyl (meth)acrylate.

Examples of the (meth) acrylate having an aromatic ring include phenyl (meth) acrylate.

Examples of the non-crosslinkable acrylamide include acrylamide and methacrylamide.

Examples of the (meth) acrylate having a non-crosslinkable tertiary amino group include (N,N-dimethylamino)ethyl (meth)acrylate and (meth)acrylic acid (N, N). -Dimethylamino)propyl ester.

The other copolymer component in the acrylic copolymer is preferably a copolymer component derived from a monomer having a ring containing a nitrogen atom from the viewpoint of improving the polarity of the adhesive and improving the adhesion and adhesion.

The monomer having a ring containing a nitrogen atom may, for example, be N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpiperidone, N-vinylpiperazine, N- Vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinylmorpholine, N-vinylcaprolactam, and N-(methyl)propenylmorpholine. The monomer having a ring containing a nitrogen atom is preferably N-(methyl)propenylmorpholine.

These monomers may be used singly or in combination of two or more.

In the present embodiment, the second copolymer component is preferably a carboxyl group-containing monomer or a hydroxyl group-containing monomer, more preferably acrylic acid. When the acrylic copolymer contains a copolymer component derived from 2-ethylhexyl acrylate and a copolymer component derived from acrylic acid, the ratio of the mass of the copolymer component derived from acrylic acid is preferably 1 in the total mass of the acrylic copolymer. The mass% or less is more preferably 0.1% by mass or more and 0.5% by mass or less. When the ratio of the acrylic acid is 1% by mass or less, when the crosslinking agent is contained in the adhesive composition, crosslinking of the acrylic copolymer can be prevented from proceeding too quickly.

The acrylic copolymer may further contain a copolymer component derived from two or more kinds of functional group-containing monomers. For example, the acrylic copolymer may be a ternary copolymer. When the acrylic copolymer is a ternary copolymer, it is preferably An acrylic copolymer obtained by copolymerizing 2-ethylhexyl acrylate, a carboxyl group-containing monomer, and a hydroxyl group-containing monomer, and the carboxyl group-containing monomer is preferably acrylic acid or a hydroxyl group-containing monomer. It is 2-hydroxyethyl acrylate. In the acrylic copolymer, the ratio of the copolymer component derived from 2-ethylhexyl acrylate is preferably 80% by mass or more and 95% by mass or less, and the mass ratio of the copolymer component derived from acrylic acid is 1% by mass or less. The remainder is the copolymer component from 2-hydroxyethyl acrylate.

The weight average molecular weight (Mw) of the acrylic copolymer is preferably 300,000 or more and 2,000,000 or less, more preferably 600,000 or more and 1.5,000,000 or less, still more preferably 800,000 or more and 1.2,000,000 or less. When the weight average molecular weight Mw of the acrylic copolymer is 300,000 or more, peeling can be performed without the residue of the adhesive on the adherend. When the weight average molecular weight Mw of the acrylic copolymer is 2,000,000 or less, the adherend can be reliably attached.

The weight average molecular weight Mw of the acrylic copolymer is a standard polystyrene equivalent value measured by a Gel Permeation Chromatography (GPC) method.

The acrylic copolymer can be produced by using a conventional raw material by using various raw material monomers as described above.

The copolymerization form of the acrylic copolymer is not particularly limited, and may be any of a block copolymer, a random copolymer, or a graft copolymer.

In the present embodiment, the content of the acrylic copolymer in the adhesive composition is preferably 40% by mass or more and 90% by mass or less, more preferably 50% by mass or more and 90% by mass or less.

The adhesion aid preferably contains a rubber-based material having a reactive group as a main component. If the adhesive composition contains a reactive adhesion aid, the residual glue can be reduced. The content of the adhesion aid in the adhesive composition is preferably 3% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 30% by mass or less. When the content of the adhesion aid in the adhesive composition is 3% by mass or more, generation of residual glue can be suppressed, and if it is 50% by mass or less, the decrease in adhesion can be suppressed.

In the present specification, the rubber-based material having a reactive group as a main component means that the mass ratio of the rubber-based material having a reactive group exceeds 50% by mass in the total mass of the adhesive auxiliary. In the present embodiment, the ratio of the rubber-based material having a reactive group in the adhesion aid is preferably more than 50% by mass, more preferably 80% by mass or more. It is also preferred that the adhesion aid consists essentially of a rubber-based material having a reactive group.

The reactive group is preferably one or more functional groups selected from the group consisting of a hydroxyl group, an isocyanate group, an amine group, an oxiranyl group, an acid anhydride group, an alkoxy group, an acryloyl group, and a methacryl group. More preferably, it is a hydroxyl group. The reactive group of the rubber-based material may be one type or two or more types. The rubber-based material having a hydroxyl group may further have the aforementioned reactive group. In addition, the number of the reactive groups may be one or two or more in one molecule constituting the rubber-based material.

The rubber-based material is not particularly limited, but is preferably a hydrogenated product of a polybutadiene-based resin and a polybutadiene-based resin, and more preferably a hydrogenated product of a polybutadiene-based resin.

The polybutadiene-based resin may, for example, be a resin having a 1,4-repeat unit. A resin having 1,2-repeat units and a resin having both 1,4-repeat units and 1,2-repeat units. The hydrogenated product of the polybutadiene resin of the present embodiment also contains a hydrogenated product of a resin having such repeating units.

The hydrogenated product of the polybutadiene resin and the polybutadiene resin preferably has a reactive group at both ends. The reactive groups at both ends may be the same or different. The reactive group at both ends is preferably one or more selected from the group consisting of a hydroxyl group, an isocyanate group, an amine group, an oxirane group, an acid anhydride group, an alkoxy group, an acrylonitrile group, and a methacryl group. Functional group; more preferably hydroxyl. In the hydride of the polybutadiene-based resin and the polybutadiene-based resin, it is more preferred that both ends are hydroxyl groups.

In addition to the acrylic copolymer and the adhesion aid, the adhesive composition of the present embodiment further preferably contains a crosslinked product obtained by crosslinking a composition of the blended crosslinking agent. Moreover, it is preferable that the solid content of the adhesive composition is substantially composed of the above-mentioned acrylic copolymer, an adhesion aid, and a crosslinked product obtained by crosslinking the crosslinking agent. Here, substantially, it means that the solid component of the adhesive composition is composed only of the crosslinked product except for a trace amount of impurities which are inevitably mixed in the adhesive.

In the present embodiment, examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, a metal clamp crosslinking agent, an amine crosslinking agent, and an amine group. Resin crosslinking agent. These crosslinking agents may be used singly or in combination of two or more.

In the present embodiment, from the viewpoint of improving heat resistance and adhesion of the adhesive composition, among these crosslinking agents, a crosslinking agent containing a compound having an isocyanate group as a main component (isocyanate crosslinking) is particularly preferable. Agent) good. Examples of the isocyanate crosslinking agent include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylene diisocyanate, 1,4-strylene diisocyanate, and diphenylmethane-4. 4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4 A polyisocyanate compound such as '-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, and isocyanuric acid isocyanate.

Further, the polyisocyanate compound may be a trimethylolpropane adduct type modified body of the above compound, a biuret type modified body which reacts with water, or a trimer isocyanate type modified with a trimerized isocyanate ring. body.

In the present specification, the crosslinking agent having a compound having an isocyanate group as a main component means that the mass of the compound having an isocyanate group accounts for 50% by mass or more of the total mass of the components constituting the crosslinking agent.

In the present embodiment, the content of the crosslinking agent in the adhesive composition is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more, based on 100 parts by mass of the acrylic copolymer. 15 parts by mass or less, more preferably 5 parts by mass or more and 10 parts by mass or less. If the content of the crosslinking agent in the adhesive composition is within such a range, the adhesion of the layer (adhesive layer) containing the adhesive composition to the adherend (for example, the substrate) can be improved, and the adhesive sheet can be shortened. The ripening period used to stabilize the adhesive properties after manufacture.

In the present embodiment, the isocyanate crosslinking agent is more preferably a compound having a trimeric isocyanate ring (trimeric isocyanate type modified body) from the viewpoint of heat resistance of the adhesive composition. Trimeric isocyanate ring The compound is preferably blended in an amount of 0.7 equivalent or more and 1.5 equivalent or less based on the hydroxyl equivalent of the acrylic copolymer. When the blending amount of the compound having a trimeric isocyanate ring is 0.7 equivalent or more, the adhesive force after heating does not become too high, and the adhesive sheet is easily peeled off, and the residual glue can be reduced. When the blending amount of the compound having a trimeric isocyanate ring is 1.5 equivalent or less, the initial adhesive strength can be prevented from becoming too low or the adhesion can be prevented from being lowered.

When the adhesive composition of the present embodiment contains a crosslinking agent, the adhesive composition preferably further contains a crosslinking accelerator. The crosslinking accelerator is preferably selected and used in accordance with the type of the crosslinking agent or the like. For example, when the adhesive composition contains a polyisocyanate compound as a crosslinking agent, it is preferred to further contain an organic metal compound-based crosslinking accelerator such as an organic tin compound.

. Polyoxygenated adhesive composition

When the adhesive layer 12 contains a polyoxynitride-based adhesive composition, the polyoxygen-based adhesive composition preferably contains an addition polymerization type polyoxyxylene resin. In the present specification, a polyfluorene-based pressure-sensitive adhesive composition containing an addition polymerization type polyoxyxylene resin is referred to as an addition reaction type polyoxo-based pressure-sensitive adhesive composition.

The addition reaction type polyoxo-based adhesive composition contains a main component and a crosslinking agent. The addition reaction type polyoxo-based adhesive composition is used only for primary hardening at a low temperature, and does not require the secondary hardening at a high temperature. Incidentally, the conventional peroxide-curable polyfluorene-based adhesive must be hardened twice at a high temperature of, for example, 150 ° C or higher.

Therefore, by using an addition reaction type polyoxo-based adhesive composition, an adhesive sheet can be produced at a relatively low temperature, which is excellent in energy economy and can also be used. The adhesive sheet 10 is produced from the substrate 11 having low heat resistance. Further, since no by-products are generated during curing as in the case of a peroxide-curable polyfluorene-based adhesive, there is no problem such as odor or corrosion.

The addition reaction type polyoxo-based adhesive composition is usually composed of a main component composed of a mixture of a polyoxyxylene resin component and a polyoxyxylene rubber component, and a crosslinking agent containing a hydroquinone alkyl group (SiH group). And a hardening catalyst used as needed.

The polyoxyxylene resin component is an organic polyoxane having a network structure obtained by subjecting an organochlorosilane or an organoalkoxysilane to hydrolysis by a dehydration condensation reaction.

The polyoxyxene rubber component is a diorganopolyoxyalkylene having a linear structure.

As the organic group, the polyoxyxylene resin component and the polyoxyxylene rubber component are each a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group or the like. A part of the aforementioned organic group is substituted with, for example, a vinyl group, a hexenyl group, an allyl group, a butenyl group, a pentenyl group, an octenyl group, a (meth) acrylonitrile group, a (meth) acryl fluorenylmethyl group, (Methyl) acrylonitrile, and an unsaturated group of cyclohexenyl. An organic group having a vinyl group which is industrially easy to obtain is preferred. In the addition reaction type polyoxo-based adhesive composition, crosslinking reaction proceeds by an addition reaction of an unsaturated group with a hydroquinone group to form a network structure, and exhibits adhesiveness.

The number of unsaturated groups such as a vinyl group is usually 0.05 or more and 3.0 or less, preferably 0.1 or more and 2.5 or less, based on 100 parts of the organic group. By reducing the number of unsaturation groups relative to 100 organic groups to 0.05 or more, the reactivity with the hydroquinone group can be prevented from being lowered. It is difficult to harden and imparts moderate adhesion. When the number of unsaturated groups per 100 organic groups is 3.0 or less, the crosslinking density of the adhesive is prevented from becoming high, and the adhesive force and the cohesive force are increased, which adversely affects the adhered surface.

The organic polyoxane as described above is specifically KS-3703 manufactured by Shin-Etsu Chemical Co., Ltd. (the number of vinyl groups is 0.6 with respect to 100 methyl groups), Toray. Dow Corning's BY23-753 (with respect to 100 methyl groups, the number of vinyl groups is 0.1) and BY24-162 (with respect to 100 methyl groups, the number of vinyl groups is 1.4). Also, you can also use Toray. Dow Corning's SD4560PSA, SD4570PSA, SD4580PSA, SD4584PSA, SD4585PSA, SD4587L, and SD4592PSA.

As described above, the organopolysiloxane of the polyoxyxylene resin component is usually used in combination with a polyoxyxene rubber component, and the polyoxyxene rubber component is KS-3800 (relative to methyl group) manufactured by Shin-Etsu Chemical Co., Ltd. 100, the number of vinyl is 7.6), Toray. Dow Corning's BY24-162 (1.4 with respect to methyl 100), BY24-843 (without unsaturated groups) and SD-7292 (relative to 100 methyl groups) The number of vinyl groups is 5.0) and the like.

A specific example of the above-described addition reaction type polyfluorene is described in, for example, Japanese Laid-Open Patent Publication No. Hei 10-219229.

One of the vinyl group-like unsaturated groups of the polyoxyxylene resin component and the polyoxyxylene rubber component is usually 0.5 or more and 10 or less hydrogen atoms bonded to the ruthenium atom, and is preferably More than 1 and 2.5 The crosslinking agent is blended in the following manner. When the amount is 0.5 or more, the reaction between the unsaturated group such as a vinyl group and the hydroquinone group is prevented from proceeding completely, and the curing failure is prevented. When the amount is 10 or less, the crosslinking agent is prevented from remaining unreacted, and the surface to be adhered is adversely affected.

The addition reaction type polyoxo-based adhesive composition is preferably accompanied by the addition reaction type polyoxo component (the main component composed of the polyoxyxylene resin component and the polyoxymethylene rubber component), and cross-linking The agent together contains a hardening catalyst.

The hardening catalyst is used to promote the hydroquinonelation reaction of the unsaturated group in the polyoxyxylene resin component and the polyoxyxylene rubber component with the Si-H group in the crosslinking agent.

The hardening catalyst may be a platinum-based catalyst, that is, a platinum chloride acid, an alcohol solution of a platinum chloride acid, a reaction product of a platinum chloride acid and an alcohol solution, a reaction of a platinum chloride acid with an olefin compound, and a chlorination. A reaction of a platinum acid with a vinyl group-containing oxane compound, a platinum-olefin complex, a platinum-vinyl group-containing alkane complex, and a platinum-phosphorus complex. Specific examples of the above-mentioned curing catalyst are disclosed in, for example, JP-A-2006-28311 and JP-A-10-147758.

More specifically, as a commercial item, Toray can be cited. SRX-212 manufactured by Dow Corning Corporation and PL-50T manufactured by Shin-Etsu Chemical Co., Ltd.

The blending amount of the curing catalyst is usually 5 ppm by mass or more and 2000 ppm by mass or less, preferably 10 ppm by mass, based on the total amount of the polyoxyxylene resin component and the polyoxyxylene rubber component in terms of the platinum component. Above 500 ppm by mass or less. When the amount is 5 ppm by mass or more, the curing property is prevented from decreasing, and the crosslinking density is lowered, that is, the adhesion and the cohesive force (retention force). When it is reduced to 2,000 ppm by mass or less, the cost can be prevented from increasing, and the stability of the adhesive layer can be maintained, and the excessively used hardening catalyst can be prevented from adversely affecting the adhered surface.

In the addition-reactive polyoxo-based adhesive composition, the adhesion is exhibited even at normal temperature by blending the above-mentioned respective components, but the addition reaction type is preferred from the viewpoint of the stability of adhesion. The polyoxygen-based adhesive composition is applied to the substrate 11 or a release sheet described later, and after bonding the substrate 11 and the release sheet, the active energy ray is heated or irradiated to promote the polymerization of the polyoxymethylene resin component and the polymerization agent by the crosslinking agent. The helium oxide rubber component undergoes a crosslinking reaction.

The heating temperature at the time of promoting the crosslinking reaction by heating is usually 60° C. or higher and 140° C. or lower, preferably 80° C. or higher and 130° C. or lower. By heating at 60 ° C or higher, the crosslinking between the polyoxyxylene resin component and the polyoxyxene rubber component is insufficient, and the adhesive force is insufficient. By heating at 140 ° C or lower, heat shrinkage wrinkles can be prevented from occurring on the substrate sheet. Deterioration, or discoloration.

When the active energy ray is irradiated to promote the crosslinking reaction, an active energy ray having an energy quantum, that is, an active light such as an ultraviolet ray or an electron beam or the like can be used among the electromagnetic wave or the charged particle beam. When the electron beam is irradiated and crosslinked, the photopolymerization initiator is not required, but when the active light such as ultraviolet rays is irradiated for crosslinking, it is preferred to have a photopolymerization initiator present.

The photopolymerization initiator which is used in the case of irradiating ultraviolet rays is not particularly limited, and any photopolymerization initiator which is conventionally used for the ultraviolet curable resin can be appropriately selected and used. The photopolymerization initiator may, for example, be a benzoin, a benzophenone, an acetophenone, an α-hydroxyketone, an α -aminoketone, an α -diketone or an α-diketone Alkyl acetals, anthraquinones, thioxanthones, other compounds, and the like.

These photopolymerization initiators may be used singly or in combination of two or more. In addition, the amount thereof is usually 0.01 parts by mass or more and 30 parts by mass or less, preferably 100 parts by mass or less based on 100 parts by mass of the total of the addition reaction type polyfluorene oxygen component and the crosslinking agent used as the main component. It is selected in the range of 0.05 part by mass or more and 20 parts by mass or less.

By crosslinking by heating or irradiating the active energy ray, an adhesive sheet having a firm adhesive force can be obtained.

The acceleration voltage of the electron beam when the electron beam is irradiated by one of the active energy rays is generally 130 kV or more and 300 kV or less, preferably 150 kV or more and 250 kV or less. By irradiating with an accelerating voltage of 130 kV or more, it is possible to prevent insufficient crosslinking between the polyoxyxylene resin component and the polyoxyxene rubber component, and the adhesion is insufficient, and the adhesion can be prevented by irradiation with an accelerating voltage of 300 kV or less. The agent layer and the substrate sheet are deteriorated or discolored. The beam current preferably has a range of 1 mA or more and 100 mA or less.

The radiation dose of the electron beam to be irradiated is preferably 1 Mrad or more and 70 Mrad or less, more preferably 2 Mrad or more and 20 Mrad or less. By irradiating with a radiation dose of 1 Mrad or more, deterioration or discoloration of the adhesive layer and the substrate sheet can be prevented, and insufficient adhesion can be prevented to cause insufficient adhesion. By irradiating with a radiation dose of 70 Mrad or less, it is possible to prevent the adhesion force due to deterioration or discoloration of the adhesive layer from being lowered, and to prevent deterioration or shrinkage of the substrate sheet.

The amount of irradiation at the time of ultraviolet irradiation is appropriately selected, and the amount of light is 100 mJ/cm ² or more and 500 mJ/cm ² or less, and the illuminance is 10 mW/cm ² or more and 500 mW/cm ² or less.

Heating and irradiation of the active energy ray are preferably carried out in a nitrogen atmosphere in order to prevent oxygen from hindering the reaction.

The thickness of the adhesive layer 12 is appropriately determined depending on the use of the adhesive sheet 10. In the present embodiment, the thickness of the adhesive layer 12 is preferably 5 μm or more and 60 μm or less, more preferably 10 μm or more and 50 μm or less. When the thickness of the adhesive layer 12 is too thin, the adhesive layer 12 cannot follow the unevenness of the circuit surface of the semiconductor wafer, and there is a gap. For example, the interlayer insulating material, the sealing resin, and the like enter the gap, and the electrode pads for wiring connection of the wafer circuit surface are blocked. When the thickness of the adhesive layer 12 is 5 μm or more, the adhesive layer 12 easily follows the unevenness of the surface of the chip circuit, and the occurrence of a gap can be prevented. Further, when the thickness of the adhesive layer 12 is too thick, the semiconductor wafer is sunk into the adhesive layer to cause a step difference between the semiconductor wafer portion and the resin portion of the sealed semiconductor wafer. If such a step is generated, there is a problem that the wiring is broken when wiring. When the thickness of the adhesive layer 12 is 60 μm or less, a step difference is less likely to occur.

In the present embodiment, the adhesive composition may contain other components insofar as the effects of the present invention are not impaired. Examples of other components which may be contained in the adhesive composition include organic solvents, flame retardants, tackifiers, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, preservatives, antifungal agents, and plasticizers. Defoamers, colorants, fillers, and wetting regulators.

The addition reaction type polyoxo-based adhesive composition may also contain, as an additive, a non-reactive polyorganosiloxane such as polydimethyl siloxane and polymethylphenyl siloxane.

(oligomer sealing layer)

The oligomer sealing layer 13 is a layer for preventing penetration of a low molecular weight component (oligomer) into the adhesive layer 12. When the adhesive sheet 10 is exposed to a high temperature condition, it is considered that the oligomer contained in the substrate 11 is deposited on the surface of the substrate 11 by heating, and when the oligomer sealing layer 13 is not provided, the adhesive is infiltrated. Layer 12, and in turn through adhesive layer 12, reaches the surface of adhesive layer 12. The oligomer sealing layer 13 preferably prevents penetration of the oligomer into the adhesive layer 12 even under high temperature conditions of 180 ° C or higher and 200 ° C or lower.

The material of the oligomer sealing layer 13 is not particularly limited as long as it can prevent the oligomer from penetrating into the adhesive layer 12.

For example, the oligomer sealing layer 13 is preferably obtained by hardening a composition containing an (A) epoxy compound, (B) a polyester compound, and (C) a polyfunctional amine-based compound oligomer sealing layer. Harden the film. In order to promote the hardening reaction, the composition for the oligomer sealing layer may further contain (D) an acidic catalyst.

. (A) epoxy compound

The (A) epoxy compound is preferably a bisphenol A type epoxy compound. Examples of the bisphenol A type epoxy compound include bisphenol A diglycidyl ether. The weight average molecular weight (Mw) of the bisphenol A type epoxy compound is preferably 1 × 10 ⁴ or more and 5 × 10 ⁴ or less. When the weight average molecular weight (Mw) of the bisphenol A type epoxy compound is 1 × 10 ⁴ or more, the crosslinking density required for the film can be obtained, and the precipitation of the oligomer can be easily prevented. When the weight average molecular weight (Mw) is 5 × 10 ⁴ or less, the film can be prevented from becoming too hard. The weight average molecular weight Mw is a standard polystyrene equivalent value measured by a gel permeation chromatography (GPC) method.

. (B) Polyester compound

The (B) polyester compound is not particularly limited and may be appropriately selected from among the known polyester compounds. The polyester compound is specifically a resin obtained by a condensation reaction of a polyhydric alcohol and a polybasic acid, and examples thereof include a condensate of a dibasic acid and a glycol or a compound which is modified by a non-drying oil fatty acid or the like. A conversion polyester compound and a condensate of a dibasic acid and a trivalent or higher alcohol, that is, a conversion polyester compound. In the present embodiment, these polyester compounds can be used.

Examples of the polyol used as the raw material of the (B) polyester compound include a diol, a triol, and a quaternary or higher polyhydric alcohol.

Examples of the glycol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, and neopentyl glycol.

Examples of the triol include glycerin, trimethylolethane, and trimethylolpropane.

Examples of the quaternary or higher polyhydric alcohol include diglycerin, triglycerin, pentaerythritol, dipentaerythritol, mannitol, and sorbitol.

The polyols may be used alone or in combination of two or more.

Examples of the polybasic acid include an aromatic polybasic acid, an aliphatic saturated polybasic acid, an aliphatic unsaturated polybasic acid, and a polybasic acid formed by a Diels-Alder reaction.

Examples of the aromatic polybasic acid include phthalic anhydride and terephthalic acid. Acid, isophthalic acid, and trimellitic anhydride.

Examples of the aliphatic saturated polybasic acid include succinic acid, adipic acid, and sebacic acid.

Examples of the aliphatic unsaturated polybasic acid include maleic acid, maleic anhydride, fumaric acid, isaconic acid, and citraconic anhydride.

Examples of the polybasic acid formed by the Dimes-Alder reaction include a cyclopentadiene-maleic anhydride adduct, a terpene-maleic anhydride adduct, and a rosin-maleic anhydride adduct.

The polybasic acid may be used singly or in combination of two or more.

Examples of the non-drying oil fatty acid of the modifier include octanoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linoleic acid, oleic acid, ricinoleic acid, and dehydrated ricinoleic acid. Or coconut oil, linseed oil, tung oil, castor oil, dehydrated castor oil, soybean oil, safflower oil, and the like. These modifiers may be used alone or in combination of two or more. Further, the polyester compound may be used alone or in combination of two or more.

(B) The polyester compound preferably has an active hydrogen group as a base point of the crosslinking reaction. Examples of the active hydrogen group include a hydroxyl group, a carboxyl group, and an amine group. The polyester compound is particularly preferably a hydroxyl group. The hydroxyl value of the polyester compound is preferably 5 mgKOH/g or more and 500 mgKOH/g or less, more preferably 10 mgKOH/g or more and 300 mgKOH/g or less.

The number average molecular weight (Mn) of the (B) polyester compound is preferably 500 or more and 10,000 or less, more preferably 1,000 or more and 5,000 or less. The aforementioned number average molecular weight is a standard determined by gel permeation chromatography (GPC). Polystyrene converted value.

(B) The glass transition temperature Tg of the polyester compound is preferably 0 ° C or more and 50 ° C or less.

By using a polyester compound having a number average molecular weight (Mn) and a glass transition temperature Tg in the above range, moderate flexibility can be imparted to the cured film forming the oligomer sealing layer 13. The glass transition temperature Tg was measured in accordance with JIS K 7121 using an input-compensated differential scanning calorimeter at a temperature range of -80 ° C to 250 ° C to determine the glass transition temperature Tg.

. (C) polyfunctional amine compounds

(C) A polyfunctional amine-based compound, for example, a melamine compound, a urea compound, a benzoguanamine compound, and a diamine can be used.

Examples of the melamine compound include hexamethoxymethyl melamine, a methylated melamine compound, and a butylated melamine compound.

Examples of the urea compound include a methylated urea compound and a butylated urea compound.

Examples of the benzoguanamine compound include a methylated benzoguanamine compound and a butylated benzoguanamine compound.

Examples of the diamines include ethylenediamine, tetramethylenediamine, hexamethylenediamine, N,N'-diphenylethylenediamine, and p-xylenediamine.

From the viewpoint of hardenability, as the (C) polyfunctional amine-based compound, hexamethoxymethylmelamine is preferred.

. (D) Acid catalyst

Examples of the acidic catalyst (D) include hydrochloric acid and p-toluenesulfonic acid.

. Hardened film

In the present embodiment, the oligomer sealing layer 13 is preferably (A) 50% by mass or more and 80% by mass or less, (B) 5% by mass or more and 30% by mass or less, and (C) 10% by mass. The above blending ratio of 40% by mass or less contains (A) a bisphenol A type epoxy compound, (B) a polyester compound, and (C) a polyfunctional amine group compound, and the oligomer sealing layer composition is cured. The hardened film obtained. When the (D) acidic catalyst is blended in the composition for the oligomer sealing layer, the content of the component (D) is preferably 1% by mass or more and 5% by mass or less.

When the cured film obtained by curing the composition for the oligomer sealing layer having the blending ratio in the above range is used, the effect of preventing the penetration of the oligomer into the adhesive layer 12 by the oligomer sealing layer 13 can be enhanced.

. Film thickness of the oligomer sealing layer

The thickness of the oligomer sealing layer 13 is preferably 50 nm or more and 500 nm or less, more preferably 80 nm or more and 300 nm or less. When the thickness of the oligomer sealing layer 13 is 50 nm or more, the penetration of the oligomer into the adhesive layer 12 can be effectively prevented. When the thickness of the oligomer sealing layer 13 is 500 nm or less, the adhesive sheet 10 is wound around the core material in a roll shape. Examples of the material of the core material include paper, plastic, and metal.

The adhesive sheet 10 of the present embodiment preferably exhibits the following adhesive force after heating. First, attach the adhesive sheet 10 to the adherend (copper foil or The polyimide film is heated at 100 ° C for 30 minutes, then heated at 180 ° C for 30 minutes, and further heated at 190 ° C for 1 hour, and the adhesive layer 12 is copper at room temperature. The adhesion of the foil and the adhesion of the adhesive layer 12 to the polyimide film at room temperature are preferably 0.7 N/25 mm or more and 2.0 N/25 mm or less, respectively. When the adhesion after such heating is 0.7 N/25 mm or more, when the substrate or the adherend is deformed by heating, the adhesive sheet 10 can be prevented from being peeled off from the adherend. Further, when the adhesive force after heating is 2.0 N/25 mm or less, the peeling force does not become excessively high, and the adhesive sheet 10 is easily peeled off from the adherend. In the present specification, the room temperature means a temperature of 22 ° C or more and 24 ° C or less. In the present specification, the adhesive force is a value measured by a 180° peeling method at a tensile speed of 300 mm/min and a width of the adhesive sheet of 25 mm.

(Method of manufacturing adhesive sheet)

The manufacturing method of the adhesive sheet 10 is not specifically limited.

For example, the adhesive sheet 10 is produced by the following steps.

First, a composition for an oligomer sealing layer is applied onto the first substrate surface 11a of the substrate 11 to form a coating film. Next, the coating film is heated and cured to form a cured film as the oligomer sealing layer 13. The conditions of heat hardening are, for example, 120 ° C or more and 170 ° C or less, 5 seconds or more and 5 minutes or less.

Next, an adhesive composition is applied onto the oligomer sealing layer 13 to form a coating film. Next, the coating film is dried to form an adhesive layer 12.

Coating the oligomer sealing layer composition to form the oligomer sealing layer 13 In the case where the adhesive layer 12 is formed by applying the adhesive composition, the composition for the oligomer sealing layer and the adhesive composition are preferably diluted with an organic solvent to prepare a coating liquid.

The organic solvent used for the preparation of the coating liquid is not particularly limited. Examples of the organic solvent include an aromatic solvent, an aliphatic solvent, an ester solvent, a ketone solvent, and an alcohol solvent. Examples of the aromatic solvent include benzene, toluene, and xylene. Examples of the aliphatic solvent include n-hexane and n-heptane. Examples of the ester solvent include ethyl acetate and butyl acetate. Examples of the ketone solvent include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone. Examples of the alcohol solvent include isopropyl alcohol and methanol.

Examples of the coating method include a spin coating method, a spray coating method, a bar coating method, a knife coating method, a roll knife coating method, a roll coating method, a knife coating method, a die coating method, and Gravure coating method, etc.

In order to prevent the organic solvent and the low boiling point component from remaining on the oligomer sealing layer 13 and the adhesive layer 12, after applying the coating liquid to the substrate 11, it is preferred to heat and dry the coating film.

When the crosslinking agent is blended in the adhesive composition, it is preferred to heat the coating film in order to increase the cohesive force in order to progress the crosslinking reaction.

(Use of adhesive sheets)

The adhesive sheet 10 is used when sealing a semiconductor element. The adhesive sheet 10 is preferably used for sealing a semiconductor element which is not mounted on a metal lead frame and is attached to the adhesive sheet 10. Specifically, the adhesive sheet 10 is preferably not mounted on a metal lead frame. When the semiconductor element of the holder is used, it is used when sealing the semiconductor element in a state of being attached to the adhesive layer 12. A form in which a semiconductor element is packaged without using a metal lead frame includes a panel scale package (PSP) and a wafer level package (WLP).

The adhesive sheet 10 is preferably used in a process of attaching a frame member having a plurality of openings to the adhesive sheet 10, and attaching the semiconductor wafer to an opening exposed to the frame member. The step of applying the adhesive layer 12, the step of coating the semiconductor wafer with a sealing resin, and the step of thermally curing the sealing resin.

(Method of Manufacturing Semiconductor Device)

A method of manufacturing a semiconductor device using the adhesive sheet 10 of the present embodiment will be described.

2A to 2E are schematic views showing a method of manufacturing the semiconductor device of the embodiment.

In the method of manufacturing a semiconductor device of the present embodiment, the frame member 20 having the plurality of openings 21 is placed on the adhesive sheet 10 (adhesive sheet adhering step), and the semiconductor wafer CP is attached to the exposed surface. a step (joining step) of the adhesive layer 12 of the opening portion 21 of the frame member 20, a step of coating the semiconductor wafer CP with the sealing resin 30 (sealing step), a step of thermally curing the sealing resin 30 (thermal curing step), and The step of peeling off the adhesive sheet 10 after heat hardening (peeling step). The reinforcing member 40 may be attached to the sealed tree after the thermal hardening step as needed. The step of sealing the sealing body 50 with the grease 30 (the reinforcing member is attached to the step). The steps are explained below.

. Adhesive sheeting step

Fig. 2A is a schematic view showing a step of attaching the frame member 20 to the adhesive layer 12 of the adhesive sheet 10.

The frame member 20 of the present embodiment is formed in a lattice shape and has a plurality of openings 21. The frame member 20 is preferably formed of a material having heat resistance. The material of the frame member 20 is, for example, a metal such as copper or stainless steel, or a heat-resistant resin such as a polyimide resin or a glass epoxy resin.

The opening portion 21 is a hole that penetrates the front and back surfaces of the frame member 20. The shape of the opening portion 21 is not particularly limited as long as the semiconductor wafer CP can be housed in the frame. The depth of the hole of the opening portion 21 is not particularly limited as long as it can accommodate the semiconductor wafer CP.

. Joining step

2B is a schematic view showing a step of attaching the semiconductor wafer CP to the adhesive layer 12.

When the adhesive sheet 10 is attached to the frame member 20, the adhesive layer 12 is exposed in accordance with the shape of the opening 21 in each of the openings 21. A semiconductor wafer CP is attached to the adhesive layer 12 of each of the openings 21. The semiconductor wafer CP is attached so that its circuit surface is covered with the adhesive layer 12.

The semiconductor wafer CP is manufactured, for example, by performing a back grinding step of grinding the back surface of the semiconductor wafer on which the circuit is formed, and Manufactured by a dicing step of semiconductor wafer singulation. In the dicing step, the semiconductor wafer is diced by a cutting means such as a dicing saw by attaching a semiconductor wafer to the adhesive layer of the dicing sheet to obtain a semiconductor wafer CP (semiconductor element).

The cutting device is not particularly limited, and a known cutting device can be used. Further, the cutting conditions are also not particularly limited. Further, a laser cutting method, a stealth dicing method, or the like may be used instead of the cutting method using a cutting blade.

After the dicing step, an extended dicing sheet may be implemented to expand the interval between the plurality of semiconductor wafers CP. By performing the expansion step, the semiconductor wafer CP can be picked up using a transfer means such as a collet. Further, by performing the expansion step, the adhesion force of the adhesive layer of the dicing sheet is reduced, and it becomes easy to pick up the semiconductor wafer CP.

When the energy ray polymerizable compound is blended in the adhesive composition of the dicing sheet or the adhesive layer, the energy ray is irradiated to the adhesive layer by the base material side of the dicing sheet to cure the energy ray polymerizable compound. When the energy ray polymerizable compound is cured, the cohesive force of the adhesive layer is increased, and the adhesion of the adhesive layer can be reduced. The energy line may, for example, be ultraviolet (UV), electron beam (EB) or the like, and is preferably ultraviolet light. The irradiation of the energy ray can be performed at any stage after attachment of the semiconductor wafer or before peeling (pickup) of the semiconductor wafer. For example, the energy line can be illuminated before or after cutting, or the energy line can be illuminated after the expanding step.

. Sealing step and thermal hardening step

2C is a schematic view showing a step of sealing the semiconductor wafer CP and the frame member 20 which are adhered to the adhesive sheet 10.

The material of the sealing resin 30 is a thermosetting resin, and examples thereof include an epoxy resin. The epoxy resin used as the sealing resin 30 may include, for example, a phenol resin, an elastomer, an inorganic filler, and a curing accelerator.

The method of coating the semiconductor wafer CP and the frame member 20 with the sealing resin 30 is not particularly limited.

In the present embodiment, an aspect in which the sheet-like sealing resin 30 is used will be described as an example. The sheet-shaped sealing resin 30 is placed so as to cover the semiconductor wafer CP and the frame member 20, and the sealing resin 30 is heat-cured to form the sealing resin layer 30A. In this manner, the semiconductor wafer CP and the frame member 20 are buried in the sealing resin layer 30A. When the sheet-like sealing resin 30 is used, it is preferable to seal the semiconductor wafer CP and the frame member 20 by vacuum lamination. By this vacuum lamination, it is possible to prevent a gap from being generated between the semiconductor wafer CP and the frame member 20. The temperature condition range of heating by vacuum lamination is, for example, 80 ° C or more and 120 ° C or less.

In the sealing step, a laminated sheet obtained by supporting a sheet-like sealing resin 30 on a resin sheet such as polyethylene terephthalate may be used. At this time, the laminated sheet may be placed so as to cover the semiconductor wafer CP and the frame member 20, and then the resin sheet may be peeled off from the sealing resin 30 to heat-harden the sealing resin 30. As such a laminated sheet, for example, an ABF film (manufactured by Ajinomoto Fine-Techno Co., Ltd.) can be cited.

The method of sealing the semiconductor wafer CP and the frame member 20 may also employ a transfer molding method. At this time, for example, inside the mold of the sealing device, the accommodating sticker The semiconductor wafer CP and the frame member 20 are adhered to the sheet 10. A fluid resin material is injected into the mold to harden the resin material. In the case of the transfer molding method, the conditions of heating and pressure are not particularly limited. An example of the usual conditions of the transfer molding method is to maintain a temperature of 150 ° C or higher and a pressure of 4 MPa or more and 15 MPa or less for 30 seconds or more and 300 seconds or less. Thereafter, the pressurization is released, and the cured product is taken out by the sealing device, and placed in an oven, and maintained at a temperature of 150 ° C or higher for 2 hours or longer and 15 hours or shorter. In this manner, the semiconductor wafer CP and the frame member 20 are sealed.

When the sheet-like sealing resin 30 is used in the sealing step described above, the first heating pressing step may be performed before the step of thermally curing the sealing resin 30 (thermal curing step). In the first heating and pressing step, the semiconductor wafer CP covered with the sealing resin 30 and the adhesive sheet 10 of the frame member 20 are sandwiched between the both surfaces by a plate member, and pressed under conditions of specific temperature, time, and pressure. The sealing resin 30 is also easily filled in the gap between the semiconductor wafer CP and the frame member 20 by performing the first heating pressing step. Further, by performing the heat pressing step, the unevenness of the sealing resin layer 30A composed of the sealing resin 30 can be flattened.

After the thermal curing step, when the adhesive sheet 10 is peeled off, the semiconductor wafer CP and the frame member 20 sealed by the sealing resin 30 can be obtained. Hereinafter, it is called a sealing body 50.

. Reinforcing member attached step

2D is a schematic view showing a step of attaching the reinforcing member 40 to the sealing body 50.

After the adhesive sheet 10 is peeled off, a rewiring step and a bump fixing step of forming a rewiring layer on the circuit surface of the exposed semiconductor wafer CP are performed. In order to improve the operability of the sealing body 50 in the rewiring step and the bump fixing step, the sealing member 50 may be attached to the reinforcing member 40 as needed (the reinforcing member attaching step). When the reinforcing member adhering step is carried out, it is preferably carried out before the adhesive sheet 10 is peeled off. As shown in FIG. 2D, the sealing body 50 is supported in a state in which the adhesive sheet 10 and the reinforcing member 40 are sandwiched therebetween.

In the present embodiment, the reinforcing member 40 is provided with a heat-resistant reinforcing plate 41 and a heat-resistant adhesive layer 42. The reinforcing plate 41 is, for example, a plate-shaped member containing a heat-resistant resin such as glass epoxy resin. Next, the layer 42 is followed by the reinforcing plate 41 and the sealing body 50. The adhesive layer 42 is appropriately selected depending on the material of the reinforcing plate 41 and the sealing resin layer 30A.

In the step of attaching the reinforcing member, it is preferable that the sealing layer 30A and the reinforcing plate 41 are sandwiched between the sealing layer 50 and the reinforcing layer 41, and further sandwiched between the reinforcing plate 41 side and the adhesive sheet 10 side by the plate member. a second heated pressing step that is pressed at a specific temperature, time, and pressure. The sealing body 50 and the reinforcing member 40 are temporarily fixed by the second heating pressing step. After the second heating and pressing step, in order to harden the adhesive layer 42, it is preferred to heat the temporarily sealed sealing body 50 and the reinforcing member 40 under a specific temperature and time. The conditions for heat curing are appropriately set depending on the material of the adhesive layer 42, and are, for example, 185 ° C, 80 minutes, and 2.4 MPa. In the second heating and pressing step, for example, a metal plate such as stainless steel may be used as the plate member.

. Stripping step

Fig. 2E is a schematic view showing a step of peeling off the adhesive sheet 10.

In the present embodiment, when the base material 11 of the adhesive sheet 10 is bendable, the frame member 20, the semiconductor wafer CP, and the sealing resin layer 30A can be easily peeled off while the adhesive sheet 10 is bent. The peeling angle θ is not particularly limited, and it is preferable to peel the adhesive sheet 10 at a peeling angle θ of 90 degrees or more. When the peeling angle θ is 90 degrees or more, the adhesive sheet 10 can be easily peeled off from the frame member 20, the semiconductor wafer CP, and the sealing resin layer 30A. The peeling angle θ is preferably 90 degrees or more and 180 degrees or less, more preferably 135 degrees or more and 180 degrees or less. By peeling the adhesive sheet 10 while bending, the peeling of the adhesive sheet 10 can be performed while reducing the load on the frame member 20, the semiconductor wafer CP, and the sealing resin layer 30A, and the semiconductor due to the peeling of the adhesive sheet 10 can be suppressed. Damage to the wafer CP and the sealing resin layer 30A. After the adhesive sheet 10 is peeled off, the above-described rewiring step, bump fixing step, and the like are performed. After the adhesive sheet 10 is peeled off, the reinforcing member attaching step may be performed as needed before performing the rewiring step, the bump fixing step, and the like.

When the reinforcing member 40 is attached, after the rewiring step, the bump fixing step, and the like are performed, the reinforcing member 40 is peeled off from the sealing body 50 at a stage where the reinforcing member 40 is not required to be supported.

Thereafter, the sealing body 50 is singulated in units of semiconductor wafers CP (single step). The method of singulating the sealing body 50 is not particularly limited. For example, singulation can be performed by the same method as that used when dicing the semiconductor wafer. The step of singulating the sealing body 50 can be The sealing body 50 is placed in a state of being attached to a dicing sheet or the like. The semiconductor package of the semiconductor wafer CP unit is manufactured by singulating the sealing body 50, and the semiconductor package is mounted on a printed wiring board or the like in the constitutional step.

According to this embodiment, it is possible to provide the adhesive sheet 10 which can be prevented from being contaminated by the surface of the adherend even after the step of applying the high temperature condition.

The adherend to which the adhesive layer 12 is in contact is, for example, a semiconductor wafer CP and a frame member 20. The semiconductor wafer CP and the frame member 20 are exposed to high temperature conditions in a state of being in contact with the adhesive layer 12. Since the adhesive sheet 10 is adhered between the substrate 11 and the adhesive layer 12, even if the adhesive sheet 10 is exposed to high temperature conditions, the oligomer-to-adhesive layer 12 in the substrate 11 is prevented. Infiltration. Therefore, according to the adhesive sheet 10, surface contamination of the semiconductor wafer CP and the frame member 20 can be prevented.

[Second embodiment]

The second embodiment differs from the first embodiment in that it has an oligomer sealing layer on both surfaces of the substrate of the adhesive sheet. The second embodiment is the same as the first embodiment, and thus the description will be omitted or simplified.

Fig. 3 is a schematic cross-sectional view showing the adhesive sheet 10A of the second embodiment.

The adhesive sheet 10A has a substrate 11, an adhesive layer 12, an oligomer sealing layer 13 (first oligomer sealing layer), and an oligomer sealing layer 14 (second oligomer sealing layer).

The adhesive sheet 10A has oligomer sealing layers 13 and 14 on both surfaces of the substrate 11 (the first substrate surface 11a and the second substrate surface 11b). Adhesive In the sheet 10A, the oligomer sealing layer 13 is laminated on the first substrate surface 11a, and the oligomer sealing layer 14 is laminated on the second substrate surface 11b. Preferably, the first substrate surface 11a is covered with the oligomer sealing layer 13, and the second substrate surface 11b is covered with the oligomer sealing layer 14. As in the first embodiment, the oligomer sealing layer 13 is provided between the substrate 11 and the adhesive layer 12. The shape of the adhesive sheet 10A may be any shape such as a sheet shape, a belt shape, or a label shape.

The oligomer sealing layer 13 (first oligomer sealing layer) is the same as that of the first embodiment.

The oligomer sealing layer 14 (second oligomer sealing layer) is a layer which is heated to prevent the oligomer deposited on the second substrate surface 11b of the substrate 11 from adhering to other members to cause contamination. The oligomer sealing layer 14 is preferably formed of the same material as the oligomer sealing layer 13.

The thickness of the oligomer sealing layer 14 is not particularly limited, but is preferably the same as the thickness of the oligomer sealing layer 13 described in the first embodiment. The more the thickness of the oligomer sealing layer is increased, the more the effect of the oligomer sealing is improved, but the thickness of the oligomer sealing layer 13 and the oligomer sealing layer 14 is, for example, from the viewpoint of productivity and cost of the adhesive sheet. It may be 100 nm or more and 200 nm or less, or may be about 150 nm.

The method for producing the adhesive sheet 10A is also not particularly limited.

For example, the adhesive sheet 10A is produced by the following steps. First, a composition for an oligomer sealing layer is applied onto the first substrate surface 11a of the substrate 11 to form a coating film. Next, the coating film is heated and hardened to form the oligomer sealing layer 13. Next, the oligo is coated on the second substrate surface 11b of the substrate 11. A composition for a polymer sealing layer forms a coating film. Next, the coating film is heated and hardened to form the oligomer sealing layer 14. Next, an adhesive composition is applied onto the oligomer sealing layer 13 to form a coating film. Next, the coating film is dried to form an adhesive layer 12.

The adhesive sheet 10A can also be used in the same manner as the adhesive sheet 10 in the same manner as the adhesive sheet 10, and can be used in the method of manufacturing a semiconductor device.

According to the adhesive sheet 10A, similarly to the adhesive sheet 10, even after the step of applying a high temperature condition, the surface of the adherend can be prevented from being contaminated.

Further, since the oligomer sealing layer 14 is also formed on the second substrate surface 11b in accordance with the adhesive sheet 10A, it is possible to prevent the oligomer deposited on the second substrate surface 11b from adhering to members and devices other than the adherend. create pollution. For example, in the method of manufacturing a semiconductor device, contamination of the plate member in contact with the adhesive sheet 10A in the heat pressing step can be prevented.

[Changes in the embodiment]

The present invention is not limited to the above-described embodiments, and variations and improvements of the scope of the invention can be included in the present invention. In the following description, the same components as those in the above-described embodiments are denoted by the same reference numerals, and their description is omitted or simplified.

Further, the adhesive sheet may be provided in a single piece or in a state in which a plurality of adhesive sheets are laminated. In this case, for example, the adhesive layer may be covered by the substrate of the other adhesive sheet laminated.

Further, the adhesive sheet may be a long-shaped sheet or may be provided in a state of being wound into a roll shape. The adhesive sheet wound in a roll shape can be used by being wound up by a drum and cut into a desired size or the like.

The adhesive layer of the adhesive sheet may also be coated with a release sheet. The release sheet is not particularly limited. For example, from the viewpoint of ease of handling, the release sheet preferably has a release substrate and a release agent layer formed by applying a release agent to the release substrate. Further, the release sheet may have a release agent layer only on one side of the release substrate, or may have a release agent layer on both sides of the release substrate. Examples of the release substrate include a paper substrate, a laminate paper in which a thermoplastic resin such as polyethylene is laminated on the paper substrate, and a plastic film. Examples of the paper substrate include cellophane, coated paper, and glass powder paper. Examples of the plastic film include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; and polyolefin films such as polypropylene and polyethylene. Examples of the release agent include an olefin resin, a rubber elastomer (for example, a butadiene resin or an isoprene resin), a long-chain alkyl resin, an alkyd resin, a fluorine resin, and polyoxyl Resin.

The thickness of the release sheet is not particularly limited. The thickness of the release sheet is usually 20 μm or more and 200 μm or less, preferably 25 μm or more and 150 μm or less.

The thickness of the release agent layer is not particularly limited. When the release agent-containing solution is applied to form a release agent layer, the thickness of the release agent layer is preferably 0.01 μm or more and 2.0 μm or less, more preferably 0.03 μm or more and 1.0 μm or less.

When a plastic film is used as a release substrate, the thickness of the plastic film is It is preferably 3 μm or more and 50 μm or less, more preferably 5 μm or more and 40 μm or less.

An adhesive sheet having a release sheet is produced, for example, by the following steps. First, an adhesive composition is applied onto a release sheet to form a coating film. Next, the coating film is dried to form the adhesive layer 12. Further, as described in the above embodiment, the oligomer sealing layer 13 is formed in advance on the first substrate surface 11a of the substrate 11. The adhesive layer 12 on the release sheet is bonded to the oligomer sealing layer 13 on the substrate 11. In the case of the aspect of the oligomer sealing layer 14, after the oligomer sealing layers 13 and 14 are formed on both surfaces of the substrate 11, the adhesive layer 12 and the oligomer sealing layer 13 are bonded together.

In the above embodiment, the material of the sealing resin 30 is described as an example of a thermosetting resin, but the present invention is not limited to such a form. For example, the sealing resin 30 may be an energy ray-curable resin which is hardened by an energy ray such as ultraviolet rays.

In the above-described embodiment, the description of the method of manufacturing the semiconductor device is described by taking the frame member 20 on the adhesive sheet 10 as an example. However, the present invention is not limited to such a form. The adhesive sheet 10 may be used in a method of manufacturing a semiconductor device in which a semiconductor element is sealed without using a frame member.

[Examples]

Hereinafter, the present invention will be described in further detail by way of examples. The invention is not limited by these examples.

[evaluation method]

The evaluation of the adhesive sheet was carried out in accordance with the method shown below.

[Confirmation of residue]

A semiconductor wafer is attached to the adhesive layer of the adhesive sheet to obtain an adhesive sheet with a semiconductor wafer attached thereto.

The adhesive sheet with the semiconductor wafer was heated at 190 ° C for 1 hour. After heating, the adhesive sheet was peeled off. The adhered surface of the semiconductor wafer after peeling was observed with a digital microscope (manufactured by KEYENCE, DIGITAL MICROSCOPE; VHX-1000), and the presence or absence of residue was confirmed. The observation magnification was set to 500 times. When the residue was not confirmed, it was judged as "A", and when the residue was confirmed, it was judged as "B".

Further, whether or not the residue was an oligomer derived from the substrate was carried out by the following method. The spectrum of the residue was measured by Raman spectroscopic analysis, and the spectrum was confirmed to be the oligomer derived from the substrate by the characteristics of the substrate of the adhesive sheet.

[Production of adhesive sheets] (Example 1) (1) Preparation of coating oligomer solvent sealant

The coating oligo of Example 1 was prepared by blending the following (A) bisphenol A epoxy compound, (B) polyester compound, (C) polyfunctional amine compound, and (D) acidic catalyst, and stirring well. Polymer sealant liquid (composition for oligomer sealing layer).

(A) bisphenol A epoxy compound

"EPICLON H-360" (trade name) manufactured by DIC Corporation, solid content concentration: 40% by mass, weight average molecular weight: 25000

(B) Polyester compound

"Vylon GK680" (trade name) manufactured by Toyobo Co., Ltd., number average molecular weight: 6000, glass transition temperature: 10 °C

(C) polyfunctional amine compounds

Hexamethoxymethyl melamine, "Cymel 303" (trade name) manufactured by Cytec Industries, Japan

(D) Acid catalyst

Methanol solution of p-toluenesulfonic acid (solid content concentration: 50% by mass)

Specifically, to 100 parts by mass of the above (A) bisphenol A epoxy compound, 14.29 parts by mass of the toluene diluted solution (solid content concentration: 30%) of the above (B) polyester compound, and the above (C) Rokko 11.4 parts by mass of oxymethyl melamine was further diluted with a mixed solvent of toluene/methyl ethyl ketone = 50% by mass/50% by mass to a solid content of 3% by mass, and stirred. To the stirred solution, 2.9 parts by mass of a (D) p-toluenesulfonic acid methanol solution (solid content concentration: 50% by mass) (relative to 100 parts by mass of (A) bisphenol A type epoxy compound) was obtained. Oligomer sealant solution for cloth.

(2) Fabrication of oligomer sealing layer

The prepared coating oligomer solvent liquid was applied to a biaxially stretched polyethylene terephthalate film (Diafoil T-100 (trade name) manufactured by Mitsubishi Plastics Co., Ltd., thickness: 50 μm, at 100 ° C) ^On one side of the storage modulus of 3.2 × 10 ⁹ Pa), the coating was uniformly applied by a Meyer bar coating method so that the thickness after drying became 150 nm. The coated film was passed through the inside of the oven, and the coating film was heat-hardened to obtain an oligomer sealing layer. The blowing condition of the hot air in the oven was a temperature of 150 ° C, a wind speed of 8 m / min, and the processing speed in the oven was adjusted so that the coated film passed through the inside of the oven in 20 seconds.

(3) Production of adhesive composition

The coating adhesive liquid (adhesive composition) of Example 1 was prepared by blending the following materials (polymer, adhesion aid, crosslinking agent, and diluent solvent) and stirring well.

. Polymer: acrylate copolymer, 40 parts by mass (solid content)

The acrylate copolymer was prepared by copolymerizing 92.8% by mass of 2-ethylhexyl acrylate, 7.0% by mass of 2-hydroxyethyl acrylate, and 0.2% by mass of acrylic acid.

. Adhesive Additive: Hydroxyhydrogenated polybutadiene at both ends [Japan Soda Co., Ltd.; GI-1000], 5 parts by mass (solid content)

. Crosslinking agent: aliphatic isocyanate having hexamethylene diisocyanate (trimeric isocyanate type modified body of hexamethylene diisocyanate) [manufactured by Polyurethane Industrial Co., Ltd.; Coronate HX], 3.5 parts by mass (solid content)

. Dilution solvent: methyl ethyl ketone was used, and the solid content concentration of the coating adhesive liquid was 30% by mass.

(4) Production of adhesive layer

The coating adhesive liquid to be applied was applied to a 38 μm provided with a polyoxynitride-based release layer so as to have a thickness of 50 μm after drying using a notch coater (Comma coater, registered trademark). The transparent polyethylene terephthalate film release film [LINTEC (manufactured by the company); SP-PET382150] on the peeling layer side, heated at 90 ° C and 90 seconds, followed by heating at 115 ° C and 90 seconds, so that the coating The film is dry.

(5) Production of adhesive sheets

The adhesive layer prepared on the surface of the release film was bonded to the oligomer sealing layer formed on the surface of the substrate to obtain an adhesive sheet of Example 1.

(Example 2)

The adhesive sheet of Example 2 was produced in the same manner as in Example 1 except that the polymer contained in the adhesive layer was different from that of Example 1.

The polymer used in Example 2 was obtained by copolymerizing 8-0.8% by mass of 2-ethylhexyl acrylate, 7% by mass of 2-hydroxyethyl acrylate, and 12% by mass of 4-propenylmorpholine, and 0.2% by mass of acrylic acid. Formulated by polymerization.

(Comparative Example 1)

The adhesive sheet of Comparative Example 1 was produced in the same manner as in Example 1 except that the adhesion aid contained in the adhesive layer was different from that of Example 1, the substrate was different, and the oligomer sealing layer was not provided.

The adhesion aid used in Comparative Example 1 was tributyl ethyl citrate [made by Tadaoka Chemical Industry Co., Ltd.]. Further, tributyl citrate does not have the aforementioned reactive group.

The substrate used in Comparative Example 1 was a polyethylene terephthalate film [manufactured by Mitsubishi Plastics Co., Ltd.; PET 50T-100, thickness 50 μm, storage modulus at 100 ° C 3.2 × 10 ⁹ Pa]. The adhesive layer prepared on the surface of the release film was bonded to the substrate to obtain an adhesive sheet of Comparative Example 1.

(Comparative Example 2)

The adhesive sheet of Comparative Example 2 was produced in the same manner as in Comparative Example 1, except that the adhesive auxiliary contained in the adhesive layer was different from Comparative Example 1.

The adhesion aid used in Comparative Example 2 was a hydrogenated polybutadiene at both ends (manufactured by Nippon Soda Co., Ltd.; GI-1000).

(Comparative Example 3)

The adhesive sheet of Comparative Example 3 was carried out except that the adhesive contained in the adhesive layer was different from that of Example 1, the thickness of the adhesive layer was different, the substrate was different, and the oligomer sealing layer was not provided. Example 1 was produced in the same manner.

In Comparative Example 3, a polyfluorene-based adhesive was used.

In Comparative Example 3, 18 parts by mass of a polyfluorene-based adhesive Ad1 (SD4580PSA) was blended. (solid content), 40 parts by mass of solid polyoxygen adhesive Ad2 (SD4587L) (solid content), catalytic monomer Cat1 (NC-25 CAT) 0.3 parts by mass (solid content), catalyst Cat2 (CAT-SRX-212) 0.65 parts by mass (solid content) and 5 parts by mass (solid content) of the primer (BY24-712) were thoroughly stirred to prepare a coating adhesive liquid (adhesive composition). The materials used in the adhesive composition of Comparative Example 3 were all Toray. Dow Corning (share) system.

The coating adhesive liquid of Comparative Example 3 was applied and dried on the peeling layer side of the release film so as to have a thickness of 30 μm after drying to prepare an adhesive layer. Drying conditions were 130 ° C and 2 minutes. The substrate used in Comparative Example 3 was a polyethylene terephthalate film [manufactured by Mitsubishi Plastics Co., Ltd.; Diafoil PET50 T-100, thickness 50 μm, storage modulus at 100 ° C 3.2 × 10 ⁹ Pa]. The adhesive layer prepared on the surface of the release film was bonded to the substrate to obtain an adhesive sheet of Comparative Example 3.

Table 1 shows the evaluation results of the adhesive sheets of Example 1, Example 2, and Comparative Examples 1 to 3.

The adhesive sheets of Comparative Examples 1 to 3 do not have an oligomer sealing layer between the adhesive layer and the substrate, and therefore it is considered that the residue is deposited on the surface of the adherend (semiconductor wafer) under exposure to a high temperature of 190 ° C. .

On the other hand, the adhesive sheets of Example 1 and Example 2 have an oligomer sealing layer between the adhesive layer and the substrate, so that even when exposed to a high temperature of 190 ° C, the adherend (semiconductor wafer) No residue is deposited on the surface.

10‧‧‧Adhesive sheets

11‧‧‧Substrate

11a‧‧‧First substrate surface

11b‧‧‧Second substrate surface

12‧‧‧Adhesive layer

13‧‧‧ oligomer sealing layer

Claims (9)

An adhesive sheet which is used for sealing a semiconductor element on an adhesive sheet, comprising a substrate, an adhesive layer containing an adhesive, and an oligomer disposed between the substrate and the adhesive layer Sealing layer. The adhesive sheet according to claim 1, wherein the oligomer sealing layer is a cured film obtained by curing an epoxy compound, a polyester compound, and a composition for an oligomer sealing layer of a polyfunctional amine-based compound. The adhesive sheet according to claim 2, wherein the composition for the oligomer sealing layer contains (A) 50% by mass or more and 80% by mass or less of a bisphenol A type epoxy compound, and (B) 5% by mass or more and 30% A polyester compound having a mass % or less and (C) a polyfunctional amino compound of 10% by mass or more and 40% by mass or less. The adhesive sheet of claim 1, wherein the substrate has a storage modulus of 100 × C or more of 1 × 10 ⁷ Pa or more. The adhesive sheet according to claim 1, wherein the adhesive layer contains an acrylic adhesive composition or a polyoxygen adhesive composition. An adhesive sheet according to claim 5, wherein The acrylic pressure-sensitive adhesive composition contains an acrylic copolymer containing 2-ethylhexyl acrylate as a main monomer. The adhesive sheet according to claim 5, wherein the polyfluorene-based adhesive composition contains an addition polymerization type polyoxyxylene resin. The adhesive sheet of claim 1, wherein the substrate comprises a polyester resin. The adhesive sheet according to any one of claims 1 to 8, wherein the aforementioned oligomer sealing layer is provided on both sides of the substrate.