KR20240055794A - Semiconductor device manufacturing method and semiconductor device - Google Patents

Abstract

Among the processing processes of semiconductor devices having irregularities on the surface of a semiconductor chip with bumps or a PCB with bumps, the generation and adhesion of outgass during high temperature processing, including the use of an adhesive sheet that can accurately follow and adhere to the irregularities. Provision of a method for manufacturing a semiconductor device without adhesive residue on the surface of the adherend when peeling off the sheet. A protection process of attaching the adhesive sheet having a sheet-like base material and an adhesive layer formed on the base material to the bumped surface of the semiconductor device, a UV irradiation process of curing the adhesive layer by applying UV irradiation to the adhesive sheet, and the adhesive sheet. A method of manufacturing a semiconductor device comprising a peeling step of peeling and removing from an adherend surface on which a bump is formed, wherein the adhesive layer is a cured product of an adhesive composition, and the adhesive composition includes a resin (A) represented by the following general formula (1-1): A method for manufacturing a semiconductor device, which includes a photopolymerization initiator (B) and wherein the weight average molecular weight of the resin (A) is 50,000 to 550,000.

Description

Semiconductor device manufacturing method and semiconductor device

The present invention relates to a method of manufacturing a semiconductor device and a semiconductor device.

In the semiconductor manufacturing process, various adhesive sheets are used. Specifically, there are protective sheets to protect the wafer in the back grinding (back grind) process of semiconductor wafers, and fixing sheets used in the cutting and dividing (dicing) process of semiconductor wafers into device pieces. These adhesive sheets are adhesive sheets of a re-peelable type that are attached to a semiconductor wafer as an adherend and are peeled off from the adherend after a predetermined processing process is completed.

Recently, with the miniaturization and high density of electronic devices, flip chip mounting has become the mainstream method of mounting semiconductor devices in the minimum area. In flip chip mounting, a semiconductor chip (for example, a Through Silicon Via (TSV) chip) having a protruding electrode (bump) having a tip made of solder is used to achieve bonding between chips. The semiconductor chip on which this bump is formed is electrically bonded to and mounted with another semiconductor chip or substrate through a reflow process in which the chip is heated to a temperature higher than the melting temperature of solder (usually 200°C or higher). Additionally, when a semiconductor chip is mounted on a communication electronic device, communication interference may occur due to electromagnetic waves generated from inside the chip. To prevent this, a sputtering process (usually above 150°C) is sometimes used to deposit a metal film on the outer periphery of the semiconductor chip as an electromagnetic wave shield. In the reflow process or sputtering process, a re-peelable adhesive sheet is used to protect the bump surface.

BACKGROUND A printed circuit board (PCB) with bumps formed on it is widely used in semiconductor devices. When fixing a PCB on which bumps are formed to a separate board or housing, adhesive tape may be used. In the semiconductor chip mounting process, the PCB on which these bumps are formed sometimes goes through a reflow process or sputtering process.

Patent Document 1 is an adhesive tape having an ultraviolet curing type adhesive layer that can be operated by attaching it to a semiconductor chip on which a bump is formed, curing the adhesive layer by irradiating ultraviolet rays, and peeling it off after a high temperature treatment process, wherein the adhesive layer is cured. An adhesive tape that satisfies the following relationship: -5≤B-exp(A/30) when the previous gel fraction is A (%) and the tensile modulus of elasticity of the adhesive layer after light irradiation at 3000 mJ/cm2 is B (MPa). is disclosed.

Japanese Patent Publication No. 2020-94199

Semiconductor chips with bumps and PCBs with bumps have large irregularities on their surfaces, so when protecting them with a releasable adhesive sheet, the adhesive sheets must accurately follow the irregularities and adhere closely during the processing process. . In addition, the adhesive sheet is required to have high heat resistance so that no outgassing is generated during high temperature processing such as a reflow process or no adhesive residue is left on the semiconductor chip when the adhesive sheet is peeled off.

However, conventional adhesive sheets did not satisfy all of the above conditions. In Patent Document 1, because the adhesive layer was not flexible enough to follow the bumps, there were cases where the adhesion to the unevenness of the sheet attachment surface was insufficient. Additionally, due to the additives, there were cases where outgassing was generated after the heating process and adhesive residue was generated when the adhesive sheet was peeled off.

The present invention has been made in consideration of the above circumstances, and includes the use of an adhesive sheet that can accurately follow the irregularities and adhere closely to them during the processing process of a semiconductor device having irregularities on the surface of a semiconductor chip with bumps or a PCB with bumps. The object is to provide a method for manufacturing a semiconductor device that does not generate outgas during high-temperature treatment and does not cause adhesive residue on the surface of the adherend when peeling off the adhesive sheet.

Additionally, the present invention aims to provide a semiconductor device manufactured by the above manufacturing method.

The present inventors have found that the weight average molecular weight obtained by the addition reaction of a carboxyl group-containing resin (b) obtained by polymerizing a carboxyl group-containing ethylenically unsaturated monomer (a) as an essential monomer component and an alicyclic epoxy group-containing ethylenically unsaturated compound (c) is The above problem can be solved by providing a protection process in which an adhesive sheet formed using an adhesive composition containing 50,000 to 550,000 resin (A) and a photopolymerization initiator (B) as essential components is attached to the adherend surface on which bumps are formed. I found something I could do.

The present invention includes the following aspects.

[One]

A protection process of attaching an adhesive sheet having a sheet-like substrate and an adhesive layer formed on the substrate to the bumped surface of the semiconductor device,

A UV irradiation step of curing the adhesive layer by applying UV irradiation to the adhesive sheet, and

A method of manufacturing a semiconductor device comprising a peeling process of peeling and removing the adhesive sheet from the adhered surface on which the bump is formed,

The adhesive layer is a cured product of the adhesive composition,

A method of manufacturing a semiconductor device in which the adhesive composition includes a resin (A) and a photopolymerization initiator (B) represented by the following general formula (1-1), and the weight average molecular weight of the resin (A) is 50,000 to 550,000. .

(In equation (1-1), k, l, m and n represent the molar composition ratio when k+l+m+n=100. k is greater than 0 and less than or equal to 92. l is 0 to 50. m is greater than 0 and less than or equal to 90. n is 5 to _35. R ^{1 to} R ⁵ are carbon atoms. R ⁶ is an alkyl group with 1 to 16 carbon atoms, or _an aromatic hydrocarbon group ^with 6 _to 20 carbon atoms. j in the formula is 1 or 2.) R ⁸ is a group represented by the general formula (1-2) or (1-3). p and q are any one selected from 0, 1, and 2. When p is 0, R ⁹ is ₁ .

[2]

The method for manufacturing a semiconductor device according to [1], wherein n in the formula (1-1) is 7 to 33.

[3]

The method for manufacturing a semiconductor device according to [1] or [2], wherein in the formula (1-1), k is 45 to 90, l is 4 to 40, and m is 1 to 20.

[4]

The method for manufacturing a semiconductor device according to any one of [1] to [3], wherein the adhesive composition further contains a crosslinking agent (C).

[5]

The method for manufacturing a semiconductor device according to any one of [1] to [4], wherein the resin (A) has a glass transition temperature of -80 to 0°C.

[6]

The method for manufacturing a semiconductor device according to any one of [1] to [5], comprising a heating process of 150° C. or higher between the protection process and the peeling process.

[7]

The method for manufacturing a semiconductor device according to any one of [1] to [6], comprising a processing step between the protection step and the peeling step.

[8]

The method for manufacturing a semiconductor device according to any one of [1] to [5], comprising a heating process of 150° C. or higher between the protection process and the UV irradiation process.

[9]

The method for manufacturing a semiconductor device according to any one of [1] to [6], comprising a processing step between the protection step and the UV irradiation step.

[10]

The method for manufacturing a semiconductor device according to any one of [1] to [5], comprising a heating process of 150° C. or higher between the UV irradiation process and the peeling process.

[11]

The method for manufacturing a semiconductor device according to any one of [1] to [6], comprising a processing step between the UV irradiation step and the peeling step.

[12]

A semiconductor device manufactured by the method according to any one of [1] to [11].

The pressure-sensitive adhesive composition containing the resin (A) and the photopolymerization initiator (B) has good heat resistance because the resin (A) has a structure derived from an alicyclic compound. Additionally, since the weight average molecular weight of the resin (A) is 50,000 to 550,000, flexibility is provided to the adhesive layer. Therefore, the adhesive composition can form an adhesive layer with good adhesion to electronic components such as a semiconductor chip with uneven bumps on the surface and a PCB with bumps. Furthermore, because the weight average molecular weight of the resin (A) is 50,000 to 550,000, outgass generated from the adhesive layer during high temperature treatment can be reduced. In addition, the adhesive strength of the adhesive layer containing the cured product of the adhesive composition changes by irradiating ultraviolet (UV) rays so that the unsaturated bonds in the resin (A) form a three-dimensional crosslinked structure and cure. Specifically, before irradiating UV to the adhesive composition, it exhibits sufficient adhesion to the adherend, and after irradiating UV, the adhesive strength decreases, resulting in excellent easy peelability and sufficient removal of adhesion residue to the adherend after peeling. It can be prevented.

By using the semiconductor device manufacturing method of the present invention, even during the processing process of a semiconductor device having irregularities on the surface of a semiconductor chip with bumps or a PCB with bumps, the adhesive sheet can accurately follow the irregularities and adhere to them, allowing high temperature treatment. A semiconductor device can be manufactured without generating any outgassing or adhesive residue on the adhered surface on which the bump is formed when peeling off the adhesive sheet.

Hereinafter, the semiconductor device manufacturing method and semiconductor device of the present invention will be described in detail. However, the present invention is not limited to the embodiments shown below.

[Method for manufacturing semiconductor devices]

A method of manufacturing a semiconductor device of one embodiment includes:

A protection process of attaching an adhesive sheet having a sheet-like substrate and an adhesive layer formed on the substrate to the bumped surface of the semiconductor device,

A UV irradiation process of curing the adhesive layer by applying UV irradiation to the adhesive sheet, and

It includes a peeling process of peeling and removing the adhesive sheet from the adhered surface on which the bumps are formed.

[Protection process]

In the protection process, an adhesive sheet is attached to the bumped surface of the semiconductor device on which the bump electrode is formed. As a result, the adhered surface on which the bumps of the semiconductor device are formed is protected. Examples of the semiconductor device include semiconductor devices with irregularities on the surface, such as a semiconductor chip with bumps, a printed wiring board (PCB) with bumps, and an FPC board with bumps. These semiconductor devices are subjected to various processing processes in the manufacturing process up to the mounting process for connecting the bump electrode to another electronic device. By protecting the adhered surface on which the bump is formed during the processing process, damage, breakage, contamination, etc. of the adhered surface on which the bump is formed can be prevented. The protection process may also serve as a temporary fixation of the semiconductor device for subsequent processing processes.

When a semiconductor device has a plurality of adhered surfaces on which bumps are formed, in the protection process, an adhesive sheet is attached to some or all of the adhered surfaces on which bumps are formed. For example, when stacking semiconductor chips disclosed in Japanese Patent Application Laid-Open No. 2014-225546 or the like, an adhesive sheet can be attached to the non-mounted surface other than the mounted surface of the adhered surface on which the bump is formed.

[Adhesive sheet]

The adhesive sheet of one embodiment has a sheet-like substrate and an adhesive layer formed on the substrate.

It is preferable that a release sheet (separator) is provided on the surface of the adhesive layer opposite to the base material. When a release sheet is provided on the adhesive layer, the adhesive layer can be protected by the release sheet until use. When a release sheet is provided on the adhesive layer, the operation of peeling off the release sheet to expose the adhesive layer and pressing the adhesive layer (attachment surface) to the adherend can be performed efficiently.

The adhesive sheet may be used as an adhesive tape formed into a shape according to the shape of the adherend by a punching method or the like. The adhesive sheet may be wound and cut to be used as a roll-shaped adhesive tape.

As a base material, a known sheet-like material can be appropriately selected and used. As a base material, it is preferable to use a resin sheet made of a transparent resin material.

Resin materials include, for example, polyolefins such as polyethylene (PE) and polypropylene (PP); polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN); polyvinyl chloride (PVC); polyamide (PA); polyimide (PI); polyphenylene sulfide (PPS); ethylene vinyl acetate (EVA); and polytetrafluoroethylene (PTFE). Among these resin materials, it is preferable to use PE, PP, or PET because a sheet with appropriate flexibility can be obtained. Resin materials may be used individually, or two or more types may be mixed.

When using a resin sheet as a base material, the resin sheet may be a single layer or may have a multilayer structure of two or more layers (for example, a three-layer structure). In a resin sheet having a multilayer structure, the number of resin materials constituting each layer may be one or two or more types.

The thickness of the base material can be appropriately selected depending on the purpose of the adhesive sheet, the material of the base material, etc. When a resin sheet is used as a base material, the adhesive sheet protects a semiconductor chip with bumps or a flexible printed circuit board (FPC) with bumps when performing a reflow process or sputtering treatment, and the thickness of the base material is preferably It is 5 to 1000 μm, more preferably 10 to 300 μm. If the thickness of the base material is 5 μm or more, the rigidity of the adhesive sheet becomes high (elasticity becomes strong). Therefore, when attaching the adhesive sheet to an adherend such as a semiconductor chip or peeling it off from the adherend, it becomes difficult for the adhesive sheet to be wrinkled or warped. Additionally, if the thickness of the base material is 5 μm or more, the adhesive sheet attached to the adherend becomes easy to peel from the adherend, and good workability (handleability, handling) is obtained. If the thickness of the base material is 1000 μm or less, the rigidity of the adhesive sheet becomes too high (elasticity becomes strong), thereby preventing workability from deteriorating.

When using a resin sheet as a base material, the base material can be manufactured by appropriately employing conventionally known general sheet molding methods (e.g., extrusion molding, T-die molding, inflation molding, uniaxial or biaxial stretch molding, etc.).

The surface of the base material on the side in contact with the adhesive layer may be subjected to surface treatment to improve the adhesion between the base material and the adhesive layer.

Examples of surface treatment include corona discharge treatment, acid treatment, ultraviolet irradiation treatment, plasma treatment, and primer application.

The pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of one embodiment includes a cured product of the pressure-sensitive adhesive composition described later.

The thickness of the adhesive layer is preferably 1 to 1000 μm, more preferably 5 to 750 μm, and still more preferably 10 to 500 μm. If the thickness of the adhesive layer is 1 μm or more, the uniformity of the thickness of the adhesive layer is good. If the thickness of the adhesive layer is 1000 μm or less, the adhesive layer can be sufficiently adhered to the unevenness of the surface without lifting.

When a release sheet is provided on the surface opposite to the base material of the adhesive layer, a known sheet-like material can be appropriately selected and used as the release sheet. As a release sheet, the same thing as the above-mentioned resin sheet used as a base material can be used.

The thickness of the release sheet can be appropriately selected depending on the purpose of the adhesive sheet, the material of the release sheet, etc. When using a resin sheet as a release sheet, the thickness of the release sheet is preferably 5 to 300 μm, more preferably 10 to 200 μm, and still more preferably 25 to 100 μm.

If necessary, the release surface of the release sheet (the surface disposed in contact with the adhesive layer) may be subjected to a release treatment using a conventionally known release agent such as silicone-based, long-chain alkyl-based, or fluorine-based.

[Method of manufacturing adhesive sheet]

The adhesive sheet of one embodiment can be manufactured, for example, by the method shown below.

First, an adhesive solution is prepared by dissolving or dispersing the adhesive composition described later in a solvent. The above-mentioned adhesive composition may be used as is as an adhesive solution.

Next, the adhesive solution is applied onto the substrate, and if it contains a solvent, the solvent is removed by heating and drying to form an adhesive layer. After that, a release sheet is bonded on the adhesive layer as needed. Additionally, an adhesive sheet can be obtained by curing the obtained sheet in an oven for a certain period of time as needed and forming a crosslinked structure.

As another method of producing an adhesive sheet, the above adhesive solution is applied onto a release sheet, and if it contains a solvent, the solvent is removed by heating and drying to form an adhesive layer. After that, the release sheet with the adhesive layer is placed on the substrate with the side on the adhesive layer side facing the substrate, the adhesive layer is transferred (attached) onto the substrate, and, if necessary, cured in an oven for a certain period of time to form a crosslinked structure. There are ways to do it.

As a method of applying the above pressure-sensitive adhesive solution onto the substrate (or onto the release sheet), a known method can be used. Specifically, a method of application using a common coater, such as a gravure roll coater, reverse roll coater, kiss roll coater, deep roll coater, bar coater, knife coater, spray coater, comma coater, direct coater, etc. there is.

The conditions for heating and drying the applied adhesive solution above are not particularly limited, but are usually heated and dried at 25 to 180°C, preferably 60 to 150°C, for 1 to 20 minutes, preferably 1 to 10 minutes. do it By performing heat drying under the above conditions, the solvent contained in the adhesive solution can be removed. The conditions for curing the heat-dried adhesive sheet in an oven for a certain period of time are not particularly limited, but curing is usually performed at 25 to 100°C, preferably 30 to 80°C, for 1 to 7 days, preferably 1 to 3 days. By curing under the above conditions, the resin (A) and the crosslinking agent (C) can be crosslinked, and the gel fraction of the adhesive layer can be adjusted to a desired range.

[Adhesive composition]

The pressure-sensitive adhesive composition of one embodiment includes a resin (A) and a photopolymerization initiator (B).

<Resin (A)>

Resin (A) contained in the adhesive composition of one embodiment is a compound represented by the following general formula (1-1).

(In equation (1-1), k, l, m and n represent the molar composition ratio when k+l+m+n=100. k is greater than 0 and less than or equal to 92. l is 0 to 50. m is greater than 0 and less than or equal to 90. n is 5 to _35. R ^{1 to} R ⁵ are carbon atoms. R ⁶ is an alkyl group with 1 to 16 carbon atoms, or _an aromatic hydrocarbon group ^with 6 _to 20 carbon atoms. j in the formula is 1 or 2.) R ⁸ is a group represented by the general formula (1-2) or (1-3). p and q are any one selected from 0, 1, and 2. When p is 0, R ⁹ is ₁ .

In equation (1-1), k, l, m, and n represent the molar composition ratio when k+l+m+n=100. k is greater than 0 and less than or equal to 92. l is 0 to 50. m is greater than 0 and less than or equal to 90. The sum of k, l and m is 65 to 95. If the sum of k, l, and m is 65 or more, a pressure-sensitive adhesive layer with sufficient adhesion to the adherend can be formed before UV irradiation. The sum of k, l, and m is preferably 70 to 94, and more preferably 75 to 90.

In equation (1-1), the repeating unit shown within the parentheses enclosed by k (hereinafter referred to as “repeating unit k”) is an essential repeating unit. The repeating unit k contributes to the adhesive strength of the adhesive composition before UV irradiation. The number of repetitions k of the repeating unit k is greater than 0 to 92 or less, preferably 45 to 90, and more preferably 60 to 88.

In equation (1-1), the repeating unit (hereinafter referred to as “repeating unit l”) indicated within the parentheses enclosed by l may be omitted. In other words, the number of repetitions of repetition unit l may be 0. The repeating unit l contributes to the heat resistance of the adhesive composition. The number of repetitions l of the repeating unit l is 0 to 50, preferably 4 to 40, and more preferably 5 to 30.

In equation (1-1), the repeating unit shown in the parentheses enclosed by m (hereinafter referred to as “repeating unit m”) is an essential repeating unit. The repeating unit m contributes to the adhesive strength and heat resistance of the adhesive composition before UV irradiation. Additionally, when the pressure-sensitive adhesive composition contains a cross-linking agent having a functional group that reacts with a carboxyl group, the repeating unit m reacts with the cross-linking agent to provide cohesion to the pressure-sensitive adhesive layer. The number of repetitions m of the repeating unit m is greater than 0 and less than or equal to 90, preferably 1 to 20, and more preferably 1 to 10.

In equation (1-1), the repeating unit shown within the parentheses enclosed by n (hereinafter referred to as “repeating unit n”) is an essential repeating unit. The repeating unit n contributes to the heat resistance of the adhesive composition. The repeating number n of repeating unit n is 5 to 35, preferably 7 to 33, and more preferably 10 to 30. If the repeating unit n is 35 or less, by UV irradiation, the unsaturated bonds in the resin (A) form a three-dimensional crosslinked structure and harden, forming an adhesive layer whose adhesive strength is reduced to an appropriate range. When n is 5 or more, the effect of improving heat resistance due to the structure derived from the alicyclic compound can be obtained.

Due to the synergistic effect of the functions contributed by each of these repeating units, the adhesive composition containing the resin (A) has a much better balance between the adhesive strength before ultraviolet (UV) irradiation and the adhesive strength after UV irradiation. As a result, it is possible to obtain an adhesive composition in which sufficient adhesive strength to the adherend is obtained before UV irradiation, and after UV irradiation, the adhesive strength decreases and superior easy peelability is obtained. In addition, this adhesive composition does not increase the adhesive strength excessively even if it is heated to a high temperature before UV irradiation and then returned to room temperature, and excellent easy peelability is obtained after UV irradiation. In addition, adhesive residue on the adherend after peeling is unlikely to be generated. difficult.

In repeating unit k, R ¹ is -H or -CH ₃ , and is preferably -H. R ⁵ is an alkyl group with 1 to 16 carbon atoms, preferably an alkyl group with 1 to 8 carbon atoms, and particularly preferably an alkyl group with 2, 4 or 8 carbon atoms.

The repeating unit k may be a plurality of different repeating units of R ¹ and/or R ⁵ . When the repeating unit k includes multiple types of repeating units, the repeat number k of the repeating unit k represents the sum of the repeat numbers of the multiple types of repeating units. For example, if repeat unit k includes different repeat units A and B of R ¹ and/or R ⁵ and includes 2 repeat units A and 3 repeat units B, the repeat number k is the number of A. The sum of the numbers of and B becomes “5”.

In repeating unit 1, R ² is -H or -CH ₃ , and is preferably -H. R ⁶ is an alicyclic hydrocarbon group with 3 to 30 carbon atoms or an aromatic hydrocarbon group with 6 to 20 carbon atoms, and is an alicyclic hydrocarbon group with 6 to 20 carbon atoms or an aromatic hydrocarbon group with 6 to 12 carbon atoms. desirable.

The repeating unit l may be a plurality of different repeating units of R ² and/or R ⁶ . When the repeating unit l includes multiple types of repeating units, the repeat number l of the repeating unit l represents the sum of the repeat numbers of the multiple types of repeating units.

In the repeating unit m, R ³ is -H or -CH ₃ , and is preferably -H. R ⁷ is -H or -(CH ₂ ) _j -COOH (j in the formula is 1 or 2), and is preferably -H.

The repeating unit m may be a plurality of different repeating units of R ³ and/or R ⁷ . When the repeating unit m includes multiple types of repeating units, the repeat number m of the repeating unit m represents the sum of the repeat numbers of the multiple types of repeating units.

In repeating unit n, R ⁴ is -H or -CH ₃ , and is preferably -H. R ⁸ is a group represented by formula (1-2) or (1-3). The groups represented by formula (1-2) or (1-3) all contain structures derived from alicyclic compounds and have a function of improving the heat resistance of the adhesive composition. In formula (1-2) or (1-3), p and q are any one selected from 0, 1, and 2. s is 0 when p is 0 and 1 when p is 1 or 2. R ⁹ is -H or -CH ₃ .

The repeating unit n may be a plurality of different repeating units of R ⁴ and/or R ⁸ . When the repeating unit n includes multiple types of repeating units, the repeat number n of the repeating unit n represents the sum of the repeat numbers of the multiple types of repeating units.

The resin (A) represented by formula (1-1) may be any of random copolymers, block copolymers, and alternating copolymers consisting of repeating unit k, repeating unit l, repeating unit m, and repeating unit n. . The resin (A) represented by formula (1-1) does not need to contain the repeating unit l, and may be selected from random copolymers, block copolymers, and alternating copolymers consisting of a repeating unit k, a repeating unit m, and a repeating unit n. Any one is fine.

The weight average molecular weight of the resin (A) is 50,000 to 550,000, preferably 100,000 to 500,000, and more preferably 260,000 to 450,000. If the weight average molecular weight of the resin (A) is 50,000 or more, when a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer containing a cured product of the pressure-sensitive adhesive composition is attached to an adherend and then peeled off, the pressure-sensitive adhesive layer is likely to remain on the adherend. It gets difficult. If the weight average molecular weight of the resin (A) is 550,000 or less, the adhesive layer can be sufficiently adhered to surface irregularities such as bumps without gaps. The weight average molecular weight of resin (A) is a value measured by the method described in the Examples.

The glass transition temperature (Tg) of the resin (A) is preferably -80 to -0°C, more preferably -60 to -10°C, and even more preferably -50 to -10°C. If the glass transition temperature of the resin (A) is in the range of -80°C to 0°C, the adhesive strength of the adhesive composition before UV irradiation is good. The Tg of the resin (A) is a value measured by the method described in the Examples.

The acid value of the resin (A) is preferably greater than 0 to 25 mgKOH/g, and more preferably 3 to 20 mgKOH/g. If the acid value of the resin (A) is within the range of more than 0 to 25 mgKOH/g, contamination of the adherend (adhesive residue) after heating can be reduced. When the pressure-sensitive adhesive composition contains a cross-linking agent, if the acid value of the resin (A) is within the above range, the resin (A) and the cross-linking agent can react to effectively increase the cohesion of the pressure-sensitive adhesive composition, thereby preventing contamination (adhesion) of the adherend after heating. residue) can be further reduced. The acid value of the resin (A) is the value measured by the method described in the Examples.

(Method for producing resin (A))

Resin (A) can be manufactured, for example, by the method shown below.

First, the carboxyl group-containing ethylenically unsaturated monomer (a) and the raw material monomer containing the ethylenically unsaturated monomer (d) are polymerized to produce the carboxyl group-containing resin (b). The ethylenically unsaturated monomer (d) may contain a monomer that forms the repeating unit k after polymerization, and may also contain a monomer that forms the skeleton of the repeating unit l.

Next, resin (A) can be produced by addition reaction between the carboxyl group-containing resin (b) and a specific alicyclic epoxy group-containing ethylenically unsaturated compound (c).

(Carboxyl group-containing ethylenically unsaturated monomer (a))

The carboxyl group-containing ethylenically unsaturated monomer (a) used in producing the carboxyl group-containing resin (b) is a monomer that polymerizes to form the skeleton of the repeating unit m. The carboxyl group-containing ethylenically unsaturated monomer (a) has one carboxyl group.

Examples of the carboxyl group-containing ethylenically unsaturated monomer (a) include (meth)acrylic acid, carboxymethyl (meth)acrylate, and β-carboxyethyl (meth)acrylate.

Among these, it is preferable to use (meth)acrylic acid and/or β-carboxyethyl (meth)acrylate as the carboxyl group-containing ethylenically unsaturated monomer (a) from the viewpoint of reactivity.

In the present disclosure, (meth)acrylic means “acrylic” or “methacryl.” (meth)acrylate means “acrylate” or “methacrylate.” (meth)acryloyl means “acryloyl” or “methacryloyl.”

(Carboxyl group-containing resin (b))

The carboxyl group-containing resin (b) is a copolymerization of a carboxyl group-containing ethylenically unsaturated monomer (a) and a raw material monomer containing at least an ethylenically unsaturated monomer (d) copolymerizable with the carboxyl group-containing ethylenically unsaturated monomer (a).

Carboxyl group-containing resin (b) is a component that becomes the skeleton of resin (A) represented by formula (1-1). The repeating unit k, the repeating unit l, and the repeating unit m are all repeating units derived from the carboxyl group-containing resin (b).

As the ethylenically unsaturated monomer (d), one or more types of monomers that form the skeleton of the repeating unit k by polymerization are used. As the ethylenically unsaturated monomer (d), one or more types of monomers that form the skeleton of the repeating unit l by polymerization may be used together with the monomer that polymerizes to form the skeleton of the repeating unit l.

The ethylenically unsaturated monomer (d) that polymerizes to form the skeleton of the repeating unit k is an alkyl (meth)acrylate having 1 to 16 carbon atoms, and from the viewpoint of adjusting the peel strength of the adhesive composition, 2 to 16 carbon atoms. It is preferable that it contains an alkyl (meth)acrylate, and it is more preferable that it contains an alkyl (meth)acrylate with 4 to 12 carbon atoms. Alkyl (meth)acrylates having 1 to 16 carbon atoms specifically include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, and tert. -Butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-hexyl (meth)acrylate, isooctyl (meth)acrylate , and lauryl (meth)acrylate. Among these, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and isooctyl (meth)acrylate are preferable. In the present disclosure, the number of carbon atoms used in relation to (meth)acrylate refers to the number of carbon atoms in the residue excluding the (meth)acryloyloxy group.

Examples of the ethylenically unsaturated monomer (d) that polymerizes to form the skeleton of the repeating unit l include (meth)acrylate containing a cyclic alkyl group with 3 to 30 carbon atoms, and (meth)acrylate containing an aromatic group with 6 to 20 carbon atoms ( Meta)acrylate may be mentioned.

Examples of (meth)acrylates containing a cyclic alkyl group having 3 to 30 carbon atoms used as the ethylenically unsaturated monomer (d) that forms the skeleton of the repeating unit l by polymerization include cyclohexyl (meth)acrylate and norbor. Nyl(meth)acrylate, isobornyl(meth)acrylate, dicyclopentenyl(meth)acrylate, dicyclopentenyloxyethyl(meth)acrylate, dicyclofentanyl(meth)acrylate, and dicyclopentenyl(meth)acrylate. Fentanyloxyethyl (meth)acrylate can be mentioned. Among these, it is particularly preferable to use isobornyl (meth)acrylate. If a cyclic alkyl group-containing (meth)acrylate is contained in the raw material monomer of the carboxyl group-containing resin (b), the heat resistance of the adhesive composition containing the resin (A) manufactured using the carboxyl group-containing resin (b) can be increased.

Examples of aromatic group-containing (meth)acrylates having 6 to 20 carbon atoms used as the ethylenically unsaturated monomer (d) that forms the skeleton of the repeating unit l by polymerization include benzyl (meth)acrylate and phenoxyethyl. (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, phenoxypropyl (meth)acrylate, and phenoxypolypropylene glycol (meth)acrylate. Among these, it is particularly preferable to use benzyl (meth)acrylate. If an aromatic group-containing (meth)acrylate is included in the raw material monomer of the carboxyl group-containing resin (b), the heat resistance of the adhesive composition containing the resin (A) manufactured using the carboxyl group-containing resin (b) can be increased.

Among the raw material monomers of the carboxyl group-containing resin (b), not only the carboxyl group-containing ethylenically unsaturated monomer (a) and the ethylenically unsaturated monomer (d), but also carboxyl group-containing ethylenically unsaturated monomers other than the carboxyl group-containing ethylenically unsaturated monomer (d) A monomer copolymerizable with monomer (a) may be contained.

Examples of ethylenically unsaturated monomers copolymerizable with the carboxyl group-containing ethylenically unsaturated monomer (a) other than the ethylenically unsaturated monomer (d) include alkoxyalkyl (meth)acrylate and alkoxy (poly)alkylene glycol (meth). Acrylates, hydroxy group-containing (meth)acrylates, fluorinated alkyl (meth)acrylates, dialkylaminoalkyl (meth)acrylates, and (meth)acrylamide compounds can be mentioned.

Examples of alkoxyalkyl (meth)acrylate include ethoxyethyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, and 2-methoxyethoxyethyl (meth)acrylate. ate, and 2-ethoxyethoxyethyl (meth)acrylate.

Examples of alkoxy (poly) alkylene glycol (meth)acrylate include methoxydiethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, and methoxydipropylene glycol (meth)acrylate. there is.

Examples of hydroxy group-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 1,3-butanediol. (meth)acrylate, 1,4-butanediol (meth)acrylate, 1,6-hexanediol (meth)acrylate, and 3-methylpentanediol (meth)acrylate.

Examples of fluorinated alkyl (meth)acrylates include octafluoropentyl (meth)acrylate.

Examples of dialkylaminoalkyl (meth)acrylate include N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate.

Examples of (meth)acrylamide compounds include (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, and N-isopropyl (meth)acrylamide. ) Acrylamide, N-hexyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, (meth)acryloylmorpholine, and diacetone acrylamide. can be mentioned.

Specific examples of monomers other than the ethylenically unsaturated monomer (d) copolymerizable with the carboxyl group-containing ethylenically unsaturated monomer (a) include acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, Vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl toluene, N-vinylpyridine, N-vinylpyrrolidone, itaconic acid dialkyl ester, fumaric acid dialkyl ester, allyl alcohol, hydroxyl Butyl vinyl ether, hydroxyethyl vinyl ether, 4-hydroxymethylcyclohexylmethyl vinyl ether, triethylene glycol monovinyl ether, diethylene glycol monovinyl ether, methyl vinyl ketone, allyl trimethyl ammonium chloride, and dimethyl allyl vinyl ketone. I can hear it.

The method for producing the carboxyl group-containing resin (b) is not particularly limited. For example, the carboxyl group-containing resin (b) is obtained by copolymerizing raw material monomers containing the carboxyl group-containing ethylenically unsaturated monomer (a) and the ethylenically unsaturated monomer (d) by a known polymerization method. (b) can be obtained. Specifically, as a polymerization method, solution polymerization method, emulsion polymerization method, bulk polymerization method, suspension polymerization method, alternating copolymerization method, etc. can be used. Among these polymerization methods, considering the addition reaction between the carboxyl group-containing resin (b) and the alicyclic epoxy group-containing ethylenically unsaturated compound (c) obtained after polymerization, it is preferable to use the solution polymerization method in terms of ease of reaction.

When producing the carboxyl group-containing resin (b) by solution polymerization, a radical polymerization initiator and/or solvent are used as needed.

The radical polymerization initiator is not particularly limited and can be appropriately selected from known ones.

Examples of radical polymerization initiators include 2,2'-azobis(isobutylonitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and 2,2'- Azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2' -Azo-based polymerization initiators such as azobis(2,4,4-trimethylpentane) and dimethyl-2,2'-azobis(2-methylpropionate); and benzoyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, 1,1-bis(t-butylperoxy)-3,3,5. - Oil-soluble polymerization initiators such as peroxide-based polymerization initiators such as trimethylcyclohexane and 1,1-bis(t-butylperoxy)cyclododecane.

These radical polymerization initiators may be used individually or in combination of two or more types.

The amount of the radical polymerization initiator used is preferably 0.01 to 5 parts by mass, more preferably 0.02 to 4 parts by mass, and still more preferably 0.03 to 3 parts by mass, based on a total of 100 parts by mass of the raw material monomers of the carboxyl group-containing resin (b). .

As a polymerization solvent used when producing the carboxyl group-containing resin (b), various general solvents can be used. Examples of solvents include esters such as ethyl acetate, n-propyl acetate, and n-butyl acetate; Aromatic hydrocarbons such as toluene, xylene, and benzene; Aliphatic hydrocarbons such as n-hexane and n-heptane; Alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; Glycols such as ethylene glycol, propylene glycol, and dipropylene glycol; Glycol ethers such as methyl cellosolve, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether; and glycol esters such as ethylene glycol diacetate and propylene glycol monomethyl ether acetate.

These solvents may be used individually, or two or more types may be used in combination.

When producing the carboxyl group-containing resin (b), the carboxyl group-containing ethylenic monomer in the raw material monomers including the carboxyl group-containing ethylenically unsaturated monomer (a), the ethylenically unsaturated monomer (d), and other monomers contained as necessary. The content of the unsaturated monomer (a) is preferably 5 to 40 mass%, more preferably 7 to 30 mass%, and still more preferably 10 to 25 mass%. Resin (A) prepared by addition reaction between the carboxyl group-containing resin (b) and the alicyclic epoxy group-containing ethylenically unsaturated compound (c) by setting the content of the carboxyl group-containing ethylenically unsaturated monomer (a) in the raw material monomer within the above range. ) The adhesive strength of the adhesive layer obtained from the adhesive composition containing is good before UV irradiation.

(alicyclic epoxy group-containing ethylenically unsaturated compound (c))

The ethylenically unsaturated compound containing an alicyclic epoxy group (c) is a compound containing an ethylenically unsaturated group having an alicyclic epoxy group, and is a compound that gives a structure of general formula (1-2) or general formula (1-3). The alicyclic epoxy group in the present disclosure refers to an epoxy group formed by one oxygen bonding to two adjacent carbon atoms on the ring of an alicyclic hydrocarbon compound.

The ethylenically unsaturated compound (c) containing an alicyclic epoxy group is obtained by adding the following partial structural formula (1-2') or (1-3') to the repeating unit n of the resin (A) represented by formula (1-1). It is used to do this. The partial structural formula (1-2') or (1-3') in the repeating unit n in formula (1-1) is a group derived from an alicyclic epoxy group-containing ethylenically unsaturated compound (c).

(In formulas (1-2') and (1-3'), q is any one selected from 0, 1, and 2. R ⁹ is -H or -CH _3. )

Examples of the alicyclic epoxy group-containing ethylenically unsaturated compound (c) include compounds represented by the following formula (1) or (2).

(In formula (1), R ⁹ is -H or -CH _3. q is any one selected from 0, 1, and 2.)

(In formula (2), R ⁹ is -H or -CH _3. q is any one selected from 0, 1, and 2.)

In formula (1), R ⁹ is -H or -CH ₃ . q is any one selected from 0, 1, and 2, and it is preferred that q is 1.

In formula (2), R ⁹ is -H or -CH ₃ . q is any one selected from 0, 1, and 2, and it is preferred that q is 1.

The alicyclic epoxy group-containing ethylenically unsaturated compound (c) is preferably a compound represented by formula (1), and is particularly preferably 3,4-epoxycyclohexylmethyl (meth)acrylate.

The alicyclic epoxy group-containing ethylenically unsaturated compound (c) may be used individually or in combination of two or more types.

Resin (A) can be produced by adding the alicyclic epoxy group of an ethylenically unsaturated compound (c) containing an alicyclic epoxy group to the carboxyl group of the carboxyl group-containing resin (b).

Resin (A) is an ethylenically unsaturated compound containing an alicyclic epoxy group in an amount of preferably 0.2 to 0.99 mol, more preferably 0.3 to 0.95 mol, and even more preferably 0.6 to 0.95 mol, based on 1 mol of carboxyl groups of the carboxyl group-containing resin (b). It is preferable to produce (c) by addition reaction. The adhesive composition containing the resin (A) obtained by using the carboxyl group-containing resin (b) and the alicyclic epoxy group-containing ethylenically unsaturated compound (c) in the above ratio shows sufficient adhesion to the adherend before UV irradiation, and UV irradiation shows sufficient adhesion to the adherend. Afterwards, the adhesive strength decreases and more excellent easy peelability is obtained. In addition, this adhesive composition makes it difficult for the adhesive strength to increase even if it is brought to room temperature after being brought to a high temperature before UV irradiation, so excellent easy peelability is obtained after UV irradiation, and more effectively prevents adhesive residue on the adherend after peeling. You can.

The temperature of addition reaction when producing resin (A) is preferably 80 to 130°C, and particularly preferably 90 to 120°C. If the temperature of the addition reaction is 80°C or higher, a sufficient reaction rate can be obtained. If the temperature of the addition reaction is 130°C or lower, it is possible to prevent the double bond from being crosslinked by radical polymerization due to heat and forming a gelled product.

For the addition reaction when producing resin (A), a known catalyst can be used as needed. Examples of catalysts include primary amines such as n-butylamine, n-hexylamine, and benzylamine; Triethylamine, tributylamine, dimethylbenzylamine, 1,8-diazabicyclo[5.4.0]undeca-7-ene, 1,5-diazabicyclo[4.3.0]nona-5-ene, 1 Tertiary amines such as 4-diazabicyclo[2.2.2]octane; Aromatic amines such as aniline, toluidine, phenylenediamine, and 1,8-diaminonaphthalene; Pyridine compounds such as pyridine, 2,6-lutidine, and 4-N,N-dimethylaminopyridine; Quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, and tetrabutylammonium bromide; Alkyl urea such as tetramethyl urea; Alkylguanidine such as tetramethylguanidine; and triphenylphosphine, dimethylphenylphosphine, tricyclohexylphosphine, tributylphosphine, tris(4-methylphenyl)phosphine, tris(4-methoxyphenyl)phosphine, and tris(2,6-dimethylphenyl). ) Phosphines such as phosphine, tris(2,6-dimethoxyphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, and tris(2,4,6-trimethoxyphenyl)phosphine. Compounds may be mentioned.

Among the above, as a catalyst for the addition reaction, it is preferable to use a tertiary amine, a pyridine compound, or a phosphine compound from the viewpoint of reactivity.

The amount of catalyst used in the addition reaction is preferably 0.01 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, based on a total of 100 parts by mass of the carboxyl group-containing resin (b) and the alicyclic epoxy group-containing ethylenically unsaturated compound (c). , 0.1 to 5 parts by mass is most preferable.

Additionally, during the addition reaction, a gas having a polymerization inhibitory effect may be introduced into the reaction system, or a polymerization inhibitor may be added. Gelation during addition reaction can be prevented by introducing a gas with a polymerization inhibitory effect into the reaction system or adding a polymerization inhibitor.

Gases that have a polymerization-inhibiting effect include gases containing oxygen at a level that does not fall within the explosion range of substances in the system, such as air.

Known polymerization inhibitors can be used and are not particularly limited, but examples include 4-methoxyphenol, hydroquinone, methoquinone, 2,6-di-t-butylphenol, and 2,2'-methylenebis. (4-methyl-6-t-butylphenol), and phenothiazine. These polymerization inhibitors may be used individually, or two or more types may be used in combination.

The amount of the polymerization inhibitor used is preferably 0.005 to 5 parts by mass, more preferably 0.03 to 3 parts by mass, based on a total of 100 parts by mass of the carboxyl group-containing resin (b) and the alicyclic epoxy group-containing ethylenically unsaturated compound (c). 1.5 parts by mass is most preferable. If the amount of the polymerization inhibitor is too small, the polymerization inhibitory effect may not be sufficient. On the other hand, if the amount of the polymerization inhibitor is too large, there is a risk that the exposure sensitivity of the resin (A) upon UV irradiation may decrease.

It is more preferable to use a gas with a polymerization inhibitory effect in combination with a polymerization inhibitor because the amount of polymerization inhibitor used can be reduced or the polymerization inhibitory effect can be increased.

Examples of the photopolymerization initiator (B) contained in the adhesive composition include benzophenone, benzyl, benzoin, ω-bromoacetophenone, chloroacetone, acetophenone, 2,2-diethoxyacetophenone, and 2,2-dimeth. Toxy-2-phenylacetophenone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, 2-chlorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone, benzoin methyl ether, benzoin isobutyl ether, benzoin-n-butyl ether, benzyl methyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane -1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, methylbenzoyl formate, 2,2-diethoxyacetophenone, 4-N,N'- and carbonyl-based photopolymerization initiators such as dimethylacetophenone and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one.

Examples of the photopolymerization initiator (B) include sulfide-based photopolymerization initiators such as diphenyl disulfide, dibenzyl disulfide, tetraethylthiuram disulfide, and tetramethylammonium monosulfide; Acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide; Quinone-based photopolymerization initiators such as benzoquinone and anthraquinone; Sulfochloride-based photopolymerization initiator; Alternatively, thioxanthone-based photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, and 2-methylthioxanthone may be used.

Among these photopolymerization initiators (B), it is preferable to use 1-hydroxycyclohexylphenyl ketone and/or 2,4,6-trimethylbenzoyldiphenylphosphine oxide from the viewpoint of solubility in the adhesive composition.

These photopolymerization initiators (B) may be used individually, or may be used in combination of two or more types.

The photopolymerization initiator (B) contained in the adhesive composition is preferably 0.1 to 5.0 parts by mass, more preferably 0.5 to 2.0 parts by mass, based on 100 parts by mass of the resin (A). If the content of the photopolymerization initiator (B) relative to 100 parts by mass of the resin (A) is 0.1 parts by mass or more, the adhesive composition can be cured at a sufficiently fast curing rate by UV irradiation, thereby increasing the adhesive strength of the adhesive composition after UV irradiation. It can be made small enough. If the content of the photopolymerization initiator (B) relative to 100 parts by mass of the resin (A) is 5.0 parts by mass or less, when the adhesive sheet having an adhesive layer containing the adhesive composition is peeled off after attaching it to an adherend, the adhesive layer is peeled off. It becomes difficult to remain in the complex. Even if the content of the photopolymerization initiator (B) exceeds 5.0 parts by mass with respect to 100 parts by mass of the resin (A), an effect commensurate with the content of the photopolymerization initiator (B) is not observed. Therefore, by setting the content to 5.0 parts by mass or less, it is economically possible. An adhesive composition can be prepared.

<Cross-linking agent (C)>

The adhesive composition may contain not only the resin (A) and the photopolymerization initiator (B) but also a crosslinking agent (C). By containing the crosslinking agent (C), an adhesive composition with a better balance of adhesive strength before UV irradiation and adhesive strength after UV irradiation can be obtained.

The crosslinking agent (C) is not particularly limited, but a compound having two or more functional groups reactive with the hydroxyl group of the repeating unit n, or the hydroxyl group of the repeating unit n and the carboxyl group of the repeating unit m is preferable.

Examples of the crosslinking agent (C) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hydrogenated tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, and diphenyl. Methane-4,4-diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, isocyanurate form of hexamethylene diisocyanate, tetramethylxylylene diisocyanate, 1,5- Isocyanate-based compounds such as naphthalene diisocyanate, tolylene diisocyanate adduct of trimethylol propane, xylylene diisocyanate adduct of trimethylol propane, triphenylmethane triisocyanate, and methylenebis(4-phenylmethane)triisocyanate; 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane, bisphenol A epichlorohydrin type epoxy resin, N,N'-[1,3-phenylenebis(methylene)] Bis[bis(oxiran-2-ylmethyl)amine], ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol Epoxy-based compounds such as diglycidyl ether, trimethylol propane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, and diglycerol polyglycidyl ether. ; Tetramethylolmethane-tri-β-aziridinylpropionate, trimethylolpropane-tri-β-aziridinylpropionate, N,N'-diphenylmethane-4,4'-bis(1- Aziridine-based compounds such as aziridine carboxyamide) and N,N'-hexamethylene-1,6-bis(1-aziridine carboxyamide); and melamine-based compounds such as hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine, hexapentyloxymethylmelamine, and hexahexyloxymethylmelamine.

Among these crosslinking agents (C), it is preferable to use epoxy-based compounds and/or isocyanate-based compounds because they have good reactivity with the resin (A).

These crosslinking agents (C) may be used individually, or two or more types may be used in combination.

The crosslinking agent (C) contained in the adhesive composition is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and still more preferably 0.1 to 1.0 parts by mass, based on 100 parts by mass of the resin (A). If the content of the crosslinking agent (C) is 0.05 parts by mass or more relative to 100 parts by mass of the resin (A), a three-dimensional crosslinked structure is sufficiently formed in the adhesive composition. As a result, the adhesive force of the adhesive composition after UV irradiation can be sufficiently reduced. If the content of the crosslinking agent (C) is 10 parts by mass or less per 100 parts by mass of the resin (A), the adhesive strength of the adhesive composition before UV irradiation is good.

<Other ingredients>

The adhesive composition may, if necessary, contain other components other than the resin (A), photopolymerization initiator (B), and crosslinking agent (C) described above. Other components include, for example, tackifiers, solvents, and various additives.

(Tackifier)

As a tackifier, a conventionally known agent can be used without particular limitation. Examples of tackifiers include terpene-based tackifier resin, phenol-based tackifier resin, rosin-based tackifier resin, aliphatic petroleum resin, aromatic petroleum resin, copolymer petroleum resin, alicyclic petroleum resin, xylene resin, and epoxy. Examples include tackifier-based tackifier resins, polyamide-based tackifier resins, ketone-based tackifier resins, and elastomer-based tackifier resins. These tackifiers may be used individually, or two or more types may be used in combination.

When the adhesive composition contains a tackifier, its content is preferably 30 parts by mass or less, and more preferably 5 to 20 parts by mass, based on 100 parts by mass of the resin (A).

(menstruum)

When applying the adhesive composition, the solvent can be used to dilute the adhesive composition for the purpose of adjusting the viscosity of the adhesive composition.

Examples of solvents include methyl ethyl ketone, methyl isobutyl ketone, acetone, ethyl acetate, n-propyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, n-propanol, isopropanol, etc. Organic solvents can be used. These solvents may be used individually, or two or more types may be mixed and used.

(additive)

Additives include, for example, plasticizers, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, light stabilizers such as benzotriazoles, phosphoric acid esters and other flame retardants, and surfactants. , and antistatic agents.

[Method for producing adhesive composition]

The adhesive composition can be manufactured by conventionally known methods.

For example, the above-mentioned resin (A) and photopolymerization initiator (B), a crosslinking agent (C) contained as necessary, and other components such as a tackifier, solvent, and various additives are mixed using a conventionally known method. It can be prepared by mixing and stirring.

The pressure-sensitive adhesive composition of one embodiment is suitable as a material for forming the pressure-sensitive adhesive layer of a pressure-sensitive adhesive sheet, and is particularly preferable as a material for forming the pressure-sensitive adhesive layer of a releasable pressure-sensitive adhesive sheet.

Since the adhesive composition of one embodiment contains the resin (A) and the photopolymerization initiator (B) represented by formula (1-1), sufficient adhesive strength to the adherend can be achieved by using it as a material for forming the adhesive layer of the adhesive sheet. A pressure-sensitive adhesive sheet can be obtained. In addition, this adhesive sheet achieves excellent easy peelability after UV irradiation even when the adherend to which the adhesive sheet is attached is brought to a high temperature and then returned to room temperature to peel, and adhesive residue is unlikely to be generated.

[Manufacturing process]

The semiconductor device manufacturing method may include a processing step between the protection step and the peeling step described later.

As the processing process, conventionally known processing processes used for manufacturing semiconductor devices can be applied without particular restrictions. For example, when the adhesive sheet used in the protection process is used as a wafer dicing tape, the adhesive sheet is attached to a wafer on which a plurality of parts are formed through the protection process, and then the wafer is cut into individual parts as a processing process. A dicing process is performed to cut and divide (dice) the parts into small elements (chips). When carrying out the semiconductor chip stacking process as a processing process, only the non-mounted surface of the adhered surface on which the bump is formed is protected in the protection process, and the mounted surfaces to which the adhesive sheet is not attached are brought into contact with each other and electrically connected during stacking.

[Heating process]

The semiconductor device manufacturing method may include a heating process between the protection process and the peeling process described later. When the semiconductor device manufacturing method includes a processing step after the protection step, the order of the processing step and the heating step is not limited, but from the viewpoint of maximizing the protection function and temporary fixation function of the adhesive sheet, that is, the adhesion performance, the processing step is not limited. It is preferable that the and heating processes are carried out simultaneously, or that the processing process is carried out before the heating process.

As the heating process, conventionally known heating processes used in the manufacture of semiconductor devices can be applied without particular restrictions. Examples of the heating process include an after-cure process for a PCB on which bumps are formed, a sputtering process for a semiconductor chip, and a reflow process after stacking the semiconductor chip.

The conditions of the heating process are not particularly limited. By carrying out the above-described protection process before the heating process, the adherend surface on which the bumps are formed can be well protected even when high temperature treatment of, for example, 150°C or higher, 180°C or higher, or 200°C or higher is performed. The upper limit temperature of the heating process is not particularly limited, but is preferably 300°C or lower, more preferably 270°C or lower, from the viewpoint of heat resistance of the adhesive sheet. The heating time is not particularly limited, but is, for example, 1 minute to 180 minutes, preferably 1 minute to 120 minutes, more preferably 1 minute to 60 minutes.

[UV irradiation process]

In the UV irradiation process, UV is usually irradiated from the substrate side of the adhesive sheet. If the adherend has light transparency, UV may be irradiated from the adherend toward the adhesive sheet. UV irradiation can crosslink and cure the adhesive layer, improve the heat resistance of the adhesive sheet, or provide easy peelability to the adhesive sheet. The UV irradiation process may be performed between the protection process and the peeling process described later, and the order of the processing process and the heating process is not limited.

Light sources used when UV irradiating the adhesive sheet before peeling attached to the adherend include, for example, LED lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, carbon arc lamps, xenon lamps, metal halide lamps, chemical lamps, and black lights. I can hear it. It is desirable to use an LED lamp, high-pressure mercury lamp, or metal halide lamp for UV irradiation.

The amount of UV irradiation applied to the adhesive sheet is preferably 50 to 3000 mJ/cm2, and more preferably 100 to 600 mJ/cm2. If the amount of UV irradiation applied to the adhesive sheet is 50 mJ/cm2 or more, the adhesive layer can be cured at a sufficiently fast curing rate by UV irradiation, and thereby the adhesive force of the adhesive layer after UV irradiation can be sufficiently reduced. Even if the amount of UV irradiation applied to the adhesive sheet exceeds 3000 mJ/cm2, the appropriate effect is not obtained. Therefore, by setting the amount of UV irradiation applied to the adhesive sheet to 3000 mJ/cm2 or less, the effect of UV irradiation on the adherend can be reduced and it can be economical. The adhesive sheet can be peeled off.

[Peeling process]

In the peeling process, after curing the adhesive layer by UV irradiation, the adhesive sheet is peeled and removed from the adhered surface on which the bumps are formed. When UV is irradiated, the unsaturated bonds in the adhesive form a three-dimensional crosslinked structure and harden. As a result, the adhesive strength of the adhesive layer decreases. Thereafter, the adhesive sheet is peeled from the semiconductor device.

The processing step may be performed between the protection step and the UV irradiation step, or may be performed between the UV irradiation step and the peeling step. The heating process may be performed between the protection process and the UV irradiation process, or may be performed between the UV irradiation process and the peeling process.

According to the method for manufacturing a semiconductor device of one embodiment, even when a heating process is performed, a semiconductor device can be obtained without generating outgas and without adhesive residue on the surface of the adherend on which the bump is formed, so that the obtained semiconductor A continuous mounting process can be performed on the device without any problems.

Example

Hereinafter, the present invention will be described in more detail through examples and comparative examples. Additionally, the present invention is not limited to the following examples.

[Preparation Example 1: Preparation of resin (A)]

<Preparation of first mixed solution>

As shown in Table 1, 23.9 parts by mass of acrylic acid, which is a carboxyl group-containing ethylenically unsaturated monomer (a), 71.8 parts by mass of n-butylacrylate, which is an ethylenically unsaturated monomer (d) copolymerizable with the above (a), and 2-ethylhexyl. A first containing 2.39 parts by mass of 2,2'-azobis(isobutylonitrile) as a polymerization initiator based on a total of 100 parts by mass of the raw material monomer containing 143.6 parts by mass of acrylate and the raw material monomer of the carboxyl group-containing resin (b) A mixed solution was prepared.

<Preparation of second mixed solution>

As shown in Table 1, 59.8 parts by mass of 3,4-epoxycyclohexylmethylmethacrylate, which is an ethylenically unsaturated compound (c) containing an alicyclic epoxy group, a carboxyl group-containing resin (b) obtained using the first mixed solution, and an alicyclic Contains 1.5 parts by mass of tris(4-methylphenyl)phosphine (TPTP) as a catalyst, 100.0 parts by mass of n-butyl acetate, and 91.1 parts by mass of toluene as a solvent, based on a total of 100 parts by mass of the ethylenically unsaturated compound (c) containing an epoxy group. A second mixed solution was prepared.

175.6 parts by mass of n-butyl acetate was added as a solvent to a four-necked flask equipped with a stirrer, dropping funnel, cooling pipe, and nitrogen introduction pipe, and the temperature was raised to 80°C in a nitrogen gas atmosphere. Then, while maintaining the reaction temperature at 80°C ± 2°C, the first mixed solution was uniformly added dropwise to the four-necked flask over 4 hours, and after the dropwise addition was completed, the mixture was incubated at a temperature of 80°C ± 2°C for an additional 6 hours. Stirring was continued to perform polymerization, and carboxyl group-containing resin (b) was obtained. Thereafter, 0.15 parts by mass of 4-methoxyphenol as a polymerization inhibitor was added to the reaction system for a total of 100 parts by mass of the carboxyl group-containing resin (b) and the alicyclic epoxy group-containing ethylenically unsaturated compound (c).

The reaction system to which 4-methoxyphenol was added was heated to 100°C, the second mixed solution was added dropwise over 0.5 hours, and stirring was continued for 8 hours at a temperature of 100°C to synthesize resin (A-1). , cooled to room temperature (23°C).

Resin (A-1) was identified by nuclear magnetic resonance (NMR) and was found to be a compound represented by general formula (2-1). The repeating unit k of the compound represented by general formula (2-1) is two types of repeating units (k-1, k-2) with different R ⁵ .

(In equation (2-1), k-1 is 33.6, k-2 is 46.6, m is 1.6, and the sum of k-1, k-2, and m is 81.8. n is 18.2 .)

Resin (A-1) was examined for weight average molecular weight and glass transition temperature by the method shown below. The acid value of resin (A-1) was measured according to JIS K 0070:1992.

<Weight average molecular weight (Mw)>

It was measured at room temperature using gel permeation chromatography (Showa Denko Co., Ltd., Shodex (registered trademark) GPC-101) under the following conditions, and calculated in terms of polystyrene.

Column: Showa Denko Co., Ltd., Shodex (registered trademark) LF-804

Column temperature: 40℃

Sample: 0.2% by mass tetrahydrofuran solution of resin (A)

Flow rate: 1mL/min

Eluent: Tetrahydrofuran

Detector: RI detector

<Glass transition temperature (Tg)>

A 10 mg sample was taken from resin (A-1). Using a differential scanning calorimeter (DSC), differential scanning calorimetry was performed by changing the temperature of the sample from -100°C to 200°C at a temperature increase rate of 10°C/min, and the endothermic onset temperature due to the observed glass transition was expressed as Tg. did. When two or more endothermic onset temperatures were observed, Tg was taken as the simple average value of the two or more endothermic onset temperatures.

[Production Examples 2 to 12]

A first mixed solution was prepared in the same manner as in Production Example 1 except that the carboxyl group-containing ethylenically unsaturated monomer (a), ethylenically unsaturated monomer (d), and polymerization initiator were used in the amounts (parts by mass) shown in Table 1. did.

A second mixed solution was prepared in the same manner as in Production Example 1, except that the alicyclic epoxy group-containing ethylenically unsaturated compound (c) and a catalyst were used in the content (parts by mass) shown in Table 1.

Resins (A-2) to (A-12) were obtained in the same manner as in Production Example 1 except that the first mixed solution and the second mixed solution were used.

Resins (A-2) to (A-12) were each identified in the same manner as in Production Example 1, and were found to be compounds represented by general formulas (2-2) to (2-12). The repeating unit k of the compounds represented by general formulas (2-2) to (2-7) and (2-10) is two types of repeating units in which R ⁵ is different or both R ¹ and R ⁵ are different. It is (k-1, k-2).

Resin (A-2) is a compound represented by the following general formula (2-2).

Resin (A-3) is a compound represented by the following general formula (2-3).

Resin (A-4) is a compound represented by the following general formula (2-4).

Resin (A-5) is a compound represented by the above general formula (2-5).

Resin (A-6) is a compound represented by the following general formula (2-6).

Resin (A-7) is a compound represented by the following general formula (2-7).

Resin (A-8) is a compound represented by the following general formula (2-8).

Resin (A-9) is a compound represented by the following general formula (2-9).

Resin (A-10) is a compound represented by the following general formula (2-10).

Resin (A-11) is a compound represented by the following general formula (2-11).

Resin (A-12) is a compound represented by the following general formula (2-12).

(In equation (2-2), k-1 is 31.9, k-2 is 47.6, m is 1.8, and the sum of k-1, k-2, and m is 81.3. n is 18.7.)

(In equation (2-3), k-1 is 69.7, k-2 is 16.0, m is 1.2, and the sum of k-1, k-2, and m is 86.9. n is 13.1.)

(In equation (2-4), k-1 is 52.3, k-2 is 34.1, m is 2.9, and the sum of k-1, k-2, and m is 89.3. n is 10.7.)

(In equation (2-5), k-1 is 10.6, k-2 is 51.7, m is 4.4, the sum of k-1, k-2, and m is 66.7, and n is 33.3.)

(In equation (2-6), k-1 is 56.4, k-2 is 23.6, m is 0.2, and the sum of k-1, k-2, and m is 80.2. n is 19.8.)

(In equation (2-7), k-1 is 14.4, k-2 is 72.2, m is 1.1, and the sum of k-1, k-2, and m is 87.7. n is 12.3.)

(In equation (2-8), k is 76.4, m is 3.5, and the sum of k and m is 79.9. n is 20.1.)

(In equation (2-9), k is 79.9, m is 11.5, and the sum of k and m is 91.4. n is 8.6.)

(In equation (2-10), k-1 is 33.5, k-2 is 46.6, m is 4.4, and the sum of k-1, k-2, and m is 84.5. n is 15.5.)

(In equation (2-11), k is 65.9, l is 11.7, m is 1.8, and the sum of k, l, and m is 79.4. n is 20.6.)

(In equation (2-12), k is 55.5, l is 23.0, m is 1.7, and the sum of k, l, and m is 80.2. n is 19.8.)

Resins (A-2) to (A-12) were each tested for weight average molecular weight, glass transition temperature, and acid value in the same manner as for Resin (A-1). The results are shown in Table 2.

Table 1 shows the carboxyl group-containing ethylenically unsaturated monomer (a) used in the production of resins (A-1) to (A-12), the ethylenically unsaturated monomer (d) copolymerizable with (a), the polymerization initiator, and the alicyclic epoxy group. The types and usage amounts (parts by mass) of the ethylenically unsaturated compound (c), catalyst, polymerization inhibitor, and solvent contained are shown, respectively.

[Table 1-1]

[Table 1-2]

[Table 2]

Ethyl acetate as a diluting solvent was added to the reaction solution of resins (A-1) to (A-12) synthesized in Production Examples 1 to 12, and the content of resins (A-1) to (A-12) was 30. It was adjusted to be mass %. An adhesive composition was obtained by the method shown below using a solution of Resin (A-1) to (A-12) containing 30% by mass of Resin (A-1) to (A-12).

In a room where active rays are blocked, add the resin (A), photopolymerization initiator (B), and crosslinking agent (C) shown in Tables 3 and 4 to a plastic container in the amounts (parts by mass) shown in Tables 3 and 4, respectively. By stirring, the adhesive compositions of Examples 1 to 11 and Comparative Examples 1 to 6 were obtained.

The values of resins (A-1) to (A-12) in Table 3 and Table 4 are for resins (A-1) to (A-) in which the content of resins (A-1) to (A-12) is 30% by mass. 12) The solid content of the solution, that is, the amount (mass parts) of resins (A-1) to (A-12) used. The numerical value of the photopolymerization initiator (B) is the amount (parts by mass) of the photopolymerization initiator (B) used relative to 100 parts by mass of the resin (A). The numerical value of the cross-linking agent (C) is the amount (parts by mass) of the cross-linking agent (C) used relative to 100 parts by mass of the resin (A).

“TETRAD-C”, “TETRAD-X”, “HX”, and “TPO” in Tables 3 and 4 are respectively shown below.

"TETRAD-C": 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd., brand name: TETRAD-C)

"TETRAD-X": N, N'-[1,3-phenylenebis(methylene)]bis[bis(oxiran-2-ylmethyl)amine] (manufactured by Mitsubishi Gas Chemical Co., Ltd., brand name: TETRAD -X)

“HX”: Isocyanurate form of hexamethylene diisocyanate (manufactured by Tosoh Corporation, brand name: Coronate (registered trademark) HX)

“TPO”: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF, brand name: L-TPO)

[Manufacture of adhesive sheet for measuring adhesive force]

The adhesive compositions of Examples 1 to 11 and Comparative Examples 1 to 6 were applied as is on a substrate so that the dried film thickness was 20 μm, and dried by heating at 100°C for 2 minutes to form an adhesive layer. Thereafter, the adhesive sheets of Examples 1 to 11 and Comparative Examples 1 to 6 were obtained by bonding a release sheet onto the adhesive layer. As a substrate, a polyamide (PA) film with a thickness of 25 μm was used. As a release sheet, a polyethylene terephthalate (PET) film with a thickness of 25 μm was used.

[Manufacture of adhesive sheet for bump protection]

The adhesive compositions of Examples 1 to 11 and Comparative Examples 1 to 6 were applied as is on a substrate so that the dried film thickness was 100 μm, and dried by heating at 100°C for 2 minutes to form an adhesive layer. After that, a release sheet was laminated onto the adhesive layer, cured in an oven at 40°C for 3 days, and the adhesive layer was crosslinked and cured to obtain adhesive sheets of Examples 1 to 11 and Comparative Examples 1 to 6. As a substrate, a polyamide (PA) film with a thickness of 25 μm was used. As a release sheet, a polyethylene terephthalate (PET) film with a thickness of 25 μm was used.

The items shown below were evaluated for the adhesive sheets of Examples 1 to 11 and Comparative Examples 1 to 6 obtained in this way by the method shown below. The results are shown in Tables 3 and 4.

The adhesive sheet for measuring adhesive force was cut to a size of 25 mm in length and 100 mm in width, and the release sheet was peeled off to expose the adhesive layer. Next, the adhesive sheet was attached to the glass plate so that the exposed adhesive layer (measurement surface) was in contact with the glass plate, and a 2 kg rubber roller (width: about 50 mm) was rotated once to obtain a sample for measuring peel strength before UV irradiation.

The obtained measurement sample was left in an environment with a temperature of 23°C and a humidity of 50% for 24 hours. After that, a tensile test was performed in the 180° direction at a peeling speed of 300 mm/min according to JIS Z 0237:2009, and the peeling strength (N/25 mm) of the adhesive sheet against the glass plate was measured.

A sample similar to a sample for measuring the peeling strength before UV irradiation was prepared, and irradiated with ultraviolet rays (UV) from the side of the adhesive sheet under the condition of an irradiation dose of 1000 mJ/cm2 to obtain a sample for measuring the peeling strength after UV irradiation. For UV irradiation, a conveyor-type ultraviolet irradiation device (manufactured by iGraphics, 2KW lamp, 80W/cm) was used.

About the obtained sample for measurement, the peeling strength (N/25 mm) of the adhesive sheet to the glass plate was measured in the same manner as the "peeling strength before UV irradiation".

[Adhesive residue after heating test]

The release sheet of the bump protection adhesive sheet was peeled off to expose the adhesive layer. Next, the exposed adhesive layer and the PCB with the bumps (bump diameter ϕ=20㎛, distance between bumps 30㎛, bump height 45㎛) were treated at 40°C for 10 minutes using a mounter (Huglu Electronics HS7800). Attachment was performed. Next, heat treatment was performed at 200°C for 2 hours, and after cooling, ultraviolet rays (UV) were irradiated from the base material side of the adhesive sheet under conditions of an irradiation dose of 1000 mJ/cm2. For UV irradiation, a conveyor-type ultraviolet irradiation device (manufactured by iGraphics, 2KW lamp, 80W/cm) was used. Afterwards, the adhesive sheet is peeled off, and the PCB on which the bump is formed is observed with an optical microscope. If the area of the adhesive residue is 5% or less of the total PCB on which the bump is formed, it is classified as “A”; if it is greater than 5% and less than 20%, it is classified as “A”. The adhesive residue was evaluated as "B", and the case of 20% or more was considered "C".

[Step filling 1]

The release sheet of the bump protection adhesive sheet was peeled off to expose the adhesive layer. Next, the PCB (bump diameter ϕ = 20 ㎛, distance between bumps 30 ㎛, bump height 45 ㎛) with the exposed adhesive layer and bumps formed was treated at 40°C for 5 minutes using a mounter (HS7800 manufactured by Huglu Electronics). Attachment was performed. Observe with an optical microscope from the bump protection adhesive sheet side, “A” if the area containing air bubbles is 1% or less of the total PCB on which the bump is formed, “B” if it is greater than 1% and less than 10%, and “B” if the area containing bubbles is 10% or more. The case was set as "C" and the step filling property of 1 was evaluated.

[Step filling 2]

A blade (“SDC200 R100NMR” manufactured by Tokyo Seimitsu Co., Ltd., kerf width: 0.3 mm, blade rotation speed: 28000 rpm, cutting speed: 30 mm) was applied to the bump-formed PCB obtained by the operation of Step Filling Performance 1 and attached with an adhesive sheet for bump protection. Dicing was performed at /sec, depth of cut: 100 μm). A PCB on which bumps have been formed into small pieces by dicing is observed with an optical microscope from the bump protection adhesive sheet side, and the case where the area containing air bubbles is 1% or less of the total PCB on which the bumps were formed is “A”, and is greater than 1%. The step filling property 2 was evaluated as “B” when it was less than 10%, and “C” when it was 10% or more.

[Step filling 3]

A heat treatment was performed at 200°C for 2 hours on the PCB on which the bump was formed, which was reduced into pieces by the operation of Step Filling 2 and attached with an adhesive sheet for bump protection. After allowing the PCB on which the bumps were formed to cool, observe it with an optical microscope from the bump protection adhesive sheet side, “A” if the area containing air bubbles is 1% or less of the total PCB on which the bumps were formed, and “A” if it is greater than 1% but less than 10%. The step filling property 3 was evaluated as "B", and the case of 10% or more was evaluated as "C".

As shown in Table 3, the adhesive sheets of Examples 1 to 11 all had “adhesive residue after heat test” of A or B. In addition, these adhesive sheets were rated A in all evaluations of “step filling 1”, “step filling 2”, and “step filling 3”, and had good adhesion to the PCB on which bumps were formed.

In contrast, as shown in Table 4, the adhesive sheets of Comparative Examples 1 to 6 in which the molecular weight of the resin (A) exceeded 550,000 had “adhesive residue after heat test” of all A, but “step filling 1”, Regarding “step filling 2” and “step filling 3”, it was B or C, and the adhesion to the PCB on which the bump was formed was insufficient.

[Table 3-1]

[Table 3-2]

[Table 4]

Claims (12)

A protection process of attaching an adhesive sheet having a sheet-like substrate and an adhesive layer formed on the substrate to the bumped surface of the semiconductor device,
A UV irradiation step of curing the adhesive layer by applying UV irradiation to the adhesive sheet, and
A method of manufacturing a semiconductor device comprising a peeling process of peeling and removing the adhesive sheet from the adhered surface on which the bump is formed,
The adhesive layer is a cured product of the adhesive composition,
A method for manufacturing a semiconductor device, wherein the adhesive composition includes a resin (A) and a photopolymerization initiator (B) represented by the following general formula (1-1), and the weight average molecular weight of the resin (A) is 50,000 to 550,000.


(In equation (1-1), k, l, m and n represent the molar composition ratio when k+l+m+n=100. k is greater than 0 and less than or equal to 92. l is 0 to 50. m is greater than 0 and less than or equal to 90. n is 5 to _35. R ^{1 to} R ⁵ are carbon atoms. R ⁶ is an alkyl group with 1 to 16 carbon atoms, or _an aromatic hydrocarbon group ^with 6 _to 20 carbon atoms. j in the formula is 1 or 2.) R ⁸ is a group represented by the general formula (1-2) or (1-3). p and q are any one selected from 0, 1, and 2. When p is 0, R ⁹ is ₁ . According to claim 1,
A method of manufacturing a semiconductor device where n in the above formula (1-1) is 7 to 33. The method of claim 1 or 2,
A method of manufacturing a semiconductor device where k in the formula (1-1) is 45 to 90, l is 4 to 40, and m is 1 to 20. The method of claim 1 or 2,
A method of manufacturing a semiconductor device, wherein the adhesive composition further contains a crosslinking agent (C). The method of claim 1 or 2,
A method of manufacturing a semiconductor device wherein the glass transition temperature of the resin (A) is -80 to 0°C. The method of claim 1 or 2,
A method of manufacturing a semiconductor device having a heating process of 150° C. or higher between the protection process and the peeling process. The method of claim 1 or 2,
A method of manufacturing a semiconductor device having a processing step between the protection step and the peeling step. The method of claim 1 or 2,
A method of manufacturing a semiconductor device having a heating process of 150° C. or higher between the protection process and the UV irradiation process. The method of claim 1 or 2,
A method of manufacturing a semiconductor device having a processing step between the protection step and the UV irradiation step. The method of claim 1 or 2,
A method of manufacturing a semiconductor device having a heating process of 150° C. or higher between the UV irradiation process and the peeling process. The method of claim 1 or 2,
A method of manufacturing a semiconductor device having a processing step between the UV irradiation step and the peeling step. A semiconductor device manufactured by the method according to claim 1 or 2.