JP6714004B2 - Adhesive sheet - Google Patents

Description

The present invention relates to an adhesive sheet.

The adhesive sheet used in the manufacturing process of semiconductor devices is required to have various characteristics. In recent years, the pressure-sensitive adhesive sheet is required not to stain the devices, members, and adherends used in the manufacturing process even after undergoing a process under high temperature conditions. Further, after peeling the pressure-sensitive adhesive sheet at room temperature after the step of high temperature conditions, there is little problem that the pressure-sensitive adhesive remains on the adherend (so-called adhesive residue) and the peeling force is also small.

For example, Patent Document 1 describes a mask sheet for suppressing adhesive residue of an adhesive and stably producing a QFN (Quad Flat Non-lead) semiconductor package. In Patent Document 1, by making a mask sheet using a specific heat-resistant film and a silicone-based adhesive, it is possible to endure an environment of 1 hour to 6 hours at 150°C to 180°C in a die attach step and a resin sealing step. It is described as getting.

JP, 2002-275435, A

However, since the heat-resistant film such as a polyimide film and the silicone-based adhesive used in the production of the mask sheet described in Patent Document 1 are expensive, the mask sheet is used for some applications such as a QFN package. Limited
In recent years, pressure-sensitive adhesive sheets have been used even in processes that are subject to high temperature conditions such as 180° C. or higher and 200° C. or lower. In such a high temperature process, for example, when an inexpensive film (for example, a film such as polyethylene terephthalate) having a lower heat resistance than a polyimide film is used as a base material, it is There is a possibility that the oligomer may adhere to the equipment and the member to be contaminated, or the equipment and the member may be fused to the base material. When the base material is fused to the equipment and members, it becomes difficult to peel off the pressure-sensitive adhesive sheet, and even if it can be peeled off, the oligomer or the like of the base material remains on the equipment and members, and the equipment and members may be contaminated. For example, if high temperature conditions are imposed in the step of resin-sealing the semiconductor element attached to the adhesive layer of the adhesive sheet, the surface of the semiconductor element may be contaminated and the semiconductor device may be defective.

An object of the present invention is to provide a pressure-sensitive adhesive sheet capable of preventing contamination of equipment and members and preventing fusion with the equipment and members even after a step in which high temperature conditions are imposed. ..

According to one aspect of the present invention, a pressure-sensitive adhesive sheet used when sealing a semiconductor element on a pressure-sensitive adhesive sheet, having a first surface and a second surface opposite to the first surface, A base material containing 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 A pressure-sensitive adhesive sheet is provided, wherein the layer is a cured film formed by curing an organic-inorganic hybrid material.

In the pressure-sensitive adhesive sheet according to one aspect of the present invention, it is preferable that the shrinkage rate in the direction along any surface of the substrate is 1.7% or less after heating at 190° C. for 1 hour.

In the pressure-sensitive adhesive sheet according to one aspect of the present invention, the polyester resin is preferably a resin selected from the group consisting of polyethylene terephthalate resin, polyethylene naphthalate resin, and polybutylene terephthalate resin.

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

In the pressure-sensitive adhesive sheet according to one aspect of the present invention, the pressure-sensitive adhesive layer further has a second hard coat layer between the base material, and the second hard coat layer may include a polyfunctional acrylic resin. preferable.

In the pressure-sensitive adhesive sheet according to one aspect of the present invention, it is preferable that the organic-inorganic hybrid material includes a material in which silica fine particles are combined with an organic compound having a polymerizable unsaturated group, and an active energy ray curable resin.

Advantageous Effects of Invention According to the present invention, it is possible to provide a pressure-sensitive adhesive sheet that can prevent contamination of equipment and members, and can prevent fusion with equipment and members even after a step in which high temperature conditions are imposed. ..

It is a cross-sectional schematic diagram of the adhesive sheet which concerns on 1st embodiment. It is a figure explaining a part of manufacturing process of the semiconductor device using the adhesive sheet which concerns on 1st embodiment. It is a figure explaining a part of manufacturing process of the semiconductor device using the adhesive sheet which concerns on 1st embodiment. It is a figure explaining a part of manufacturing process of the semiconductor device using the adhesive sheet which concerns on 1st embodiment. It is a figure explaining a part of manufacturing process of the semiconductor device using the adhesive sheet which concerns on 1st embodiment. It is a figure explaining a part of manufacturing process of the semiconductor device using the adhesive sheet which concerns on 1st embodiment. It is a cross-sectional schematic diagram of the adhesive sheet which concerns on 2nd embodiment.

[First embodiment]
(Adhesive sheet)
FIG. 1 shows a schematic sectional view of the pressure-sensitive adhesive sheet 10 of the present embodiment.
The pressure-sensitive adhesive sheet 10 includes a base material 11, a pressure-sensitive adhesive layer 12, and a hard coat layer 13.
The base material 11 has a first surface 11a and a second surface 11b opposite to the first surface 11a. In the pressure-sensitive adhesive sheet 10 of the present embodiment, the pressure-sensitive adhesive layer 12 is laminated on the first surface 11a, and the hard coat layer 13 is laminated on the second surface 11b.
In this embodiment, a release sheet RL is laminated on the pressure-sensitive adhesive layer 12 as shown in FIG. The adhesive sheet 10 may have any shape such as a sheet shape, a tape shape, and a label shape.

(Base material)
The base material 11 includes a polyester resin. The base material 11 is more preferably made of a material containing a polyester resin as a main component. In the present specification, the material containing a polyester resin as a main component means that the mass ratio of the polyester resin to the total mass of the materials constituting the substrate is 50 mass% or more. The polyester resin is, for example, any resin selected from the group consisting of polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, and copolymer resin of these resins. Is more preferable, a resin selected from the group consisting of polyethylene terephthalate resin, polyethylene naphthalate resin, and polybutylene terephthalate resin is more preferable, and polyethylene terephthalate resin is still more preferable.
As the base material 11, a polyethylene terephthalate film or a polyethylene naphthalate film is preferable, and a polyethylene terephthalate film is more preferable. The oligomer contained in the polyester film is derived from polyester-forming monomers, dimers, trimers and the like.

In order to improve the adhesion between the base material 11 and the adhesive layer 12 and the adhesion between the base material 11 and the hard coat layer 13, the first surface 11a and the second surface 11b are treated with a primer, a corona, and a plasma. At least one surface treatment such as treatment may be applied. A pressure-sensitive adhesive may be applied to the first surface 11a and the second surface 11b of the base material 11 to perform a pressure-sensitive adhesive treatment. Examples of the pressure-sensitive adhesive used for the pressure-sensitive adhesive treatment of the base material include acrylic-based, rubber-based, silicone-based, and urethane-based pressure-sensitive adhesives.

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

After heating the pressure-sensitive adhesive sheet 10 at 190° C. for 1 hour, the shrinkage rate in the direction along any surface of the substrate 11 is preferably 1.7% or less.
After heating the pressure-sensitive adhesive sheet 10 under the conditions of 190° C. and 1 hour, it is preferable that at least the shrinkage rate in the MD direction of the base material 11 is 1.7% or less.
The manufacturing process of the semiconductor device includes a heating step at 180° C. to 190° C. for about 1 hour. If the shrinkage rate is 1.7% or less, the pressure-sensitive adhesive sheet 10 is adhered to the adherend due to the shrinkage of the base material 11. It can be prevented from peeling off. By preventing the pressure-sensitive adhesive sheet 10 from being peeled off from the adherend in the heating step, it is possible to prevent a conveyance problem during the manufacturing process. In addition, when the pressure-sensitive adhesive sheet 10 is peeled off, the surface of the adherend (for example, the circuit surface of the semiconductor chip) may be exposed and contaminated, but if the condition of the contraction rate described above is satisfied, such a case may occur. It can also prevent pollution.
In the present specification, the MD (MD: Machine Direction) direction of the base material 11 is a direction parallel to the longitudinal direction of the original fabric that gives the base material 11 (the feed direction during the production of the original fabric).

(Hard coat layer)
The hard coat layer 13 is a layer made 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 in which an organic component and an inorganic component are intimately mixed and cured in a state of being dispersed at a molecular level or a particle size close to the molecular level. Specifically, the organic component or the inorganic component is dispersed, for example, with a particle size of 100 nm or less. The organic-inorganic hybrid material used in the present embodiment is preferably a material capable of forming a cured film (hard coat film) by reacting with an inorganic component and an organic component to be cured by irradiation with an active energy ray. Examples of the active energy ray include ultraviolet rays and electron rays.
In addition, the particle size 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 device (Nanotrack Wave-UT151 manufactured by Microtrac Bell). ..

As the organic-inorganic hybrid material, an active energy ray-curable resin and an active energy ray-sensitive composition containing silica fine particles are preferable. By irradiating the active energy ray-sensitive composition with the above active energy ray, the composition is crosslinked and cured to obtain an organic-inorganic hybrid cured resin.
The organic-inorganic hybrid material in the present embodiment preferably contains a material in which silica fine particles are combined with an organic compound having a polymerizable unsaturated group, and an active energy ray curable resin. Since the organic-inorganic hybrid material contains silica fine particles, it is possible to reduce shrinkage during curing and prevent the pressure-sensitive adhesive sheet 10 from curling.

(Active energy ray curable resin)
In the present embodiment, the active energy ray-curable resin is a polymerizable compound that crosslinks and cures when irradiated with an active energy ray. By using a resin that cures with active energy rays, the thermal history of the base material 11 can be reduced. Examples of the active energy ray include electromagnetic waves such as ultraviolet rays and electron rays, and charged particle rays 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. As the polyfunctional acrylic resin, at least one resin selected from the group consisting of a polyfunctional (meth)acrylate monomer and a (meth)acrylate prepolymer is preferable, and a polyfunctional (meth)acrylate monomer is used. More preferable.
In the present specification, “(meth)acrylate” is a notation used to represent both acrylate and methacrylate, and the same applies to other similar terms.

Examples of the polyfunctional (meth)acrylate-based monomer include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di. (Meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone modified dicyclopentenyl di(meth)acrylate, ethylene oxide modified phosphoric acid di(meth)acrylate, ethylene oxide modified Dipentaerythritol hexa(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanurate di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid modified dipentaerythritol Tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl)isocyanurate, propionic acid modified dipentaerythritol penta(meth)acrylate, dipentaerythritol Hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate and the like can be mentioned.
The polyfunctional (meth)acrylate-based monomers may be used alone or in combination of two or more.

Examples of (meth)acrylate prepolymers include polyester (meth)acrylate prepolymers, epoxy (meth)acrylate prepolymers, urethane (meth)acrylate prepolymers, and polyol (meth)acrylate prepolymers. Can be mentioned.

The polyester (meth)acrylate prepolymer is obtained by, for example, obtaining a polyester oligomer having hydroxyl groups at both ends by condensation of a polyvalent carboxylic acid and a polyhydric alcohol, and further esterifying the hydroxyl groups with (meth)acrylic acid. Can be obtained by The polyester (meth)acrylate prepolymer is obtained, for example, by adding an alkylene oxide to a polyvalent carboxylic acid to obtain an oligomer, and esterifying the terminal hydroxyl group of this oligomer with (meth)acrylic acid. You can

The epoxy (meth)acrylate-based prepolymer can be obtained by, for example, reacting (meth)acrylic acid with the oxirane ring of a bisphenol type epoxy resin or a novolac type epoxy resin having a relatively low molecular weight to esterify.

The urethane (meth)acrylate prepolymer can be obtained, for example, by reacting a polyether polyol or polyester polyol with a polyisocyanate to obtain a polyurethane oligomer, and esterifying the polyurethane oligomer with (meth)acrylic acid. it can.

The polyol (meth)acrylate prepolymer can be obtained by esterifying the hydroxyl groups of the polyether polyol with (meth)acrylic acid.
In addition, these prepolymers may be used alone, two or more kinds may be used in combination, and may be used in combination with the polyfunctional (meth)acrylate-based monomer.

(Silica fine particles)
The average particle size of the silica fine particles is preferably 0.5 nm or more and 500 nm or less, and more preferably 1 nm or more and 100 nm or less. The average particle size of the silica fine particles is a value measured by the BET method, for example.

Among the silica fine particles, from the viewpoint of forming a strong bond with the active energy ray-curable resin, silica surface-modified with an organic compound having a polymerizable unsaturated group capable of reacting with the above active energy ray-curable resin. Fine particles (reactive silica fine particles) are preferred.

A silica fine particle surface-modified with an organic compound having a polymerizable unsaturated group is a polymerizable unsaturated group having a (meth)acryloyl group which is a functional group capable of reacting with the silanol group on the surface of the silica fine particle. It can be obtained by reacting the contained organic compound.
In the present embodiment, the organic compound having a polymerizable unsaturated group that modifies the surface of the silica fine particles may be a compound corresponding to the above active energy ray-curable resin. However, the compound that modifies the surface of the silica fine particles is included as a constituent element of the silica fine particles and is distinguished from the above active energy ray-curable resin.

As the polymerizable unsaturated group-containing organic compound having a functional group capable of reacting with the silanol group, for example, a compound represented by the following general formula (I) is preferable.

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

Examples of the polymerizable unsaturated group-containing organic compound include (meth)acrylic acid, (meth)acrylic acid chloride, 2-isocyanatoethyl (meth)acrylate, glycidyl (meth)acrylate, and (meth)acrylic acid 2 , 3-iminopropyl, 2-hydroxyethyl (meth)acrylate, and (meth)acrylic acid derivatives such as (meth)acryloyloxypropyltrimethoxysilane.
These polymerizable unsaturated group-containing organic compounds may be used alone or in combination of two or more.

The content of the silica fine particles in the organic-inorganic hybrid material is preferably 80 parts by mass or more and 400 parts by mass or less, and 100 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the active energy ray-curable resin. Is more preferable.

(Photopolymerization initiator)
The organic-inorganic hybrid material preferably contains a photopolymerization initiator.
Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]- 2-morpholino-propan-1-one, 4-(2-hydroxyethoxy)phenyl-2(hydroxy-2-propyl)ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2- Methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl Examples thereof include dimethyl ketal, acetophenone dimethyl ketal, and p-dimethylaminobenzoic acid ester.
Note that these photopolymerization initiators may be used alone or in combination of two or more kinds.

Commercially available organic-inorganic hybrid materials containing these active energy ray-curable resins, silica fine particles, and photopolymerization initiators include, for example, "OPSTAR Z7530", "OPSTAR Z7524", and "OPSTAR TU4086" (product The names include all manufactured by JSR Corporation.

The active energy ray-sensitive composition contains, if necessary, an ultraviolet absorber, a light stabilizer, an antioxidant, an infrared absorber, an antistatic agent, a leveling agent, an antifoaming agent within a range that does not impair the effects of the present invention. And at least one additive selected from the group consisting of Among these additives, from the viewpoint of improving light resistance, it is preferable to include at least one selected from the group consisting of an ultraviolet absorber and a light stabilizer.

(UV absorber)
The active energy ray-sensitive composition may contain an ultraviolet absorber.
Examples of the UV absorber include benzotriazole-based UV absorbers, hindered amine-based UV absorbers, benzophenone-based UV absorbers, and triazine-based UV absorbers. These ultraviolet absorbers may be used alone or in combination of two or more. Among these, radical-polymerizable ultraviolet absorbers having a radical-polymerizable double bond in the molecule are preferable.
The content of the ultraviolet absorber is preferably 0.2 parts by mass or more and 10 parts by mass or less, more preferably 0 parts by mass with respect to 100 parts by mass in total of the active energy ray-curable resin, the silica fine particles, and the photopolymerization initiator. It is not less than 0.5 parts by mass and not more than 7 parts by mass.

(Light stabilizer)
The active energy ray-sensitive composition may contain a light stabilizer.
Examples of the light stabilizer include hindered amine light stabilizers, benzophenone light stabilizers, and benzotriazole light stabilizers. These light stabilizers may be used alone or in combination of two or more kinds.
The content of the light stabilizer is preferably 0.2 parts by mass or more and 10 parts by mass or less, more preferably 0 parts by mass with respect to 100 parts by mass in total of the active energy ray-curable resin, the silica fine particles, and the photopolymerization initiator. It is not less than 0.5 parts by mass and not more than 7 parts by mass.

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 the thickness is 3.0 μm or less, curling of the pressure-sensitive adhesive sheet 10 can be suppressed.

As an example of the active energy ray-sensitive composition used for forming the hard coat layer 13, an active energy ray-sensitive composition containing reactive silica fine particles, a polyfunctional (meth)acrylate-based monomer, and a (meth)acrylate-based prepolymer. Mold compositions are included.

(Adhesive layer)
The pressure-sensitive adhesive layer 12 according to this embodiment contains a pressure-sensitive adhesive composition. The pressure-sensitive adhesive contained in this pressure-sensitive adhesive composition is not particularly limited, and various kinds of pressure-sensitive adhesives can be applied to the pressure-sensitive adhesive layer 12. Examples of the adhesive contained in the adhesive layer 12 include rubber-based, acrylic-based, silicone-based, polyester-based, and urethane-based adhesives. The type of the pressure-sensitive adhesive is selected in consideration of the use and the type of adherend to be attached.

The pressure-sensitive adhesive composition contained in the pressure-sensitive adhesive layer 12 preferably contains an acrylic copolymer having 2-ethylhexyl acrylate as a main monomer. In the present specification, the term "2-ethylhexyl acrylate as a main monomer" means that the proportion of the mass of the copolymer component derived from 2-ethylhexyl acrylate in the total mass of the acrylic copolymer is 50% by mass or more. Means In the present embodiment, the proportion 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, and 60% by mass or more and 95% by mass or less. Is more preferable, 80 mass% or more and 95 mass% or less is more preferable, and 85 mass% or more and 93 mass% or less is further preferable. When the proportion of the copolymer component derived from 2-ethylhexyl acrylate is 50% by mass or more, the adhesive strength does not become too high after heating and the adhesive sheet is more easily peeled off from the adherend, and 80% by mass or more. If so, it becomes easier to peel. When the proportion of the copolymer component derived from 2-ethylhexyl acrylate is 95% by mass or less, the initial adhesive force is insufficient and the base material is deformed during heating, or the deformation causes the pressure-sensitive adhesive sheet to peel off from the adherend. Can be prevented.

The type and number of 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 preferable. When the crosslinking agent described below is used, the reactive functional group of the second copolymer component is preferably a functional group capable of reacting with the crosslinking agent. This reactive functional group is preferably, for example, at least one substituent selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group, a substituted amino group, and an epoxy group, and at least one of a carboxyl group and a hydroxyl group. That substituent is more preferable, and a carboxyl group is still more preferable.

Examples of the monomer having a carboxyl group (carboxyl group-containing monomer) include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid. Among the carboxyl group-containing monomers, acrylic acid is preferable from the viewpoint of reactivity and copolymerizability. The carboxyl group-containing monomer may be used alone or in combination of two or more kinds.

Examples of the monomer having a hydroxyl group (hydroxyl group-containing monomer) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 2 -Hydroxybutyl, 3-hydroxybutyl (meth)acrylate, and hydroxyalkyl ester of (meth)acrylic acid such as 4-hydroxybutyl (meth)acrylic acid. Among the hydroxyl group-containing monomers, 2-hydroxyethyl (meth)acrylate is preferable from the viewpoint of reactivity of the hydroxyl group and copolymerizability. The hydroxyl group-containing monomer may be used alone or in combination of two or more kinds. In addition, in this specification, "(meth)acrylic acid" is a notation used to represent both "acrylic acid" and "methacrylic acid", and the same applies to other similar terms.

Examples of acrylic acid esters having an epoxy group include glycidyl acrylate and glycidyl methacrylate.

Other copolymer components in the acrylic copolymer include (meth)acrylic acid alkyl esters having an alkyl group with 2 to 20 carbon atoms. Examples of the alkyl (meth)acrylate include ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate, and n-(meth)acrylate. -Hexyl, 2-ethylhexyl methacrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, myristyl (meth)acrylate, palmityl (meth)acrylate, and ( Stearyl (meth)acrylate and the like can be mentioned. Among these (meth)acrylic acid alkyl esters, from the viewpoint of further improving the adhesiveness, a (meth)acrylic acid ester having an alkyl group having 2 to 4 carbon atoms is preferable, and (meth)acrylic acid n-butyl is more preferable. preferable. The (meth)acrylic acid alkyl ester may be used alone or in combination of two or more kinds.

Other copolymer components in the acrylic copolymer include, for example, alkoxyalkyl group-containing (meth)acrylic acid ester, (meth)acrylic acid ester having an aliphatic ring, and (meth)acrylic acid having an aromatic ring. A copolymer component derived from at least one monomer selected from the group consisting of ester, non-crosslinkable acrylamide, non-crosslinkable (meth)acrylic acid ester having a tertiary amino group, vinyl acetate, and styrene, Can be mentioned.
Examples of the alkoxyalkyl group-containing (meth)acrylic acid ester include methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, and ethoxyethyl (meth)acrylate. ..
Examples of the (meth)acrylic acid ester having an aliphatic ring include cyclohexyl (meth)acrylate.
Examples of the (meth)acrylic acid ester having an aromatic ring include phenyl (meth)acrylate.
Non-crosslinkable acrylamides include, for example, acrylamide and methacrylamide.
Examples of the non-crosslinkable (meth)acrylic acid ester having a tertiary amino group include (meth)acrylic acid (N,N-dimethylamino)ethyl and (meth)acrylic acid (N,N-dimethylamino). Examples include propyl.
These monomers may be used alone 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 copolymer component derived from acrylic acid accounts for the total mass of the acrylic copolymer. The mass ratio is preferably 1% by mass or less, and more preferably 0.1% by mass or more and 0.5% by mass or less. When the proportion of acrylic acid is 1% by mass or less, when the pressure-sensitive adhesive composition contains a crosslinking agent, it is possible to prevent the acrylic copolymer from crosslinking too quickly.

The acrylic copolymer may 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, and the hydroxyl group-containing monomer is preferably 2-hydroxyethyl acrylate. The proportion of the copolymer component derived from 2-ethylhexyl acrylate in the acrylic copolymer is 80% by mass or more and 95% by mass or less, and the proportion of the mass of the copolymer component derived from acrylic acid is 1% by mass or less. It is preferable that the balance 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 1,500,000 or less, and further preferably 800,000 or more and 1,200,000 or less. preferable. When the weight average molecular weight Mw of the acrylic copolymer is 300,000 or more, it can be peeled off without a residue of the adhesive on the adherend. When the weight average molecular weight Mw of the acrylic copolymer is 2,000,000 or less, it can be reliably attached to the adherend.
The weight average molecular weight Mw of the acrylic copolymer is a standard polystyrene conversion value measured by a gel permeation chromatography (GPC) method.

The acrylic copolymer can be produced using the above-mentioned various raw material monomers according to a conventionally known method.

The form of copolymerization of the acrylic copolymer is not particularly limited, and may be a block copolymer, a random copolymer, or a graft copolymer.
In this embodiment, the content of the acrylic copolymer in the pressure-sensitive adhesive composition is preferably 40% by mass or more and 90% by mass or less, and more preferably 50% by mass or more and 90% by mass or less.

The pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer 12 preferably contains a pressure-sensitive adhesive obtained by crosslinking a composition further containing a crosslinking agent, in addition to the acrylic copolymer described above. It is also preferable that the pressure-sensitive adhesive composition substantially comprises a pressure-sensitive adhesive obtained by crosslinking the above-mentioned acrylic copolymer and a crosslinking agent as described above. Here, “substantially” means that the pressure sensitive adhesive is composed of only the pressure sensitive adhesive, except for a trace amount of impurities that are unavoidably mixed in the pressure sensitive 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 chelate crosslinking agent, an amine crosslinking agent, and an amino resin crosslinking agent. These cross-linking agents may be used alone or in combination of two or more.
In the present embodiment, from the viewpoint of improving the heat resistance and adhesive strength of the pressure-sensitive adhesive layer 12, among these crosslinking agents, a crosslinking agent containing a compound having an isocyanate group as a main component (isocyanate-based crosslinking agent) is preferable. Examples of the isocyanate cross-linking agent include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, Polyphenyl isocyanate such as diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, and lysine isocyanate Compounds.
Further, the polyvalent isocyanate compound may be a trimethylolpropane adduct type modified product of the above compound, a buret type modified product reacted with water, or an isocyanurate type modified product having an isocyanurate ring.
In the present specification, a cross-linking agent containing a compound having an isocyanate group as a main component means that the proportion of the mass of the compound having an isocyanate group in the total mass of the components constituting the cross-linking agent is 50% by mass or more. To do.

In the present embodiment, the content of the cross-linking agent in the pressure-sensitive 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 with respect to 100 parts by mass of the acrylic copolymer. It is 15 parts by mass or less, more preferably 5 parts by mass or more and 10 parts by mass or less. When the content of the crosslinking agent in the pressure-sensitive adhesive composition is within such a range, the adhesiveness between the pressure-sensitive adhesive layer 12 and the base material 11 can be improved, and the pressure-sensitive adhesive property is stabilized after the production of the pressure-sensitive adhesive sheet. It is possible to shorten the curing period for allowing it.

In the present embodiment, from the viewpoint of heat resistance of the pressure-sensitive adhesive layer 12, the isocyanate crosslinking agent is more preferably a compound having an isocyanurate ring (isocyanurate-type modified product). The compound having an isocyanurate ring is preferably blended in an amount of 0.7 equivalent or more and 1.5 equivalent or less with respect to the hydroxyl equivalent of the acrylic copolymer. When the compounding amount of the compound having an isocyanurate ring is 0.7 equivalent or more, the adhesive force does not become too high after heating, the adhesive sheet is easily peeled off, and the adhesive residue can be reduced. When the compounding amount of the compound having an isocyanurate ring is 1.5 equivalents or less, it is possible to prevent the initial adhesive force from becoming too low, or prevent the sticking property from decreasing.

When the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer 12 in the present embodiment contains a crosslinking agent, it is preferable that the pressure-sensitive adhesive composition further contains a crosslinking accelerator. It is preferable to appropriately select and use the crosslinking accelerator depending on the type of the crosslinking agent. For example, when the pressure-sensitive adhesive composition contains a polyisocyanate compound as a crosslinking agent, it is preferable that the pressure-sensitive adhesive composition further contains an organometallic compound-based crosslinking accelerator such as an organotin compound.

In the present embodiment, it is also preferable that the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer 12 contains a reactive pressure-sensitive adhesive aid (hereinafter, also simply referred to as “adhesive aid”). Examples of the reactive adhesion aid include a polybutadiene-based resin having a reactive functional group and a hydrogenated product of a polybutadiene-based resin having a reactive functional group. As the reactive functional group which the reactive adhesive aid has, one or more functional groups selected from the group consisting of a hydroxyl group, an isocyanate group, an amino group, an oxirane group, an acid anhydride group, an alkoxy group, an acryloyl group and a methacryloyl group. It is preferably a group. When the pressure-sensitive adhesive composition contains a reactive pressure-sensitive adhesive aid, it is possible to reduce adhesive residue when the pressure-sensitive adhesive sheet 10 is peeled from the adherend. The reactive adhesion promoter is not particularly limited, but hydroxylated hydrogenated polybutadiene at both ends is preferable.

The content of the reactive adhesion aid in the pressure-sensitive adhesive composition is preferably 3% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 30% by mass or less. When the content of the reactive adhesion aid in the pressure-sensitive adhesive composition is 3% by mass or more, no adhesive residue is left, and when it is 50% by mass or less, the adhesive strength is not lowered.

The pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 12 may contain other components as long as the effects of the present invention are not impaired. Other components that may be contained in the pressure-sensitive adhesive composition include, for example, organic solvents, flame retardants, tackifiers, ultraviolet absorbers, antioxidants, preservatives, antifungal agents, plasticizers, defoamers, and wetting. Examples include sex regulators.

More specific examples of the pressure-sensitive adhesive composition according to this embodiment include the following pressure-sensitive adhesive composition examples, but the present invention is not limited to such examples.
As an example of the pressure-sensitive adhesive composition according to the present embodiment, an acrylic copolymer, an adhesion promoter, and a crosslinking agent are included, and the acrylic copolymer is at least 2-ethylhexyl acrylate, a carboxyl group-containing monomer. And an acrylic copolymer obtained by copolymerizing a hydroxyl group-containing monomer, wherein the adhesion aid contains a rubber-based material having a reactive group as a main component, and the cross-linking agent is an isocyanate cross-linking agent. An adhesive composition is mentioned.
As an example of the pressure-sensitive adhesive composition according to the present embodiment, an acrylic copolymer, an adhesion promoter, and a crosslinking agent are included, and the acrylic copolymer is at least 2-ethylhexyl acrylate, a carboxyl group-containing monomer. And an acrylic copolymer obtained by copolymerizing a hydroxyl group-containing monomer, wherein the adhesive aid is hydrogenated polybutadiene having hydroxyl groups at both ends, and the cross-linking agent is an isocyanate-based cross-linking agent. Can be mentioned.
As an example of the pressure-sensitive adhesive composition according to the present embodiment, an acrylic copolymer, an adhesion aid, and a crosslinking agent are included, and the acrylic copolymer is at least 2-ethylhexyl acrylate, acrylic acid and acrylic. An acrylic copolymer obtained by copolymerizing 2-hydroxyethyl acid, wherein the adhesion aid contains a rubber material having a reactive group as a main component, and the crosslinking agent is an isocyanate crosslinking agent. An adhesive composition may be mentioned.
As an example of the pressure-sensitive adhesive composition according to the present embodiment, an acrylic copolymer, an adhesion aid, and a crosslinking agent are included, and the acrylic copolymer is at least 2-ethylhexyl acrylate, acrylic acid and acrylic. A pressure-sensitive adhesive composition, which is an acrylic copolymer obtained by copolymerizing 2-hydroxyethyl acid, wherein the adhesion promoter is hydrogenated polybutadiene at both terminals and the crosslinking agent is an isocyanate crosslinking agent. Are listed.
In these examples of the pressure-sensitive adhesive composition according to the present embodiment, the proportion of the copolymer component derived from 2-ethylhexyl acrylate in the acrylic copolymer is 80% by mass or more and 95% by mass or less, and The mass ratio of the copolymer component derived from the group-containing monomer is 1% by mass or less, and the balance is preferably another copolymer component. The other copolymer component is a copolymer derived from the hydroxyl group-containing monomer. It is preferable to include a polymer component.

The thickness of the pressure-sensitive adhesive layer 12 is appropriately determined according to the application of the pressure-sensitive adhesive sheet 10. In this embodiment, the thickness of the pressure-sensitive adhesive layer 12 is preferably 5 μm or more and 60 μm or less, and more preferably 10 μm or more and 50 μm or less. If the pressure-sensitive adhesive layer 12 is too thin, the pressure-sensitive adhesive layer 12 may not be able to follow the irregularities on the circuit surface of the semiconductor chip, and a gap may occur. For example, an interlayer insulating material, a sealing resin, or the like may enter the gap and block the electrode pads for wiring connection on the chip circuit surface. When the thickness of the pressure-sensitive adhesive layer 12 is 5 μm or more, the pressure-sensitive adhesive layer 12 easily follows the irregularities on the chip circuit surface, and it is possible to prevent the occurrence of gaps. If the pressure-sensitive adhesive layer 12 is too thick, the semiconductor chip will sink into the pressure-sensitive adhesive layer, which may cause a step between the semiconductor chip portion and the resin portion that seals the semiconductor chip. If such a step occurs, the wiring may be broken during rewiring. When the thickness of the pressure-sensitive adhesive layer 12 is 60 μm or less, a step is less likely to occur.

(Peeling sheet)
The release sheet RL is not particularly limited. For example, from the viewpoint of easy handling, the release sheet RL preferably includes a release base material and a release agent layer formed by applying a release agent on the release base material. Moreover, the release sheet RL may be provided with a release agent layer only on one surface of the release base material, or may be provided with a release agent layer on both surfaces of the release base material. Examples of the release base material include a paper base material, a laminated paper obtained by laminating a thermoplastic resin such as polyethylene on the paper base material, and a plastic film. Examples of the paper base material include glassine paper, coated paper, and cast coated 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 olefin resins, rubber elastomers (eg, butadiene resins, isoprene resins, etc.), long chain alkyl resins, alkyd resins, fluorine resins, and silicone resins.

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, and preferably 25 μm or more and 150 μm or less.
The thickness of the release agent layer is not particularly limited. When a solution containing a release agent 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, and 0.03 μm or more and 1.0 μm or less. More preferable.
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, and more preferably 5 μm or more and 40 μm or less.

The adhesive sheet 10 according to the present embodiment preferably exhibits the following adhesive force after heating. First, the pressure-sensitive adhesive sheet 10 is adhered to an adherend (copper foil or polyimide film), heated at 100° C. for 30 minutes, then heated at 180° C. for 30 minutes, and further heated at 190° C. and 1 After heating under the condition of time, the adhesive strength of the adhesive layer 12 to the copper foil at room temperature and the adhesive strength of the adhesive layer 12 to the polyimide film at room temperature are 0.7 N/25 mm or more and 2.0 N/25 mm, respectively. The following is preferable. When the adhesive force after performing such heating is 0.7 N/25 mm or more, it is possible to prevent the pressure-sensitive adhesive sheet 10 from peeling from the adherend when the base material or the adherend is deformed by heating. Further, when the adhesive force after heating is 2.0 N/25 mm or less, the peeling force does not become too high and the adhesive sheet 10 is easily peeled from the adherend.
In addition, in this specification, room temperature is a temperature of 22° C. or higher and 24° C. or lower.
In addition, in the present specification, the adhesive force is a value measured by a 180° peeling method at a peeling speed (pulling speed) of 300 mm/min and a width of the adhesive sheet of 25 mm.

(Method for manufacturing adhesive sheet)
The method for manufacturing the adhesive sheet 10 is not particularly limited.
For example, the adhesive sheet 10 is manufactured through the following steps.
First, a coating agent for a hard coat layer (hereinafter, referred to as a hard coating agent) containing the above-mentioned organic-inorganic hybrid material is prepared or prepared. In order to facilitate application of the hard coating agent, it is preferable that the hard coating agent is further added with a solvent to form a coating solution. Examples of the solvent used for the hard coating agent include aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, alcohol solvents, ketone solvents, ester solvents, cellosolve solvents, and ethers. Examples include system solvents.
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 solvent include methylene chloride and ethylene chloride.
Examples of alcohol solvents include methanol, ethanol, propanol, and butanol.
Examples of ketone solvents include acetone, methyl ethyl ketone, 2-pentanone, isophorone, and cyclohexanone.
Examples of ester solvents include ethyl acetate and butyl acetate.
Examples of the cellosolve solvent include ethyl cellosolve and the like.
Examples of the ether solvent include propylene glycol monomethyl ether and the like.

In the hard coating agent obtained by adding a solvent to the coating solution, the solid content concentration is preferably 1% by mass or more and 60% by mass or less, more preferably 5% by mass or more and 40% by mass from the viewpoint of coating property on a substrate and workability. It is not more than mass %.

Then, the hard coating agent is coated on the second surface 11b of the base material 11 to form a coating film, the coating film is dried, and then the coating film is irradiated with active energy rays to form the coating film. The hard coat layer 13 is formed by curing the. Examples of the coating method of the hard coating agent include a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, and a gravure coating method. Examples of active energy rays include ultraviolet rays and electron beams, and ultraviolet rays are preferable. Ultraviolet rays can be irradiated using, for example, a high pressure mercury lamp, an electrodeless lamp, a metal halide lamp, a xenon lamp or the like. The dose of ultraviolet rays is not particularly limited, preferably 100 mJ / cm ² or more 500 mJ / cm ² or less, more preferably 150 mJ / cm ² or more 450 mJ / cm ² or less. On the other hand, the electron beam can be irradiated using an electron beam accelerator or the like. The irradiation dose of the electron beam is not particularly limited, but is preferably 150 kV or more and 350 kV or less. When an electron beam is used, a cured film can be obtained without adding a photopolymerization initiator.

Next, the pressure-sensitive adhesive composition is applied onto the first surface 11a of the base material 11 to form a coating film. Next, this coating film is dried to form the pressure-sensitive adhesive layer 12. Then, the release sheet RL is attached so as to cover the pressure-sensitive adhesive layer 12.

Moreover, as another manufacturing method of the adhesive sheet 10, it is manufactured through the following steps. First, the pressure-sensitive adhesive composition is applied onto the release sheet RL to form a coating film. Next, the coating film is dried to form the pressure-sensitive adhesive layer 12. The pressure-sensitive adhesive sheet 10 can also be manufactured by bonding the release sheet RL having the pressure-sensitive adhesive layer 12 and the base material 11 having the hard coat layer 13 described above. In this case, the pressure-sensitive adhesive layer 12 and the first surface 11a of the base material 11 are bonded together.

When the pressure-sensitive adhesive composition is applied to form the pressure-sensitive adhesive layer 12, it is preferable to dilute the pressure-sensitive adhesive composition with an organic solvent to prepare a coating solution for use. Examples of the organic solvent include toluene, ethyl acetate, and methyl ethyl ketone. The method of applying the coating liquid is not particularly limited. 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 blade coating method, a die coating method, and a gravure coating method.
In order to prevent the organic solvent and the low boiling point component from remaining in the pressure-sensitive adhesive layer 12, it is preferable to apply the coating liquid to the base material 11 or the release sheet RL and then heat and dry the coating film. When the pressure-sensitive adhesive composition contains a crosslinking agent, it is preferable to heat the coating film in order to promote the crosslinking reaction and improve the cohesive force.

(Use of adhesive sheet)
The adhesive sheet 10 is used when sealing a semiconductor element. The adhesive sheet 10 is not mounted on a metal lead frame, and is preferably used when sealing the semiconductor element in a state of being stuck on the adhesive sheet 10. Specifically, the pressure-sensitive adhesive sheet 10 is not used when sealing the semiconductor element mounted on the metal lead frame, but seals the semiconductor element attached to the pressure-sensitive adhesive layer 12. It is preferably used on the occasion. As a form of packaging a semiconductor device without using a metal lead frame, a panel scale package (PSP) and a wafer level package (WLP) are listed.
The adhesive sheet 10 includes a step of attaching a frame member having a plurality of openings to the adhesive sheet 10, and a step of attaching a semiconductor chip to the adhesive layer 12 exposed at the opening of the frame member. It is preferably used in a process including a step of covering the semiconductor chip with a sealing resin and a step of thermally curing the sealing resin.

(Method of manufacturing semiconductor device)
A method of manufacturing a semiconductor device using the adhesive sheet 10 according to this embodiment will be described.
2A to 2E are schematic diagrams illustrating the method for manufacturing the semiconductor device according to the present embodiment.
The method for manufacturing a semiconductor device according to the present embodiment includes a step of adhering the frame member 20 having a plurality of openings 21 formed on the adhesive sheet 10 (adhesive sheet adhering step) and an opening 21 of the frame member 20. A step of bonding the semiconductor chip CP to the adhesive layer 12 exposed as a result (bonding step), a step of covering the semiconductor chip CP with a sealing resin 30 (sealing step), and a step of thermally curing the sealing resin 30 ( The heat curing step) and the step of peeling the pressure sensitive adhesive sheet 10 after the heat curing (peeling step) are performed. If necessary, a step of attaching the reinforcing member 40 to the sealing body 50 sealed with the sealing resin 30 (reinforcing member attaching step) may be performed after the thermosetting step. Each step will be described below.

-Adhesive Sheet Adhering Step FIG. 2A is a schematic diagram illustrating a step of adhering the frame member 20 to the adhesive layer 12 of the adhesive sheet 10. When the release sheet RL is attached to the adhesive sheet 10, the release sheet RL is released in advance.
The frame member 20 according to 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 heat resistant resins such as polyimide resin and glass epoxy resin.
The opening 21 is a hole that penetrates the front and back surfaces of the frame member 20. The shape of the opening 21 is not particularly limited as long as the semiconductor chip CP can be accommodated in the frame. The depth of the hole of the opening 21 is not particularly limited as long as it can accommodate the semiconductor chip CP.

-Bonding step FIG. 2B is a schematic view illustrating a step of attaching the semiconductor chip CP to the adhesive layer 12.
When the pressure-sensitive adhesive sheet 10 is attached to the frame member 20, the pressure-sensitive adhesive layer 12 is exposed in each opening 21 according to the shape of the opening 21. The semiconductor chip CP is attached to the adhesive layer 12 of each opening 21. The semiconductor chip CP is attached so that the circuit surface thereof is covered with the adhesive layer 12.

The semiconductor chip CP is manufactured by, for example, performing a back grinding step of grinding the back surface of a semiconductor wafer on which circuits are formed and a dicing step of dividing the semiconductor wafer into individual pieces. In the dicing step, the semiconductor wafer is attached to the adhesive layer of the dicing sheet, and the semiconductor wafer is diced using a cutting means such as a dicing saw to obtain semiconductor chips CP (semiconductor elements).
The dicing device is not particularly limited, and a known dicing device can be used. The dicing conditions are also not particularly limited. Instead of the dicing method using a dicing blade, a laser dicing method or a stealth dicing method may be used.

After the dicing step, the expanding step may be performed in which the dicing sheet is stretched to expand the intervals between the plurality of semiconductor chips CP. By performing the expanding process, the semiconductor chip CP can be picked up by using a transporting means such as a collet. Further, by performing the expanding step, the adhesive force of the adhesive layer of the dicing sheet is reduced, and the semiconductor chip CP is easily picked up.
When the adhesive composition of the dicing sheet, or the energy ray-polymerizable compound is mixed in the adhesive layer, the adhesive layer is irradiated with energy rays from the base material side of the dicing sheet, and the energy ray-polymerizable compound is added. Let it harden. When the energy ray-polymerizable compound is cured, the cohesive force of the adhesive layer is increased and the adhesive force of the adhesive layer can be reduced. Examples of energy rays include ultraviolet rays (UV) and electron rays (EB), and ultraviolet rays are preferable. Irradiation with energy rays may be performed at any stage after the semiconductor wafer is attached and before the semiconductor chip is separated (picked up). For example, the energy rays may be irradiated before or after the dicing, or the energy rays may be irradiated after the expanding step.

-Sealing step and thermosetting step FIG. 2C is a schematic diagram illustrating a step of sealing the semiconductor chip CP and the frame member 20 attached to the adhesive sheet 10.
The material of the sealing resin 30 is a thermosetting resin, and examples thereof include 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 covering the semiconductor chip CP and the frame member 20 with the sealing resin 30 is not particularly limited.
In the present embodiment, a mode using the sheet-shaped sealing resin 30 will be described as an example. The sheet-shaped sealing resin 30 is placed so as to cover the semiconductor chip CP and the frame member 20, and the sealing resin 30 is heat-cured to form the sealing resin layer 30A. In this way, the semiconductor chip CP and the frame member 20 are embedded in the sealing resin layer 30A. When the sheet-shaped sealing resin 30 is used, it is preferable to seal the semiconductor chip CP and the frame member 20 by a vacuum laminating method. By this vacuum laminating method, it is possible to prevent a gap from being formed between the semiconductor chip CP and the frame member 20. The temperature condition range for heating by the vacuum laminating method is, for example, 80° C. or higher and 120° C. or lower.

In the sealing step, a laminated sheet in which the sheet-shaped sealing resin 30 is supported by a resin sheet such as polyethylene terephthalate may be used. In this case, after the laminated sheet is placed so as to cover the semiconductor chip CP and the frame member 20, the resin sheet may be peeled from the sealing resin 30 and the sealing resin 30 may be cured by heating. An example of such a laminated sheet is an ABF film (manufactured by Ajinomoto Fine-Techno Co., Inc.).

As a method of sealing the semiconductor chip CP and the frame member 20, a transfer molding method may be adopted. In this case, for example, the semiconductor chip CP attached to the adhesive sheet 10 and the frame member 20 are housed inside the mold of the sealing device. A fluid resin material is injected into the mold to cure the resin material. In the case of the transfer molding method, heating and pressure conditions are not particularly limited. As an example of normal conditions in the transfer molding method, a temperature of 150° C. or higher and a pressure of 4 MPa or more and 15 MPa or less are maintained for 30 seconds or more and 300 seconds or less. After that, the pressure is released, the cured product is taken out from the sealing device, and allowed to stand in an oven to maintain a temperature of 150° C. or higher for 2 hours or more and 15 hours or less. In this way, the semiconductor chip CP and the frame member 20 are sealed.

When the sheet-shaped sealing resin 30 is used in the above-described sealing step, the first hot pressing step may be performed before the step of thermally curing the sealing resin 30 (thermosetting step). In the first hot pressing step, the semiconductor chip CP covered with the sealing resin 30 and the pressure-sensitive adhesive sheet 10 with the frame member 20 are sandwiched by plate-like members from both sides and pressed under predetermined temperature, time, and pressure conditions. .. By performing the first hot pressing step, the sealing resin 30 is easily filled in the gap between the semiconductor chip CP and the frame member 20. In addition, by carrying out the hot pressing step, it is possible to flatten the unevenness of the sealing resin layer 30A made of the sealing resin 30. In the first hot pressing step, since the hard coat layer 13 of the adhesive sheet 10 contacts the plate-shaped member, it is possible to prevent the contact between the base material 11 and the plate-shaped member. As the plate member, for example, a metal plate such as stainless steel can be used.

After the thermosetting step, the adhesive sheet 10 is peeled off to obtain the semiconductor chip CP and the frame member 20 sealed with the sealing resin 30. Hereinafter, this may be referred to as the sealing body 50.

-Reinforcement member pasting process In Drawing 2D, the schematic diagram explaining the process of pasting up reinforcing member 40 to closure 50 is shown.
After peeling off the adhesive sheet 10, a rewiring step and a bumping step of forming a rewiring layer on the exposed circuit surface of the semiconductor chip CP are performed.
In order to improve the handleability of the sealing body 50 in such a rewiring step and a bumping step, a step of attaching the reinforcing member 40 to the sealing body 50 (reinforcing member attaching step) is performed as necessary. You may. When the step of attaching the reinforcing member is performed, it is preferable to perform the step before peeling the adhesive sheet 10. As shown in FIG. 2D, the sealing body 50 is supported while being sandwiched between the adhesive sheet 10 and the reinforcing member 40.

In the present embodiment, the reinforcing member 40 includes a heat resistant reinforcing plate 41 and a heat resistant adhesive layer 42. Examples of the reinforcing plate 41 include a plate-shaped member containing a heat resistant resin such as a glass epoxy resin. The adhesive layer 42 bonds the reinforcing plate 41 and the sealing body 50 together. The adhesive layer 42 is appropriately selected according to the materials of the reinforcing plate 41 and the sealing resin layer 30A.

In the reinforcing member attaching step, the adhesive layer 42 is sandwiched between the sealing resin layer 30A of the sealing body 50 and the reinforcing plate 41, and further sandwiched between the reinforcing plate 41 side and the pressure sensitive adhesive sheet 10 side by a plate-shaped member, and a predetermined size is obtained. It is preferable to carry out the second hot pressing step of pressing under the conditions of temperature, time, and pressure. The sealing body 50 and the reinforcing member 40 are temporarily fixed by the second heat pressing step. After the second hot pressing step, it is preferable to heat the temporarily fixed sealing body 50 and the reinforcing member 40 under a condition of a predetermined temperature and time in order to cure the adhesive layer 42. The conditions for heat curing are appropriately set according to the material of the adhesive layer 42, and are, for example, conditions of 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 contacts the plate-shaped member, so that the contact between the base material 11 and the plate-shaped member can be prevented. Also in the second heating and pressing step, for example, a metal plate such as stainless steel can be used as the plate-shaped member.

-Peeling Step FIG. 2E is a schematic diagram illustrating the step of peeling the pressure-sensitive adhesive sheet 10.
In this embodiment, when the base material 11 of the adhesive sheet 10 is bendable, it can be easily peeled from the frame member 20, the semiconductor chip CP, and the sealing resin layer 30A while bending the adhesive sheet 10. The peeling angle θ is not particularly limited, but 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 from the frame member 20, the semiconductor chip CP, and the sealing resin layer 30A. The peeling angle θ is preferably 90 degrees or more and 180 degrees or less, and more preferably 135 degrees or more and 180 degrees or less. By peeling the pressure-sensitive adhesive sheet 10 while bending it in this way, it is possible to reduce the load applied to the frame member 20, the semiconductor chip CP and the sealing resin layer 30A, and by peeling the pressure-sensitive adhesive sheet 10, the semiconductor Damage to the chip CP and the sealing resin layer 30A can be suppressed. After the adhesive sheet 10 is peeled off, the above-mentioned rewiring step, bumping step and the like are performed. After the peeling of the pressure-sensitive adhesive sheet 10, before the rewiring step and the bumping step, etc., the above-mentioned reinforcing member attaching step may be performed if necessary.

When the reinforcing member 40 is attached, the reinforcing member 40 is peeled from the sealing body 50 at the stage when the supporting by the reinforcing member 40 is no longer necessary after the rewiring process and the bumping process are performed.
After that, the sealing body 50 is separated into individual semiconductor chips CP (separation step). The method for dividing the sealing body 50 into individual pieces is not particularly limited. For example, the semiconductor wafer can be diced into individual pieces by the same method as that used when dicing the semiconductor wafer. The step of dividing the sealing body 50 into individual pieces may be performed with the sealing body 50 attached to a dicing sheet or the like. By separating the sealing body 50 into individual pieces, a semiconductor package for each semiconductor chip CP is manufactured, and this semiconductor package is mounted on a printed wiring board or the like in a mounting step.

According to the present embodiment, it is possible to provide a pressure-sensitive adhesive sheet 10 capable of preventing contamination of equipment and members and preventing fusion with the equipment and members even after a process in which high temperature conditions are imposed. You can Since the hard coat layer 13 is laminated on the second surface 11b of the base material 11 of the pressure-sensitive adhesive sheet 10, for example, a plate-shaped member such as a stainless steel plate is used in the above-described first heating and pressing step and the second heating and pressing step. Contact with the base material 11 can be prevented. Therefore, even if the base material 11 contains the polyester-based resin, it is possible to prevent the equipment and members from being contaminated by the oligomers caused by the base material 11, and also to prevent the equipment and members from being fused to the base material 11.

When the pressure-sensitive adhesive sheet 10 has the pressure-sensitive adhesive layer 12 containing an acrylic copolymer whose main monomer is 2-ethylhexyl acrylate, the pressure-sensitive adhesive sheet 10 is easily peeled off from the adherend and has less adhesive residue. You can In this embodiment, the adherends with which the adhesive layer 12 is in contact are the semiconductor chip CP and the frame member 20. The adhesive layer 12 is exposed to high temperature conditions while being in contact with the semiconductor chip CP and the frame member 20. Compared with the pressure-sensitive adhesive sheet used in the conventional high-temperature process, the pressure-sensitive adhesive sheet 10 can be easily peeled off even after being exposed to high-temperature conditions, and adhesive residue on the semiconductor chip CP and the frame member 20 is small. ..

[Second embodiment]
The adhesive sheet according to the second embodiment is different from the adhesive sheet according to the first embodiment in that it has two hard coat layers. The second embodiment is similar to the first embodiment in other respects, and thus the description thereof will be omitted or simplified.

(Adhesive sheet)
FIG. 3 shows a schematic cross-sectional view of the pressure-sensitive adhesive sheet 10A of this embodiment.
The pressure-sensitive adhesive sheet 10A includes a base material 11, a pressure-sensitive adhesive layer 12, and a hard coat layer 13.
The hard coat layer 13 of this embodiment includes a first hard coat layer 13a and a second hard coat layer 13b. The base material 11 has a first surface 11a and a second surface 11b opposite to the first surface 11a, as in the above embodiment. 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 adhesive layer is on the second hard coat layer 13b. 12 are stacked.
The thickness of the second hard coat layer 13b is preferably in the same range as the hard coat layer 13 described in the first embodiment. The second hard coat layer 13b is preferably formed so as to cover the entire first surface 11a of the base material 11.

The first hard coat layer 13a is a cured film formed by curing an organic-inorganic hybrid material, and includes a cured product of the organic-inorganic hybrid material. For forming the first hard coat layer 13a, the same organic-inorganic hybrid material as in the above-described embodiment can be used.
The second hard coat layer 13b contains a polyfunctional acrylic resin. The second hard coat layer 13b is preferably not a cured film formed by curing an organic-inorganic hybrid material from the viewpoint of adhesion with the pressure-sensitive adhesive layer 12. The active energy ray-sensitive composition used for forming the second hard coat layer 13b can be prepared using the material described in the first embodiment except that it is not an organic-inorganic hybrid material. The layer 13b is preferably a cured film formed by curing the active energy ray-sensitive composition. The active energy ray-sensitive composition used for forming the second hard coat layer 13b is also at least selected from the group consisting of polyfunctional (meth)acrylate-based monomers and (meth)acrylate-based prepolymers, as in the above embodiment. It is preferable to contain one kind of resin, and it is more preferable to contain a polyfunctional (meth)acrylate-based monomer.
As an example of the active energy ray-sensitive composition used for forming the second hard coat layer 13b, pentaerythritol tri(meth)acrylate as a polyfunctional (meth)acrylate-based monomer, and ethylene oxide-modified dipentaerythritol hexa(meth) are used. ) An active energy ray-sensitive composition containing an acrylate is mentioned.
As an example of the first hard coat layer 13a according to the present embodiment, an organic-inorganic hybrid material containing reactive silica fine particles, a polyfunctional (meth)acrylate-based monomer, and a (meth)acrylate-based prepolymer is cured to The formed first hard coat layer 13a may be mentioned. As an example of the second hard coat layer 13b in this case, pentaerythritol tri(meth)acrylate as a polyfunctional (meth)acrylate-based monomer and ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, as a photopolymerization initiator The second hard coat layer 13b is formed by curing an active energy ray-sensitive composition containing 1-hydroxycyclohexyl phenyl ketone and a siloxane-modified acrylic leveling agent as a leveling agent.

The method for manufacturing the adhesive sheet 10A is not particularly limited. For example, the adhesive sheet 10A is manufactured through the following steps.
First, a hard coat agent is prepared or prepared in the same manner as in the above embodiment. Next, a hard coat agent is coated on the second surface 11b of the base material 11 to form a coating film, the coating film is dried, and then the coating film is irradiated with active energy rays to form the coating film. The first hard coat layer 13a is formed by curing the film. Next, the second hard coat layer 13b is formed by coating the first surface 11a of the base material 11 with a hard coat agent and curing the coating film in the same manner as described above.
Next, the pressure-sensitive adhesive composition is applied on the second hard coat layer 13b of the base material 11 to form a coating film. Next, this coating film is dried to form the pressure-sensitive adhesive layer 12. Then, the release sheet RL is attached so as to cover the pressure-sensitive adhesive layer 12.
Moreover, as another manufacturing method of the adhesive sheet 10A, it is manufactured through the following steps. First, the pressure-sensitive adhesive composition is applied onto the release sheet RL to form a coating film. Next, the coating film is dried to form the pressure-sensitive adhesive layer 12. The pressure-sensitive adhesive sheet 10A can also be manufactured by bonding the release sheet RL having the pressure-sensitive adhesive layer 12 and the base material 11 having the first hard coat layer 13a and the second hard coat layer 13b described above. In this case, the pressure-sensitive adhesive layer 12 and the second hard coat layer 13b of the base material 11 are bonded together.

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

According to the present embodiment, it is possible to provide a pressure-sensitive adhesive sheet 10A capable of preventing contamination of equipment and members and preventing fusion with the equipment and members even after a process in which high temperature conditions are imposed. You can
Since the pressure-sensitive adhesive sheet 10A further includes the second hard coat layer 13b between the pressure-sensitive adhesive layer 12 and the base material 11, the oligomer contained in the base material 11 can be prevented from moving to the pressure-sensitive adhesive layer 12.
In the pressure-sensitive adhesive sheet 10A, since the hard coat layers are laminated on both surfaces (first surface 11a and second surface 11b) of the base material 11, deformation of the base material due to heating can be reduced.

[Modification of Embodiment]
The present invention is not limited to the above-described embodiments, and modifications and improvements as long as the object of the present invention can be achieved are included in the present invention. In the following description, the same members as those described in the above embodiment will be designated by the same reference numerals, and the description thereof will be omitted or simplified.

The hard coat layer 13 may be formed so as to cover the entire second surface 11b of the base material 11, or may have a region where the hard coat layer 13 is not formed. In the latter case, in the process of using the pressure-sensitive adhesive sheet 10, the hard coat layer 13 may be formed so that the device and members used during the process do not come into contact with the base material 11.

In the embodiment, as the method for producing the pressure-sensitive adhesive sheet, the hard coat layer 13 was first formed and then the pressure-sensitive adhesive layer 12 was formed as an example, but the present invention is limited to such a mode. Not done. As another aspect of the method for producing a pressure-sensitive adhesive sheet, for example, a mode in which the pressure-sensitive adhesive layer 12 is first formed on the base material 11, the pressure-sensitive adhesive layer 12 is covered with the release sheet RL, and then the hard coat layer 13 is formed. May be

In the embodiment, the mode in which the pressure-sensitive adhesive layer 12 of the pressure-sensitive adhesive sheet 10 is covered with the release sheet RL has been described as an example, but the present invention is not limited to such a mode.
The adhesive sheet 10 may be a single sheet, or may be provided in a state where a plurality of adhesive sheets 10 are laminated. In this case, for example, the pressure-sensitive adhesive layer 12 may be covered with the hard coat layer 13 of another pressure-sensitive adhesive sheet to be laminated.
The adhesive sheet 10 may be a long sheet or may be provided in a rolled-up state. The pressure-sensitive adhesive sheet 10 wound into a roll can be fed from a roll and cut into a desired size for use.

In the above embodiment, the case where the sealing resin 30 is a thermosetting resin has been described as an example, but the present invention is not limited to such an aspect. For example, the sealing resin 30 may be an energy ray curable resin that is cured by energy rays such as ultraviolet rays.

In the above-described embodiment, in the description of the method for manufacturing a semiconductor device, the mode in which the frame member 20 is attached to the adhesive sheet 10 has been described as an example, but the present invention is not limited to such a mode. 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.

Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples.

〔Evaluation method〕
The pressure-sensitive adhesive sheet was evaluated according to the method described below.

[Adhesive sheet shrinkage evaluation]
The pressure-sensitive adhesive layers of the two pressure-sensitive adhesive sheets were adhered to each other and cut into a size of 12 cm (length)×12 cm (width) to obtain a pressure-sensitive adhesive sheet laminate. When the two adhesive sheets were attached together, the MD directions of the base materials of the respective adhesive sheets were aligned and attached.
On the surface of this pressure-sensitive adhesive sheet laminate, a square mark having a length of 10 cm and a width of 10 cm was written. The square mark was written so that the side of the square was along the MD direction of the substrate. The intervals between the vertices of the written quadrangle were measured using an electronic caliper, and the intervals between the vertices were used as initial values. Then, the pressure-sensitive adhesive sheet laminate was heated at 190° C. for 1 hour. After heating, the pressure-sensitive adhesive sheet laminate was returned to room temperature, and then the intervals between the vertices of the square marks were measured again. The shrinkage rate of each side was calculated based on the initial value and the measured value of the interval after heating. When the shrinkage rate of the base material in the MD direction was 1.7% or less, it was determined as "A", and when the shrinkage rate exceeded 1.7%, it was determined as "B".

[Adhesive sheet heat resistance evaluation]
The adhesive sheet was attached to a copper foil having a thickness of 80 μm and cut into a size of 7 cm×15 cm to obtain a tape with copper foil. From the upper surface side and the lower surface side of this tape with copper foil, it was sandwiched vertically using a SUS plate (#1200 finish) of the same size as the tape with copper foil. The tape with copper foil sandwiched between SUS plates was heated and pressed under the conditions of 190° C., 2.5 MPa, and 90 minutes. After heating and pressurizing, the surface state of the SUS plate that was in contact with the pressure-sensitive adhesive sheet was confirmed, and when there was no stain or fusion, it was judged as "A", and when stain was generated, it was judged as "B".

[Adhesion evaluation]
The adhesive sheet was heated under the conditions of 100° C. and 30 minutes, followed by heating under the conditions of 180° C. and 30 minutes, and then under the conditions of 190° C. and 1 hour. After that, a 1 mm-width cross-cut cross-cut is applied to the pressure-sensitive adhesive layer, and the cross-cut cross-cut pressure-sensitive adhesive layer surface has an adhesive tape (Nichiban Co., Ltd., trade name: Sellotape (registered trademark) )) is adhered and a peeling test of the adhesive tape is performed according to the cross-cut tape method (cross-cut method) of "JIS K5600-5-6", and the adhesion between the adhesive layer and the base material is determined by the following criteria. It was evaluated based on. Of the 100 squares in the grid, the number of peeled squares was 10 or less, which was determined as "A", and when the number of squares exceeded 10 was determined as "B".

[Preparation of adhesive sheet]
(Example 1)
(1) Preparation of Base Material 100 parts by mass of a hard coating agent containing an active energy ray-sensitive composition and 83 parts by mass of propylene glycol monomethyl ether as a diluting solvent are uniformly mixed, and the solid content concentration is about 40% by mass. A certain hard coat agent HC1 was prepared. The hard coat agent HC1 containing the active energy ray-sensitive composition used is "OPSTAR Z7530", a trade name manufactured by JSR Corporation, and the active energy ray-sensitive composition (70% by mass), a photopolymerization initiator (3 mass %) and methyl ethyl ketone (27 mass %), and the solid content concentration is 73 mass %. The composition of the active energy ray-sensitive composition is as follows: reactive silica fine particles (42% by mass in the hard coating agent), polyfunctional (meth)acrylate-based monomer and (meth)acrylate prepolymer (in the hard coating agent). 28% by mass).
The hard coat agent HC1 was applied to the easy-adhesion surface of a transparent polyethylene terephthalate film [Toyobo Co., Ltd.; PET50A-4300, thickness 50 μm] using a bar coater. The hard coat agent HC1 was applied such that the film thickness after drying and UV curing was 1.5 μm. The drying conditions were 70° C. and 1 minute. The UV curing was performed by irradiating 150 mJ/cm ² of ultraviolet rays with a high pressure mercury lamp. In this way, a base material HCBS1 having a hard coat layer was produced.

(2) Preparation of pressure-sensitive adhesive composition The following materials (polymer, adhesion promoter, cross-linking agent, and diluting solvent) were blended and sufficiently stirred, and the pressure-sensitive adhesive liquid for application according to Example 1 (pressure-sensitive adhesive composition Was prepared.

-Polymer: acrylic acid ester copolymer, 100 parts by mass (solid content)
The acrylic ester 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.

Adhesion assistant: 13 parts by mass (solid content) of hydrogenated polybutadiene having hydroxyl groups at both ends [manufactured by Nippon Soda Co., Ltd.; GI-1000]

-Crosslinking agent: Aliphatic isocyanate having hexamethylene diisocyanate (isocyanurate-type modified hexamethylene diisocyanate) [Nippon Polyurethane Industry Co., Ltd.; Coronate HX], 9.0 parts by mass (solid content)

-Diluting solvent: Using a mixed solvent of toluene and MEK (methyl ethyl ketone) (toluene:MEK=2:1 in volume ratio), the solid content concentration of the pressure-sensitive adhesive liquid for coating was adjusted to 30% by mass.

(3) Preparation of pressure-sensitive adhesive layer The prepared pressure-sensitive adhesive liquid for application was prepared from a transparent polyethylene terephthalate film provided with a silicone release layer so that the film thickness after drying was 50 μm using Comma Coater (registered trademark). The release film [SP-PET382150, manufactured by Lintec Co., Ltd.; thickness 38 μm] was applied to the release layer surface side and heated at 90° C. for 90 seconds. Subsequently, the coating film was dried by heating at 115° C. for 90 seconds.

(4) Preparation of pressure-sensitive adhesive sheet After drying the coating film of the pressure-sensitive adhesive liquid for coating, the pressure-sensitive adhesive layer and the substrate HCBS1 were bonded together to obtain a pressure-sensitive adhesive sheet according to Example 1. An adhesive layer was attached to the surface of the base material opposite to the surface on which the hard coat layer was formed to obtain an adhesive sheet.

(Example 2)
The pressure-sensitive adhesive sheet according to Example 2 was produced in the same manner as in Example 1 except that the type of substrate on which the hard coat layer was formed was different from that in Example 1. In Example 2, a polyethylene terephthalate film (product name: PET50 KFL12D, thickness 50 μm) manufactured by Teijin DuPont Films Ltd. was used, and the same hard coating agent HC1 as in Example 1 was applied to the easily adhesive surface of this film, A hard coat layer was formed to obtain a base material HCBS2 having a hard coat layer.

(Example 3)
The pressure-sensitive adhesive sheet according to Example 3 was produced in the same manner as in Example 2 except that the hard coat layers were formed on both sides of the base material polyethylene terephthalate film. The base material HCBS3 having the hard coat layer of Example 3 was coated with the hard coat agent HC2 of Example 3 on the surface opposite to the surface of the base material HCBS1 on which the hard coat layer was formed. Layers were formed.
The hard coating agent HC2 according to Example 3 was mixed with the components (A) to (D) in the following blending amounts (all are parts by mass (solid content ratio)) to prepare a curable resin composition. Then, it was obtained by diluting with propylene glycol monomethyl ether. The solid content concentration of the hard coat agent HC2 was 30% by mass.

Component (A) 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), 100 parts by mass (solid content).

Component (C) 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF, trade name: Irgacure 184, acetophenone photoinitiator), 10 parts by mass (solid content).

Component (D) A siloxane-modified acrylic leveling agent (manufactured by BYK Japan KK, trade name: BYK-3550), 0.2 parts by mass (solid content).

The prepared hard coating agent HC2 of Example 3 was applied to the easy-adhesion surface of the base material HCBS1 opposite to the surface on which the hard coating layer was formed so that the film thickness after drying was 3 μm using a Meyer bar. Was applied to. After the coating film is dried at 80° C. for 1 minute, it is irradiated with ultraviolet rays of 300 mJ/cm ² (accumulated light amount) by using a high pressure mercury lamp to cure the coating film and have a second hard coat layer having a film thickness of 3 μm. A base material HCBS3 was produced.
When the pressure-sensitive adhesive layer and the base material HCBS3 are bonded together, the pressure-sensitive adhesive layer is bonded to the surface opposite to the surface on which the hard coat layer using the hard coat agent HC2 is formed, and the pressure-sensitive adhesive layer is adhered. Got the sheet.

(Comparative Example 1)
The pressure-sensitive adhesive sheet according to Comparative Example 1 was prepared in the same manner as in Example 1 except that a transparent polyethylene terephthalate film [manufactured by Toyobo Co., Ltd.; PET50A-4300, thickness 50 μm] was used as a substrate without forming a hard coat layer. It was made.

(Comparative example 2)
The pressure-sensitive adhesive sheet according to Comparative Example 2 was the same as that of Example 2 except that a polyethylene terephthalate film [manufactured by Teijin DuPont Films; PET50 KFL12D, thickness 50 μm] was used as a substrate without forming a hard coat layer. It was made.

(Comparative example 3)
The pressure-sensitive adhesive sheet according to Comparative Example 3 was produced in the same manner as in Example 2 except that the hard coat layer of the base material HCBS2 used in Example 2 and the pressure-sensitive adhesive layer were bonded together.

Table 1 shows the layer configurations of the base material and the hard coat layer of the pressure-sensitive adhesive sheets according to Examples 1 to 3 and Comparative Examples 1 to 3.

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

According to the pressure-sensitive adhesive sheets of Examples 1 to 3, since the pressure-sensitive adhesive sheets have the hard coat layer, fusion with the SUS plate and contamination did not occur in the heat resistance evaluation. On the other hand, in the pressure-sensitive adhesive sheets of Comparative Examples 1 to 3, since the second surface of the base material (the surface opposite to the surface on which the pressure-sensitive adhesive layer is laminated) does not have a hard coat layer, the SUS plate and the base material The surface of the SUS plate was contaminated by being heated in contact with the PET film of.
According to the pressure-sensitive adhesive sheets of Examples 1 to 3, since the shrinkage rate was low, it is possible to suppress the occurrence of process defects in, for example, the semiconductor device manufacturing process.
According to the pressure-sensitive adhesive sheets of Examples 1 to 3, the adhesiveness between the pressure-sensitive adhesive layer and the base material is excellent. In the pressure-sensitive adhesive sheet of Example 3, the hard coat layer was provided between the base material and the pressure-sensitive adhesive layer, but since the hard coat layer was formed using the above-mentioned hard coat agent HC2, the hard coat layer and the pressure-sensitive adhesive were It is considered that the adhesion between the layer and the hard coat layer is excellent.

10, 10A... Adhesive sheet, 11... Substrate, 11a... First surface, 11b... Second surface, 12... Adhesive layer, 13... Hard coat layer, 13a... First hard coat layer, 13b... Second hard coat Layers, 20... Frame members, 21... Openings.

Claims (7)

Used when sealing the semiconductor element on the pressure-sensitive adhesive sheet with a sealing resin, which is a pressure-sensitive adhesive sheet peeled from the sealing resin after sealing ,
A first surface and a second surface opposite to the first surface, and a base material containing a polyester resin,
An adhesive layer laminated on the first surface of the substrate,
A hard coat layer laminated on the second surface of the substrate,
The hard coat layer is a pressure-sensitive adhesive sheet, which is a cured film formed by curing an organic-inorganic hybrid material. After heating at 190° C. for 1 hour, the shrinkage in the direction along any surface of the substrate is 1.7% or less,
The pressure-sensitive adhesive sheet according to claim 1. The pressure-sensitive adhesive sheet according to claim 1, wherein the polyester-based resin is a resin selected from the group consisting of polyethylene terephthalate resin, polyethylene naphthalate resin, and polybutylene terephthalate resin. The pressure-sensitive adhesive sheet according to any one of claims 1 to 3, wherein the hard coat layer has a thickness of 0.5 µm or more and 3.0 µm or less. Further having a second hard coat layer between the pressure-sensitive adhesive layer and the substrate,
The pressure-sensitive adhesive sheet according to any one of claims 1 to 4, wherein the second hard coat layer contains a polyfunctional acrylic resin. The organic-inorganic hybrid material,
The pressure-sensitive adhesive sheet according to any one of claims 1 to 5, comprising a material in which silica fine particles are combined with an organic compound having a polymerizable unsaturated group, and an active energy ray-curable resin. A step of adhering a frame member having a plurality of openings formed on the pressure-sensitive adhesive sheet; a step of adhering a semiconductor chip to an adhesive layer exposed at the openings of the frame member; The method for manufacturing a semiconductor device, comprising: a step of covering with a sealing resin; a step of thermally curing the sealing resin; and a step of peeling the adhesive sheet after the thermosetting, the method for manufacturing a semiconductor device. The pressure-sensitive adhesive sheet according to any one of 6 above.

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