TW201722723A - 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) having a first surface (11a) and a second surface (11b) on the opposite side from the first surface (11a), the substrate including a polyester resin; an adhesive agent layer (12) layered on the first surface (11a) of the substrate (11); and a hard coat layer (13) layered on the second surface (11b) of the substrate (11). The hard coat layer (13) is a cured film formed by curing an organic/inorganic hybrid material.

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.

However, since the heat-resistant film such as a polyimide film used for the production of the mask sheet described in Document 1 and the polyoxynitride-based adhesive are expensive, the use of the mask sheet is limited to a part of the use such as a QFN package.

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, when a film having a low heat resistance and a low cost such as a film such as polyethylene terephthalate or the like is used as a substrate, in a heating and pressurizing step, The method is characterized in that the oligomer in the substrate is attached to the device and the member to be contaminated, or the device and the member are fused with the substrate. When the substrate is fused to the device and the member, it is difficult to peel off the adhesive sheet, and even if it is peelable, the oligomer or the like of the substrate remains in the device and the member, and the device and the member are contaminated. 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 prevent contamination of equipment and members and prevent fusion with equipment and members even after a step of applying high temperature conditions.

According to an aspect of the present invention, there is provided an adhesive sheet which is used for sealing an adhesive sheet used for bonding a semiconductor element on a sheet, the sheet having a first side and a second side opposite to the first surface, and a base material comprising a polyester resin, an adhesive layer laminated on the first surface of the base material, and a hard coat layer laminated on the second surface of the base material, wherein the hard coat layer is organic The hardened film formed by the hardening of the inorganic hybrid material.

In the adhesive sheet of one aspect of the present invention, after being heated at 190 ° C for 1 hour, the shrinkage ratio in the direction along either side of the substrate is higher. Good is 1.7% or less.

In the adhesive sheet according to an aspect of the invention, the polyester resin is preferably selected from the group consisting of polyethylene terephthalate resin, polyethylene naphthalate resin, and polybutylene terephthalate. A resin composed of a resin.

In the adhesive sheet according to an aspect of the invention, the thickness of the hard coat layer is preferably 0.5 μm or more and 3.0 μm or less.

In an adhesive sheet according to an aspect of the present invention, preferably, the second hard coat layer is further provided between the adhesive layer and the substrate, and the second hard coat layer contains a polyfunctional acrylic resin.

In the adhesive sheet according to an aspect of the invention, the organic-inorganic hybrid material preferably contains a material obtained by bonding cerium oxide fine particles to an organic compound having a polymerizable unsaturated group, and an active energy ray-curable resin.

According to the present invention, it is possible to provide an adhesive sheet which can prevent contamination of equipment and members and prevent fusion with equipment and members even after the step of applying high temperature conditions.

10, 10A‧‧‧ adhesive sheet

11‧‧‧Substrate

11a‧‧‧ first side

11b‧‧‧ second side

12‧‧‧Adhesive layer

13‧‧‧hard coating

13a‧‧‧First hard coating

13b‧‧‧Second hard coating

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

RL‧‧‧ peeling sheet

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.

2C is a view showing a semiconductor using the adhesive sheet of the first embodiment A diagram of a portion of the manufacturing steps of the device.

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 a hard coat layer 13.

The substrate 11 has a first surface 11a and a second surface 11b on the opposite side to the first surface 11a. In the adhesive sheet 10 of the present embodiment, the adhesive layer 12 is laminated on the first surface 11a, and the hard coat layer 13 is laminated on the second surface 11b.

In the present embodiment, as shown in FIG. 1, a release sheet RL is laminated on the adhesive layer 12. 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 base material 11 contains a polyester resin. The base material 11 is more preferably made of a material containing a polyester resin as a main component. In this specification, polyester resin The material of the 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 copolymerized resins of the resins; more preferably selected from the group consisting of polyethylene terephthalate resin, polyethylene naphthalate resin, and polybutylene terephthalate resin The resulting group of resins; more preferably 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.

In order to improve the adhesion between the substrate 11 and the adhesive layer 12 and the adhesion between the substrate 11 and the hard coat layer 13, the first surface 11a and the second surface 11b may be subjected to a primer treatment, a corona treatment, or And surface treatment of at least one of plasma treatment and the like. The first surface 11a and the second surface 11b of the substrate 11 may be coated with an adhesive to perform an adhesive treatment. 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.

After the adhesive sheet 10 is heated at 190 ° C for 1 hour, the shrinkage ratio in the direction along either side of the substrate 11 is preferably 1.7% or less.

After the adhesive sheet 10 is heated at 190 ° C for 1 hour, at least the shrinkage ratio of the substrate 11 in the MD direction is preferably 1.7% or less.

In the manufacturing process of the semiconductor device, the step of heating at 180 ° C to 190 ° C for about 1 hour, and if the shrinkage ratio is 1.7% or less, the adhesive sheet 10 can be prevented from being peeled off by the adherend due to shrinkage of the substrate 11 . By preventing the adhesive sheet 10 from being peeled off from the adherend during the heating step, the conveyance failure in the manufacturing process can be prevented. Further, since the adhesive sheet 10 is peeled off, the surface of the adherend (for example, the circuit surface of the semiconductor wafer) is exposed, and there is contamination. However, if the shrinkage rate condition is satisfied, such contamination can be prevented.

The MD (Machine Direction) direction of the substrate 11 in the present specification means a direction parallel to the longitudinal direction of the original film to be applied to the substrate 11 (the transfer direction at the time of production of the original film).

(hard coating)

The hard coat layer 13 is a layer formed of a cured film formed by curing an organic-inorganic hybrid material. The hard coat layer 13 contains a cured product of an organic-inorganic hybrid material.

In the present specification, the organic-inorganic hybrid material refers to a resin obtained by mixing a mixture of an organic component and an inorganic component in a state of being densely dispersed at a molecular level or a particle size close to a molecular grade. Specifically, the organic component or the inorganic component is dispersed, for example, at a particle diameter of 100 nm or less. The organic-inorganic hybrid material used in the present embodiment is preferably a material which can be cured by an inorganic component and an organic component by irradiation with an active energy ray to form a cured film (hard coating film). Examples of active energy rays include ultraviolet rays and electrons. Bunch and so on.

In addition, the particle diameter of the organic component or the inorganic component in the present specification is a value measured by a dynamic light scattering method using a particle size distribution measuring apparatus (Nanotrac Wave-UT151, manufactured by MicrotracBEL Co., Ltd.).

The organic-inorganic hybrid material is preferably an active energy ray-sensitive composition containing an active energy ray-curable resin and cerium oxide microparticles. The active energy ray-sensitive composition is irradiated with the active energy ray to crosslink and harden, thereby obtaining an organic-inorganic hybrid hardening resin.

The organic-inorganic hybrid material in the present embodiment preferably contains a material obtained by bonding cerium oxide fine particles to an organic compound having a polymerizable unsaturated group, and an active energy ray-curable resin. Since the organic-inorganic hybrid material contains cerium oxide fine particles, shrinkage at the time of curing can be reduced, and curling of the adhesive sheet 10 can be suppressed.

(active energy ray-hardening resin)

In the present embodiment, the active energy ray-curable resin is a polymerizable compound which is crosslinked and cured by irradiation with an active energy ray. The heat history of the substrate 11 can be made small by using a resin which is hardened by the active energy ray. Examples of the active energy ray include electromagnetic waves such as ultraviolet rays and electron beams, and charged particle beams having energy quantum. The resin used for the hard coat layer 13 of the present embodiment is preferably an ultraviolet curable resin.

The active energy ray-curable resin preferably contains a polyfunctional acrylic resin. The polyfunctional acrylic resin is preferably selected from the group consisting of polyfunctional (meth)acrylate monomers and (meth)acrylate prepolymers. At least one resin of the group is more preferably a polyfunctional (meth) acrylate monomer.

In the present specification, "(meth) acrylate" is used to indicate both acrylate and methacrylate, and the same applies to other similar terms.

Examples of the polyfunctional (meth)acrylate monomer include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and neopentyl glycol. Di(meth)acrylate, polyethylene glycol di(meth)acrylate, hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate, dicyclopentyl di(meth)acrylate, Caprolactone modified dicyclopentenyl di(meth) acrylate, ethylene oxide modified di(meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, olefin Propylated cyclohexyl di(meth)acrylate, trimeric isocyanate di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid Dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, ginseng(propyleneoxyethyl)trimeric isocyanate Propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and caprolactone modified dipentaerythritol hexa (meth) propylene Esters and the like.

Further, the polyfunctional (meth) acrylate monomer may be used singly or in combination of two or more.

Examples of the (meth)acrylate prepolymer include a polyester (meth)acrylate prepolymer and a (meth)acrylic epoxy ester prepolymer. A urethane (meth) acrylate prepolymer, a polyol (meth) acrylate prepolymer, and the like.

A polyester (meth) acrylate type prepolymer, for example, a condensation of a polyvalent carboxylic acid and a polyhydric alcohol to obtain a polyester oligo having a hydroxyl group at both terminals, and further by using the hydroxy group as (meth)acrylic acid Obtained by esterification. Further, as the polyester (meth) acrylate-based prepolymer, for example, an oligomer can be obtained by adding an alkylene oxide to a polyvalent carboxylic acid, and the terminal hydroxyl group of the oligomer is esterified with (meth)acrylic acid. Get it.

(meth)acrylic acid epoxy ester prepolymer, for example, by reacting (meth)acrylic acid with an oxirane ring of a lower molecular weight bisphenol type epoxy resin or a novolak type epoxy resin Get it.

a urethane (meth) acrylate type prepolymer, for example, a polyurethane polyol or a polyester polyol, and a polyisocyanate can be obtained by reacting with a polyisocyanate, and The polyurethane oligomer is obtained by esterification with (meth)acrylic acid.

The polyol (meth) acrylate prepolymer can be obtained by esterifying a hydroxyl group of a polyether polyol with (meth)acrylic acid.

Further, these prepolymers may be used singly or in combination of two or more kinds, or may be used in combination with the above-mentioned polyfunctional (meth) acrylate monomer.

(cerium oxide microparticles)

The average particle diameter of the cerium oxide microparticles is preferably 0.5 nm or more and 500 nm or less, more preferably 1 nm or more and 100 nm or less. Furthermore, two The average particle diameter of the cerium oxide microparticles is, for example, a value measured by a BET method.

Among the cerium oxide fine particles, from the viewpoint of forming a strong bond with the active energy ray-curable resin, surface modification of an organic compound having a polymerizable unsaturated group reactive with the above active energy ray-curable resin is particularly preferable. The cerium oxide microparticles (reactive cerium oxide microparticles) are preferred.

The cerium oxide microparticles surface-modified with an organic compound having a polymerizable unsaturated group can be organicized by a polymerizable unsaturated group having a functional group capable of reacting with the sterol group, that is, a (meth) acryl fluorenyl group The compound is obtained by reacting a sterol group on the surface of the cerium oxide microparticles.

In the present embodiment, the organic compound having a polymerizable unsaturated group on the surface of the cerium oxide microparticles may be a compound corresponding to the active energy ray-curable resin. However, the compound which modifies the surface of the cerium oxide microparticles is contained as a constituent element of the cerium oxide microparticles, and is distinguished from the above-described active energy ray-curable resin.

The polymerizable unsaturated group-containing organic compound having a functional group reactive with a sterol group is preferably, for example, a compound represented by the following general formula (I).

In the above general formula (I), R ¹ is a hydrogen atom or a methyl group, and R ² is a halogen atom or a group selected from the group consisting of the groups represented by the following formulas.

-OCH ₂ CH ₂ NCO, , , -OCH ₂ CH ₂ OH, -OH, -O(CH ₂ ) ₃ -Si(OCH ₃ ) ₃

Examples of the organic compound containing a polymerizable unsaturated group include (meth)acrylic acid, (meth)acrylic acid chloride, 2-isocyanatoethyl (meth)acrylate, and glycidyl (meth)acrylate. (meth)acrylic acid derivatives such as 2,3-iminopropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and (meth)acryloxypropyltrimethoxydecane .

These organic compounds containing a polymerizable unsaturated group may be used singly or in combination of two or more.

The content of the cerium oxide microparticles in the organic-inorganic hybrid material is preferably 80 parts by mass or more and 400 parts by mass or less, more preferably 100 parts by mass or more and 300 parts by mass based on 100 parts by mass of the active energy ray-curable resin. Below the mass.

(photopolymerization initiator)

The organic-inorganic hybrid material preferably contains a photopolymerization initiator.

The photopolymerization initiator may, for example, be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin and butyl Ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl- 1-[4-(methylthio)phenyl]-2-morpholinyl-propan-1-one, 4-(2-hydroxyethoxy)phenyl-2(hydroxy-2-propyl)one, Benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylindole, 2-ethylhydrazine, 2-tert-butyl hydrazine, 2-amino hydrazine, 2-methyl thioxanthone, 2-ethyl thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-Diethylthioxanthone, benzyldimethylketal, acetophenone dimethyl ketal, and p-dimethylaminobenzoate.

Further, these photopolymerization initiators may be used singly or in combination of two or more.

Further, commercially available products of the organic-inorganic hybrid material containing the active energy ray-curable resin, the cerium oxide fine particles, and the photopolymerization initiator may, for example, be "Opstar Z7530", "Opstar Z7524", and "Opstar". TU4086" (product name, all JSR (share) system) and so on.

The active energy ray-sensitive composition may contain, as needed, an ultraviolet ray absorbing agent, a light stabilizer, an antioxidant, an infrared absorbing agent, an antistatic agent, a leveling agent, and a defoaming agent, as long as the effect of the present invention is not impaired. At least one additive of the group formed by the agent or the like. Among these additives, at least one selected from the group consisting of an ultraviolet absorber and a photosensitizer is preferable in view of improving light resistance.

(UV absorber)

The active energy ray-sensitive composition may also contain an ultraviolet absorber.

Examples of the ultraviolet absorber include a benzotriazole-based ultraviolet absorber, a hindered amine-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, and a triazine system. UV absorbers, etc. These ultraviolet absorbers may be used alone or in combination of two or more. Among these, a radically polymerizable ultraviolet absorber having a radical bond having a radical polymerizable property in the molecule is particularly preferred.

The content of the ultraviolet absorber is preferably 0.2 parts by mass or more and 10 parts by mass or less, more preferably 100 parts by mass or less based on 100 parts by mass of the total of the active energy ray-curable resin, the cerium oxide fine particles, and the photopolymerization initiator. 0.5 parts by mass or more and 7 parts by mass or less.

(light stabilizer)

The active energy ray-sensitive composition may also contain a light stabilizer.

Examples of the photostabilizer include a hindered amine light stabilizer, a benzophenone light stabilizer, and a benzotriazole light stabilizer. These light stabilizers may be used singly or in combination of two or more.

The content of the light stabilizer is preferably 0.2 parts by mass or more and 10 parts by mass or less, more preferably 100 parts by mass based on the total of the active energy ray-curable resin, the cerium oxide fine particles, and the photopolymerization initiator. It is 0.5 parts by mass or more and 7 parts by mass or less.

The thickness of the hard coat layer 13 is preferably 0.5 μm or more and 3.0 μm or less. When the thickness of the hard coat layer 13 is 0.5 μm or more, heat resistance in the manufacturing process of the semiconductor device can be improved, and when it is 3.0 μm or less, curling of the adhesive sheet 10 can be suppressed.

Examples of the active energy ray-sensitive composition used for forming the hard coat layer 13 include reactive cerium oxide microparticles, polyfunctional (meth) acrylate monomers, and (meth) acrylate systems. Prepolymer Active energy line sensing composition.

(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 composition contained in the adhesive layer 12 preferably contains an acrylic copolymer containing 2-ethylhexyl acrylate as a main monomer. 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. As the reactive functional group of the second copolymer component, when a crosslinking agent to be 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.

The acrylate having an epoxy group may, for example, be glycidol acrylate. Ester, 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. Examples of the (meth)acrylic acid alkyl esters include ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, n-amyl (meth)acrylate, and (methyl). ) n-hexyl acrylate, 2-ethylhexyl methacrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, (a) Base) Acrylic myristyl ester, palmityl (meth)acrylate, 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.

(meth) acrylate having an aliphatic ring, for example, (A Base) Cyclohexyl 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.

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, an acrylic copolymer obtained by copolymerizing 2-ethylhexyl acrylate, a carboxyl group-containing monomer, and a hydroxyl group-containing monomer is preferable. The body is preferably acrylic acid, a hydroxyl group-containing monomer, preferably 2-hydroxyethyl acrylate. Among the acrylic copolymers, copolymer components derived from 2-ethylhexyl acrylate are preferred. The ratio is 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, and the remainder is a copolymer component derived 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 adhesive composition constituting the adhesive layer 12 preferably contains an adhesive obtained by crosslinking a composition further blended with a crosslinking agent in addition to the acrylic copolymer. Further, the adhesive composition is preferably an adhesive obtained by crosslinking the acrylic copolymer and the crosslinking agent substantially as described above. Composition. Here, it is meant substantially that the adhesive is composed only of a small amount of impurities which are inevitably mixed with 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 the heat resistance and adhesion of the adhesive layer 12, among these crosslinking agents, a crosslinking agent containing a compound having an isocyanate group as a main component (isocyanate crosslinking agent) is particularly preferable. ) is better. 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 part by mass based on 100 parts by mass of the acrylic copolymer. The amount is more than 20 parts by mass, more preferably 1 part by mass or more and 15 parts by mass or less, still more preferably 5 parts by mass or more and 10 parts by mass or less. When the content of the crosslinking agent in the adhesive composition is within such a range, the adhesion between the adhesive layer 12 and the substrate 11 can be improved, and the ripening period for making the adhesive property stable after the production of the adhesive sheet can be shortened.

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 layer 12. The compound having a trimeric isocyanate ring 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 constituting the adhesive layer 12 in 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.

In the present embodiment, the adhesive composition constituting the adhesive layer 12 preferably contains a reactive adhesive auxiliary (hereinafter also referred to simply as "adhesive auxiliary"). The reactive adhesive agent is preferably a polybutadiene resin having a reactive functional group and a polybutadiene resin having a reactive functional group. Hydride, etc. The reactive functional group possessed by the reactive adhesion aid is preferably 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. More than one functional group of the group. When the adhesive composition contains a reactive adhesive agent, the residual adhesive when the adhesive sheet 10 is peeled off from the adherend can be reduced. The reactive adhesion aid is not particularly limited, and is preferably a terminal hydrogenated polybutadiene.

The content of the reactive adhesive auxiliary 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 reactive adhesive auxiliary in the adhesive composition is 3% by mass or more, there is no residual adhesive, and if it is 50% by mass or less, the adhesive strength is not lowered.

The adhesive composition constituting the adhesive layer 12 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, antioxidants, preservatives, mold inhibitors, plasticizers, antifoaming agents, and wettability adjustment. Agents, etc.

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, thereby preventing the gap. produce. 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.

(stripping sheet)

The release sheet RL is not particularly limited. For example, from the viewpoint of easiness of handling, the release sheet RL preferably has a release agent layer and a release agent layer formed by applying a release agent to the release substrate. Further, the release sheet RL may have a release agent layer only on one side of the release substrate, or may have a release agent layer on both surfaces 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 RL is not particularly limited. The thickness of the release sheet RL 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. Coating a solution containing a stripper When the release agent layer is formed, 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 the release substrate, the thickness of the plastic film is preferably 3 μm or more and 50 μm or less, more preferably 5 μm or more and 40 μm or less.

The adhesive sheet 10 of the present embodiment preferably exhibits the following adhesive force after heating. First, the adhesive sheet 10 is attached to an adherend (copper foil or polyimide film), heated at 100 ° C for 30 minutes, and then heated at 180 ° C for 30 minutes, further at 190 ° C and 1 After heating under an hour condition, the adhesion of the adhesive layer 12 to the copper foil at room temperature and the adhesion of the adhesive layer 12 to the polyimide film at room temperature are preferably 0.7 N/25 mm or more. 2.0N/25mm or less. 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 peeling speed (stretching 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 coating agent for a hard coat layer (hereinafter referred to as a hard coat agent) containing the above-described organic-inorganic hybrid material is prepared or prepared. In order to make the hard coating agent easy to apply, the hard coating agent is preferably in the form of a coating liquid by further adding a solvent. Examples of the solvent used for the hard coating agent include an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a halogenated hydrocarbon solvent, an alcohol solvent, a ketone solvent, an ester solvent, a cellosolve solvent, and an ether solvent. .

Examples of the aliphatic hydrocarbon solvent include hexane and heptane.

Examples of the aromatic hydrocarbon solvent include toluene and xylene.

Examples of the halogenated hydrocarbon-based solvent include dichloromethane and dichloroethane.

Examples of the alcohol solvent include methanol, ethanol, propanol, and butanol.

Examples of the ketone solvent include acetone, methyl ethyl ketone, 2-pentanone, isophorone, and cyclohexanone.

Examples of the ester solvent include ethyl acetate and butyl acetate.

Examples of the cellosolve-based solvent include ethyl cellosolve.

Examples of the ether solvent include propylene glycol monomethyl ether and the like.

In the hard coating agent to which the solvent is added as the coating liquid, the solid content concentration is preferably 1% by mass or more and 60% by mass or less, more preferably 5 or less, from the viewpoint of coatability and workability to the substrate. The mass% or more and 40% by mass or less.

Then, a hard coating agent is applied onto the second surface 11b of the substrate 11 to form a coating film, and after the coating film is dried, the coating film is irradiated with an active energy ray to cure the coating film, thereby forming a hard coat layer 13. . Examples of the coating method of the hard coating agent include a bar coating method, a knife coating method, a roll coating method, a knife coating method, a die coating method, and a gravure coating method. The active energy ray may, for example, be an ultraviolet ray or an electron beam, and is preferably ultraviolet ray. Ultraviolet rays can be irradiated, for example, using a high pressure mercury lamp, an electrodeless lamp, a metal halide lamp, or a xenon lamp. The amount of the ultraviolet irradiation is not particularly limited, and is preferably 100mJ / cm ² or more and 500mJ / cm ² or less, more preferably ² or less 150mJ / cm ² or more and 450mJ / cm. On the other hand, the electron beam can be irradiated using an electron beam accelerator or the like. The irradiation amount of the electron beam is not particularly limited, and is preferably 150 kV or more and 350 kV or less. Further, when an electron beam is used, a cured film can be obtained without adding a photopolymerization initiator.

Next, an adhesive composition is applied onto the first surface 11a of the substrate 11 to form a coating film. Next, the coating film is dried to form the adhesive layer 12. Thereafter, the release sheet RL is attached to the adhesive layer 12 to be applied.

Further, another manufacturing method of the adhesive sheet 10 is produced by the following steps. First, an adhesive composition is applied on the release sheet RL to form a coating film. Next, the coating film is dried to form the adhesive layer 12. The adhesive sheet 10 can also be produced by bonding the release sheet RL having the adhesive layer 12 and the substrate 11 having the hard coat layer 13. At this time, the adhesive layer 12 and the first surface 11a of the substrate 11 are bonded.

When the adhesive composition is applied to form the adhesive layer 12, it is preferred to prepare a coating liquid by diluting the adhesive composition with an organic solvent. Examples of the organic solvent include toluene, ethyl acetate, and methyl ethyl ketone. The method of applying the coating liquid is not particularly limited. The coating method may, for example, spin coating Method, spray coating method, bar coating method, knife coating method, roll knife coating method, roll coating method, blade coating method, die coating method, gravure coating method, and the like.

In order to prevent the organic solvent and the low boiling point component from remaining on the adhesive layer 12, it is preferred to apply the coating liquid to the substrate 11 or the release sheet RL, and then heat the coating film to dry. Further, 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 used not in sealing a semiconductor element mounted on a metal lead frame but in sealing a semiconductor element in a state of being adhered 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 step of adhering the reinforcing member 40 to the sealing body 50 sealed by the sealing resin 30 may be carried out after the thermosetting step as needed (the reinforcing member adhering step). The steps are explained below.

‧Adhesive sheeting step

2A is a schematic view showing a step of attaching the frame member 20 to the adhesive layer 12 of the adhesive sheet 10. Further, when the adhesive sheet 10 is attached to the release sheet RL, the release sheet RL is peeled off in advance.

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, and examples thereof include metals such as copper and stainless steel, and polyimine resins. And heat resistant resin such as 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.

‧ bonding 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 manufacture of the semiconductor wafer CP is performed, for example, by performing a back grinding step of grinding the back surface of the semiconductor wafer on which the circuit is formed, and a dicing step of singulating the semiconductor wafer. 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 cutting step, the extended cutting piece can also be implemented to expand a plurality of half The step of expanding the interval between the conductor 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 flaky sealing resin 30 is coated with a semiconductor crystal The sheet CP and the frame member 20 are placed in a manner, and the sealing resin 30 is heat-cured to form a 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 semiconductor wafer CP and the frame member 20 attached to the adhesive sheet 10 are accommodated. 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 also be performed before the step of thermally curing the sealing resin 30 (thermosetting 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. In the first heat pressing step, the hard coat layer 13 of the adhesive sheet 10 is in contact with the plate member, so that the contact of the substrate 11 with the plate member can be prevented. As the plate member, for example, a metal plate such as stainless steel can be used.

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.

‧Reinforcement components are attached to the steps

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 Figure 2D As shown in the figure, 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. Also in the second heat pressing step, the hard coat layer 13 of the adhesive sheet 10 is in contact with the plate-like member, so that the contact of the substrate 11 with the plate-like member can be prevented. In the second heating and pressing step, for example, a metal plate such as stainless steel may be used as the plate member.

‧ peeling step

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

In the embodiment, when the substrate 11 of the adhesive sheet 10 is bendable, The frame member 20, the semiconductor wafer CP, and the sealing resin layer 30A are 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 carried out with the sealing body 50 attached to the 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 the present embodiment, it is possible to provide the adhesive sheet 10 which can prevent contamination of equipment and members and prevent fusion with equipment and members even after the step of applying high temperature conditions. The second surface 11b of the substrate 11 of the adhesive sheet 10 is laminated with the hard coat layer 13, so that the plate-like member and the base of the stainless steel plate or the like can be prevented, for example, in the first heating pressing step and the second heating pressing step. Contact of material 11. Therefore, even if the base material 11 contains a polyester resin, contamination of equipment and members due to the oligomer of the substrate 11 can be prevented, and the equipment and the member can be further prevented from being fused with the substrate 11.

When the adhesive sheet 10 has the adhesive layer 12 containing the acrylic copolymer containing 2-ethylhexyl acrylate as a main monomer, the adhesive sheet 10 is easily peeled off by the adherend, and the residual adhesive can be reduced. In the present embodiment, the adherend to which the adhesive layer 12 is in contact is the semiconductor wafer CP and the frame member 20. In the state of being in contact with the semiconductor wafer CP and the frame member 20, the adhesive layer 12 is exposed to high temperature conditions. Compared with the adhesive sheet used in the conventional high-temperature process, the adhesive sheet 10 is easily peeled off even after exposure to high temperature conditions, and the residual amount of the semiconductor wafer CP and the frame member 20 is small.

[Second embodiment]

The adhesive sheet of the second embodiment differs from the adhesive sheet of the first embodiment in that it has two hard coat layers. The second embodiment is the same as the first embodiment, and thus the description will be omitted or simplified.

(adhesive sheet)

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

The adhesive sheet 10A has a substrate 11, an adhesive layer 12, and a hard coat layer 13.

The hard coat layer 13 of the present embodiment includes a first hard coat layer 13a and a second hard coat layer 13b. Similarly to the above-described embodiment, the base material 11 has a first surface 11a and a second surface 11b on the opposite side to the first surface 11a. In the adhesive sheet 10A of the present embodiment, the second hard coat layer 13b is laminated on the first surface 11a, the first hard coat layer 13a is laminated on the second surface 11b, and the second hard coat layer 13b is layered. The adhesive layer 12 is incorporated.

The thickness of the second hard coat layer 13b is preferably the same as the thickness of the hard coat layer 13 described in the first embodiment. The second hard coat layer 13b is preferably formed to cover the entire first surface 11a of the substrate 11.

The first hard coat layer 13a is a cured film formed by curing an organic-inorganic hybrid material, and contains a cured product of an organic-inorganic hybrid material. As the first hard coat layer 13a, an organic-inorganic hybrid material similar to that of the above embodiment can be used.

The second hard coat layer 13b contains a polyfunctional acrylic resin. The second hard coat layer 13b is preferably a cured film formed by curing the organic-inorganic hybrid material from the viewpoint of adhesion to the adhesive layer 12. The active energy ray-inductive composition used for forming the second hard coat layer 13b may be prepared by using the material described in the first embodiment, except that it is not an organic-inorganic hybrid material, and the second hard coat layer 13b, Better to make the live The performance amount of the wire-inductive composition is hardened to form a hardened film. The active energy ray-sensitive composition used for forming the second hard coat layer 13b preferably contains a polyfunctional (meth) acrylate monomer and (meth) acrylate, similarly to the above embodiment. At least one resin of the group of the ester-based prepolymers preferably contains a polyfunctional (meth)acrylate monomer.

An example of the active energy ray-sensitive composition used for forming the second hard coat layer 13b is exemplified by pentaerythritol tri(meth) acrylate and ethylene oxide modified dipentaerythritol hexa(meth) acrylate. An active energy ray-sensitive composition of a polyfunctional (meth) acrylate monomer.

An example of the first hard coat layer 13a of the present embodiment is an organic material containing reactive cerium oxide microparticles, a polyfunctional (meth) acrylate monomer, and a (meth) acrylate prepolymer. The inorganic hybrid material hardens the formed first hard coat layer 13a. An example of the second hard coat layer 13b at this time includes pentaerythritol tri(meth)acrylate as a polyfunctional (meth)acrylate monomer and ethylene oxide modified dipentaerythritol. The base of the acrylate, the 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator, and the active energy ray-sensitive composition of the oxime-modified acrylic leveling agent as a leveling agent Two hard coat layers 13b.

The manufacturing method of the adhesive sheet 10A is not specifically limited. For example, the adhesive sheet 10A is produced by the following steps.

First, a hard coating agent is prepared or prepared in the same manner as in the above embodiment. Connect Applying a hard coating agent to the second surface 11b of the substrate 11 to form a coating film, and after drying the coating film, the coating film is irradiated with an active energy ray to harden the coating film, thereby forming a first hard coating layer. 13a. Next, a hard coating agent is applied onto the first surface 11a of the substrate 11, and the coating film is cured in the same manner as described above to form the second hard coat layer 13b.

Next, an adhesive composition is applied onto the second hard coat layer 13b of the substrate 11 to form a coating film. Next, the coating film is dried to form the adhesive layer 12. Thereafter, the release sheet RL is attached to the adhesive layer 12 to be applied.

Further, another manufacturing method of the adhesive sheet 10A is produced by the following procedure. First, an adhesive composition is applied on the release sheet RL to form a coating film. Next, the coating film is dried to form the adhesive layer 12. The adhesive sheet 10A can also be produced by bonding the release sheet RL having the adhesive layer 12 and the substrate 11 having the first hard coat layer 13a and the second hard coat layer 13b. At this time, the adhesive layer 12 and the second hard coat layer 13b of the substrate 11 are bonded.

The adhesive sheet 10A can also be used in a manufacturing process of a semiconductor device similar to that of the above embodiment.

According to the present embodiment, it is possible to provide the adhesive sheet 10A which can prevent contamination of equipment and members and prevent fusion with equipment and members even after the step of applying high temperature conditions.

The adhesive sheet 10A further has the second hard coat layer 13b between the adhesive layer 12 and the substrate 11, so that the oligomer contained in the substrate 11 can be prevented from moving toward the adhesive layer 12.

Adhesive sheet 10A on both sides of substrate 11 (first surface 11a and The two sides 11b) are respectively laminated with a hard coat layer, so that the deformation of the substrate due to heating can be reduced.

[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.

The hard coat layer 13 may be formed to cover the entire second surface 11b of the substrate 11, or may have a region where the hard coat layer 13 is not formed. In the latter case, in the process using the adhesive sheet 10, the hard coat layer 13 may be formed so that the device and the member used in the process do not contact the substrate 11.

In the above embodiment, the method of producing the adhesive sheet is described by taking the hard coat layer 13 first and then forming the adhesive layer 12 as an example. However, the present invention is not limited to such a form. As another aspect of the method for producing the adhesive sheet, for example, the adhesive layer 12 may be formed on the substrate 11 first, and the adhesive layer 12 may be coated with the release sheet RL to form the hard coat layer 13.

In the above embodiment, the embodiment in which the adhesive layer 12 of the adhesive sheet 10 is coated by the release sheet RL is described as an example, but the present invention is not limited to such a form.

Further, the adhesive sheet 10 may be provided in a single piece or in a state in which a plurality of the adhesive sheets 10 may be laminated. At this time, for example, the adhesive layer 12, It can be covered by the hard coating 13 of the other adhesive sheets laminated.

Further, the adhesive sheet 10 may be a long-shaped sheet or may be provided in a state of being wound into a roll shape. The adhesive sheet 10 wound in a roll shape can be used by being wound around a drum and cut into a desired size or the like.

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.

[Adhesive sheet shrinkage evaluation]

The adhesive layers of the two adhesive sheets were bonded to each other, and cut into a size of 12 cm in length × 12 cm in width to obtain an adhesive sheet laminate. Fit 2 pieces When the sheets are adhered, the MD directions of the substrates of the respective adhesive sheets are made to match each other.

On the surface of the adhesive sheet laminate, a square mark of 10 cm in length × 10 cm in width was written. The square mark is written in such a manner that the sides of the square are along the MD direction of the substrate. The interval between the vertices of the written quadrilateral is measured using an electronic caliper, and the interval between the vertices is an initial value. Thereafter, the adhesive sheet laminate was heated at 190 ° C for 1 hour. After heating, the adhesive sheet laminate was returned to room temperature and the interval between the vertices of the square stamp was measured again. The shrinkage ratio of each side was calculated based on the measured values of the initial value and the interval after heating. When the shrinkage ratio in the MD direction of the substrate was 1.7% or less, it was judged as "A", and when the shrinkage ratio exceeded 1.7%, it was judged as "B".

[Adhesive evaluation of adhesive sheet]

The adhesive sheet was bonded to a copper foil having a thickness of 80 μm to obtain a copper foil-attached tape cut out to a size of 7 cm × 15 cm. From the upper side and the lower side of the copper foil-attached tape, the SUS plate (#1200 finishing) of the same size as the tape with the copper foil was sandwiched up and down. The copper foil-attached tape sandwiched between the SUS plates was heated and pressurized at 190 ° C, 2.5 MPa, and 90 minutes. After heating and pressurization, the surface state of the SUS plate which was in contact with the adhesive sheet was confirmed, and it was judged as "A" when there was no stain and fusion, and "B" when it was dirty.

[Adhesion assessment]

Heating at 100 ° C and 30 minutes, followed by 180 ° C and 30 The conditions were heated under minute conditions, and then the adhesive sheet was heated at 190 ° C for 1 hour. Thereafter, the adhesive layer was cross-cut into a checkerboard shape of 1 mm width, and the cross-cut was a checkerboard-like adhesive layer surface, and an adhesive tape (Nichiban Co., Ltd., trade name: Cellotape (registered) was attached. Trademark)), according to the "JIS K5600-5-6" board tape method (crosscut method), the adhesive tape peeling test was performed, and the adhesiveness of the adhesive layer and the base material was evaluated based on the following criteria. Among the 100 grids of the board, if the number of strips to be stripped is 10 or less, it is judged as "A", and when it exceeds 10, it is judged as "B".

[Production of Adhesive Sheet] (Example 1) (1) Fabrication of substrate

100 parts by mass of the hard coating agent containing the active energy ray-inductive composition and 83 parts by mass of propylene glycol monomethyl ether as a diluent solvent were uniformly mixed to prepare a hard coating agent HCl having a solid concentration of about 40% by mass. The hard coating agent HCl containing the active energy ray-sensitive composition is a trade name "Opstar Z7530" manufactured by JSR Co., Ltd., and contains an active energy ray-sensitive composition (70% by mass) and a photopolymerization initiator. (3% by mass) and methyl ethyl ketone (27% by mass), and the solid content concentration was 73% by mass. The composition of the active energy ray-inductive composition contains reactive cerium oxide fine particles (42% by mass in the hard coating agent), and a polyfunctional (meth) acrylate monomer and a (meth) acrylate system. Prepolymer (28% by mass in the hard coating agent).

The hard coating agent HCl was applied to a transparent polyethylene terephthalate film (manufactured by Toyobo Co., Ltd.; PET 50A-4300, thickness: 50 μm) using a bar coater. The hard coating agent HCl was applied so that the film thickness after drying and UV hardening became 1.5 μm. The drying conditions were set to 70 ° C and 1 minute. The UV curing was irradiated with ultraviolet rays of 150 mJ/cm ² with a high pressure mercury lamp. Thus, a substrate HCBS1 having a hard coat layer was produced.

(2) 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, 100 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: Hydroxylated polybutadiene at both ends (made by Japan Soda Co., Ltd.; GI-1000) 13 parts by mass (solid content)

‧ Crosslinking agent: aliphatic isocyanate having hexamethylene diisocyanate (trimeric isocyanate type modified product of hexamethylene diisocyanate) [manufactured by Polyurethane Industrial Co., Ltd.; Coronate HX], 9.0 parts by mass (solid content) )

‧Dilution solvent: a mixed solvent of toluene and MEK (methyl ethyl ketone) (toluene: MEK = 2:1 by volume), coating adhesive The solid content concentration of the liquid was prepared to be 30% by mass.

(3) Production of adhesive layer

The coating adhesive liquid to be applied is applied to a release layer provided with a polyoxynitride-based release layer by using a notch coater (Comma coater, registered trademark) so that the film thickness after drying is 50 μm. A peeling film formed of a transparent polyethylene terephthalate film (manufactured by LINTEC Co., Ltd.; SP-PET382150, thickness: 38 μm) was heated at 90 ° C for 90 seconds. Subsequently, heating at 115 ° C and 90 seconds was carried out to dry the coating film.

(4) Production of adhesive sheets

After the coating film of the coating adhesive liquid was dried, the adhesive layer and the substrate HCBS1 were bonded to each other to obtain an adhesive sheet of Example 1. The adhesive layer was bonded to the surface of the substrate opposite to the surface on which the hard coat layer was formed to obtain an adhesive sheet.

(Example 2)

The adhesive sheet of Example 2 was produced in the same manner as in Example 1 except that the type of the substrate on which the hard coat layer was formed was different from that of Example 1. In Example 2, a polyethylene terephthalate film (product name: PET50 KFL12D, thickness: 50 μm) made of Teijin DuPont Film Co., Ltd. was used, and the same adhesiveness as in Example 1 was applied to the film. The coating agent HCl forms a hard coat layer to obtain a substrate HCBS2 having a hard coat layer.

(Example 3)

The adhesive sheet of Example 3 was produced in the same manner as in Example 2 except that the hard coat layer was formed on both surfaces of the polyethylene terephthalate film of the substrate. The substrate HCBS3 having a hard coat layer of Example 3 was coated with the hard coat agent HC2 of Example 3 on the surface of the substrate HCBS1 opposite to the surface on which the hard coat layer was formed to form a hard coat layer.

The hard coating agent HC2 of Example 3 was prepared by mixing the components (A) to (D) according to the blending amounts shown below (all parts by mass (solid content ratio)), and preparing a curable resin composition, followed by propylene glycol. It is obtained by diluting monomethyl ether. The solid content concentration of the hard coating agent HC2 was 30% by mass.

(A) component

Pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-TMM-3L), 100 parts by mass (solid content).

(B) component

Ethylene oxide modified dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-DPH-12E), and 100 parts by mass (solid content).

(C) component

1-hydroxycyclohexyl phenyl ketone (manufactured by BASF Corporation, trade name: Irgacure 184, acetophenone photopolymerization initiator), 10 parts by mass (solid Body composition).

(D) component

A decane-modified acrylic leveling agent (manufactured by BYK-Chemie Japan Co., Ltd., trade name: BYK-3550) and 0.2 parts by mass (solid content).

The prepared hard coating agent HC2 of Example 3 was placed on the easy-advancing surface of the substrate HCBS1 on the opposite side to the surface on which the hard coat layer was formed, and the film thickness after drying was 3 μm using a metering bar (Meyer bar). The way to apply. After the coating film was dried at 80 ° C for 1 minute, the coating film was cured by irradiating ultraviolet rays at 300 mJ/cm ² (accumulated light amount) using a high-pressure mercury lamp to prepare a substrate HCBS3 having a second hard coat layer having a thickness of 3 μm.

When the adhesive layer and the substrate HCBS3 are bonded together, the adhesive layer is bonded to the surface opposite to the surface on which the hard coat layer using the hard coating agent HC2 is formed to obtain an adhesive sheet.

(Comparative Example 1)

The adhesive sheet of Comparative Example 1 was the same as Example 1 except that a hard coat layer was not formed and a transparent polyethylene terephthalate film (made of Toyobo Co., Ltd.; PET 50A-4300, thickness: 50 μm) was used as the substrate. Made in the same way.

(Comparative Example 2)

The adhesive sheet of Comparative Example 2, except that no hard coat layer was formed, and a polyethylene terephthalate film (manufactured by Teijin DuPont Film Co., Ltd.; PET 50) was used. KFL12D and thickness 50 μm were produced in the same manner as in Example 2 except that the substrate was used.

(Comparative Example 3)

The adhesive sheet of Comparative Example 3 was produced in the same manner as in Example 2 except that the hard coat layer of the substrate HCBS2 used in Example 2 was bonded to the adhesive layer.

Table 1 shows the layer constitution of the base material and the hard coat layer of the adhesive sheets of Examples 1 to 3 and Comparative Examples 1 to 3.

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

Since the adhesive sheets according to Examples 1 to 3 had a hard coat layer, fusion and contamination of the SUS plate did not occur in the heat resistance evaluation. On the other hand, in the adhesive sheets of Comparative Examples 1 to 3, the second side of the substrate (the surface opposite to the surface on which the adhesive layer was laminated) did not have a hard coat layer, and therefore the PET was applied to the SUS plate and the substrate. The film is heated in contact with the film, and the surface of the SUS plate is contaminated.

According to the adhesive sheets of the first to third embodiments, since the shrinkage ratio is low, it is possible to suppress the occurrence of a problem in the manufacturing process such as the manufacturing process of the semiconductor device.

According to the adhesive sheets of Examples 1 to 3, the adhesive layer and the substrate were excellent in adhesion. The adhesive sheet of Example 3 is provided with a hard coat layer between the substrate and the adhesive layer, and it is considered that the hard coat layer is formed by using the hard coat agent HC2, so that the adhesion between the hard coat layer and the adhesive layer is And the adhesion between the substrate and the hard coat layer is excellent.

10‧‧‧Adhesive sheets

11‧‧‧Substrate

11a‧‧‧ first side

11b‧‧‧ second side

12‧‧‧Adhesive layer

13‧‧‧hard coating

RL‧‧‧ peeling sheet

Claims (6)

An adhesive sheet which is used for sealing a semiconductor element on an adhesive sheet, and has a first surface and a second surface opposite to the first surface, and comprises a substrate and a layer of a polyester resin. An adhesive layer that is bonded to the first surface of the substrate and a hard coat layer that is laminated on the second surface of the substrate, and the hard coat layer is a cured film formed by curing an organic-inorganic hybrid material. The adhesive sheet according to claim 1, wherein the shrinkage ratio in the direction along any one of the substrates is 1.7% or less after heating at 190 ° C for 1 hour. The adhesive sheet according to claim 1, wherein the polyester resin is selected from the group consisting of polyethylene terephthalate resin, polyethylene naphthalate resin, and polybutylene terephthalate resin. Group of resins. The adhesive sheet of claim 1, wherein the thickness of the hard coat layer is 0.5 μm or more and 3.0 μm or less. An adhesive sheet according to claim 1, wherein a second hard coat layer is further provided between the adhesive layer and the substrate, and the second hard coat layer contains a polyfunctional acrylic resin. The adhesive sheet according to any one of Claims 1 to 5, wherein the organic-inorganic hybrid material contains a material obtained by bonding cerium oxide microparticles to an organic compound having a polymerizable unsaturated group, and Active energy ray-curable resin.