TW202335290A - Method for producing semiconductor device, and semiconductor device - Google Patents

Abstract

The present invention provides a method for producing a semiconductor device, the method using an adhesive sheet that is capable of accurately following and adhering to recesses and projections in the surface during a processing step of a semiconductor device that has recesses and projections in the surface, such as a semiconductor chip with a bump and a PCB with a bump, while being free from the generation of an outgas during a high temperature treatment or an adhesive residue on the surface of an adherend from which the adhesive sheet is removed. A method for producing a semiconductor device according to the present invention comprises: a protection step in which an adhesive sheet that has a sheet-like base material and an adhesive layer that is formed on the base material is bonded to an adherend surface of a semiconductor device, the adherend surface having a bump; a UV irradiation step in which the adhesive sheet is irradiated with UV light, thereby curing the adhesive layer; and a separation step in which the adhesive sheet is separated and removed from the adherend surface having a bump. With respect to this method for producing a semiconductor device, the adhesive layer is a cured product of an adhesive composition; the adhesive composition contains a resin (A) that is represented by general formula (1-1) and a photopolymerization initiator (B); and the resin (A) has a weight average molecular weight of 50,000 to 550,000.

Description

Manufacturing method of semiconductor device and semiconductor device

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

Various adhesive wafers are used in the manufacturing steps of semiconductors. Specifically, there are protective sheets used to protect the wafer during the back grinding step of the semiconductor wafer, and fixing sheets used in the step of dicing the semiconductor wafer into device chips. wait. These adhesive sheets are re-peelable adhesive sheets that are attached to the semiconductor wafer of the adherend and are peeled off from the adherend after a specific processing step.

In recent years, with the miniaturization and high-density of electronic equipment, flip-chip mounting has become mainstream as a method of mounting semiconductor components in the smallest area. In flip-chip mounting, semiconductor wafers (for example, Through Silicon Via (TSV) wafers) equipped with protruding electrodes (bumps) having front-end portions made of solder are used to achieve bonding between wafers. The bumped semiconductor chip is electrically bonded and mounted with other semiconductor chips or substrates through a reflow step heated to a temperature above the melting temperature of the solder (usually above 200°C). Furthermore, when a semiconductor chip is mounted on a communication electronic device, communication problems may occur due to electromagnetic radiation generated inside the chip. In order to prevent this, the electromagnetic wave shielding mask on the outer peripheral part of the semiconductor wafer may be subjected to a sputtering step of evaporating a metal film (usually at 150° C. or higher). In the reflow step or sputtering step, a releasable adhesive sheet is used to protect the bump surface.

Bumped printed circuit boards (PCBs) are widely used in semiconductor devices. When fixing a PCB with bumps to another substrate or frame, adhesive tape is sometimes used. During the installation process of semiconductor chips, the PCB with bumps sometimes undergoes a reflow step or a sputtering step.

Patent Document 1 discloses an adhesive tape that has an ultraviolet curable adhesive layer. The ultraviolet curable adhesive layer can be hardened by being attached to a semiconductor chip with bumps and then irradiated with ultraviolet rays. To use the peeling method after the high-temperature treatment step, set the gel fraction of the adhesive layer before hardening to A (%), and pull the adhesive layer after irradiation with light of 3000 mJ/cm ² When the elastic modulus is set to B (MPa), the following relationship is satisfied: -5≦B-exp(A/30). [Prior art documents] [Patent documents]

[Patent Document 1] Japanese Patent Application Publication No. 2020-94199

Semiconductor wafers with bumps and PCBs with bumps have large uneven shapes on their surfaces. Therefore, when they are protected by a releasable adhesive sheet, the adhesive sheet must correctly follow the uneven shapes during the processing steps to be closely adhered. In addition, the adhesive sheet is required to have no outgassing during high-temperature processing such as reflow steps, no residue on the semiconductor wafer when the adhesive sheet is peeled off, and high heat resistance.

However, conventional adhesive sheets cannot meet all the above conditions. In Patent Document 1, since the adhesive layer is not soft enough to follow the unevenness, the adhesion to the unevenness of the sheet attachment surface may be insufficient. In addition, there may be cases where gas is released after the heating step due to additives, and there may be residue when the adhesive sheet is peeled off.

The present invention was made in view of the above situation, and its object is to provide a method for manufacturing a semiconductor device, which includes a processing step using a semiconductor device having unevenness on the surface, such as a semiconductor wafer with bumps, a PCB with bumps, etc. , can still accurately follow the uneven and tightly adhered adhesive sheet, and this manufacturing method does not produce outgassing during high-temperature processing, and there is no residue on the surface of the adherend when the adhesive sheet is peeled off.

Furthermore, an object of the present invention is to provide a semiconductor device manufactured by the above-mentioned manufacturing method. [Means used to solve problems]

The inventors of the present invention have found that the above problems can be solved by providing a protective step of attaching an adhesive sheet formed using an adhesive composition containing resin (A) and photopolymerization to the mating surface with the bumps. The initiator (B) is an essential component, and the resin (A) is a carboxyl group-containing resin (b) obtained by polymerizing a carboxyl group-containing ethylenically unsaturated monomer (a) as an essential monomer component, and The resin obtained by the addition reaction of the ethylenically unsaturated compound (c) containing an alicyclic epoxy group has a weight average molecular weight of 50,000 to 550,000.

The present invention includes the following aspects. [1] A method of manufacturing a semiconductor device, which includes the following steps: attaching an adhesive sheet having a sheet-like base material and an adhesive layer formed on the base material to the bonded surface of a bump attached to the semiconductor device The protection step includes UV irradiation of the adhesive sheet to harden the adhesive layer, and a peeling step of peeling and removing the adhesive sheet from the bonded surface of the bumps. The adhesive layer is composed of an adhesive. The cured product of the object, the aforementioned adhesive composition includes a resin (A) represented by the following general formula (1-1) and a photopolymerization initiator (B), and the weight average molecular weight of the aforementioned resin (A) is 50,000 to 55 ten thousand, (In formula (1-1), k, l, m and n represent the molar composition ratio when k+l+m+n=100, k is more than 0~92 or less, l is 0~50, m It is more than 0 to less than 90, the total of k, l and m is 65 to 95, n is 5 to 35, R ¹ ~ R ⁴ is -H or -CH ₃ , R ⁵ is an alkyl group with 1 to 16 carbon atoms. , R ⁶ is an alicyclic hydrocarbon group with 3 to 30 carbon atoms or an aromatic hydrocarbon group with 6 to 20 carbon atoms, R ⁷ is -H or -(CH ₂ ) _j -COOH (j in the formula is 1 or 2 ), R ⁸ is a group represented by the above general formula (1-2) or (1-3). In formulas (1-2) and (1-3), p and q are selected from 0, 1 and 2. In either case, when p is 0, s represents 0, when p is 1 or 2, s represents 1, and R ⁹ represents -H or -CH ₃ ). [2] The manufacturing method of a semiconductor device as in [1], wherein n in the aforementioned formula (1-1) is 7 to 33. [3] The manufacturing method of a semiconductor device as in [1] or [2], wherein k in the aforementioned formula (1-1) 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 cross-linking agent (C). [5] The method for manufacturing a semiconductor device according to any one of [1] to [4], wherein the glass transition temperature of the resin (A) is -80~0°C. [6] The manufacturing method of a semiconductor device according to any one of [1] to [5], wherein there is a heating step of 150°C or above between the aforementioned protecting step and the aforementioned stripping step. [7] The manufacturing method of a semiconductor device according to any one of [1] to [6], wherein there is a processing step between the aforementioned protecting step and the aforementioned stripping step. [8] The manufacturing method of a semiconductor device according to any one of [1] to [5], wherein there is a heating step of 150°C or above between the aforementioned protection step and the aforementioned UV irradiation step. [9] The manufacturing method of a semiconductor device according to any one of [1] to [6], wherein there is a processing step between the aforementioned protection step and the aforementioned UV irradiation step. [10] The method for manufacturing a semiconductor device according to any one of [1] to [5], wherein there is a heating step of 150° C. or above between the UV irradiation step and the peeling step. [11] The method for manufacturing a semiconductor device according to any one of [1] to [6], wherein there is a processing step between the UV irradiation step and the peeling step. [12] A semiconductor device manufactured by the manufacturing method according to any one of [1] to [11]. [Effects of the invention]

An adhesive composition containing a resin (A) and a photopolymerization initiator (B) has good heat resistance because the resin (A) has a structure derived from an alicyclic compound. In addition, since the weight average molecular weight of the resin (A) is 50,000 to 550,000, it imparts flexibility to the adhesive layer. Therefore, the adhesive composition can form an adhesive layer with good adhesion to electronic components such as bumped semiconductor wafers and bumped PCBs with uneven surfaces. Furthermore, the weight average molecular weight of the resin (A) is 50,000 to 550,000, which can reduce the outgassing generated from the adhesive layer during high-temperature processing. Furthermore, the adhesive force of the adhesive layer containing the cured product of the adhesive composition is changed by irradiating ultraviolet (UV) to harden the unsaturated bonds in the resin (A) to form a three-dimensional cross-linked structure. Specifically, the adhesive composition shows sufficient adhesion to the adherend before UV irradiation, and the adhesion decreases after UV irradiation, enabling excellent easy peelability, and fully preventing adhesion to the adherend after peeling. The residue is blurry.

By using the manufacturing method of a semiconductor device of the present invention, it is possible to manufacture semiconductor devices with bumps and convexes on the surface, such as bumped semiconductor wafers and bumped PCBs, etc., and the adhesive sheet can accurately follow the bumps and bumps. As for the tight adhesion, there will be no outgassing during high-temperature processing and no residue residue will be generated on the bonded surface with the bumps when the adhesive sheet is peeled off.

Hereinafter, a method for manufacturing a semiconductor device and a semiconductor device according to the present invention will be described. However, the present invention is not limited to the following embodiments.

[Method for manufacturing semiconductor device] A method of manufacturing a semiconductor device according to an embodiment, which includes the following steps: A protective step of attaching an adhesive sheet having a sheet-like base material and an adhesive layer formed on the base material to the bonded surface of the bump attached to the semiconductor device, UV irradiation step of irradiating the aforementioned adhesive sheet to harden the aforementioned adhesive layer, and A peeling step of peeling and removing the adhesive sheet from the adhered surface with the bumps.

[Protection steps] The protection step involves attaching the adhesive sheet to the bump-attached surface of the semiconductor device provided with bump electrodes. Thereby, the bump-attached surface of the semiconductor device is protected. Examples of the semiconductor device include a bumped semiconductor wafer, a bumped printed wiring board (PCB), a bumped FPC substrate, and other semiconductor devices having uneven surfaces. These semiconductor devices include various processing steps in the manufacturing step before the mounting step of connecting the bump electrodes to other electronic devices. By protecting the bonded surface with bumps in the aforementioned processing steps, damage, damage, contamination, etc. of the bonded surface with bumps can be prevented. The protection step also serves as a temporary fixation function for the semiconductor device for subsequent processing steps.

When the semiconductor device has a plurality of bonded surfaces with bumps, in the protection step, an adhesive sheet is attached to part or all of the bonded surfaces with bumps. For example, when laminating semiconductor wafers disclosed in Japanese Patent Application Laid-Open No. 2014-225546, etc., an adhesive sheet can be attached to the non-mounting surface other than the mounting surface of the bonded surface with the bumps.

[Adhesive sheet] An adhesive sheet according to one embodiment includes a sheet-like base material and an adhesive layer formed on the base material.

It is preferable to provide a release sheet (separator) on the surface of the adhesive layer opposite to the base material. When a release sheet is provided on the adhesive layer, the release sheet can be used to protect the adhesive layer until use. When a peeling sheet is provided on the adhesive layer, the peeling sheet is peeled off to expose the adhesive layer, and the pressure-bonding operation of the adhesive layer (adhering surface) to the adherend can be performed efficiently.

The adhesive sheet can be used as an adhesive tape formed into a shape corresponding to the shape of the adherend by a stamping method or the like. The adhesive sheet can also be used by rolling and cutting the tape into a roll shape.

As the base material, a conventional sheet-shaped material can be appropriately selected and used. As the base material, a resin sheet made of a transparent resin material is preferably used.

Examples of the resin material include polyolefins such as polyethylene (PE) and polypropylene (PP); polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polynaphthalene. Polyesters such as ethylene dicarboxylate (PEN); polyvinyl chloride (PVC); polyamide (PA); polyimide (PI); polyphenylene sulfide (PPS); ethylene vinyl acetate (EVA) ; and polytetrafluoroethylene (PTFE). Among these resin materials, in order to obtain a sheet with moderate flexibility, PE, PP or PET is preferably used. The resin material can be used alone, or two or more types can be mixed and used.

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

The thickness of the base material can be appropriately selected according to the purpose of the adhesive sheet, the material of the base material, etc. The adhesive sheet is used to protect the semiconductor chip with bumps or the flexible printed circuit board (FPC) with bumps during the reflow step or sputtering process. When using a resin sheet as the base material, the thickness of the base material is preferably 5~ 1000μm, preferably 10~300μm. When the base material thickness is 5 μm or more, the adhesive sheet has higher rigidity (stronger stiffness). Therefore, when the adhesive sheet is attached to an adherend such as a semiconductor chip or peeled off from the adherend, there is a tendency for the adhesive sheet to become wrinkled or bulged. Moreover, when the base material thickness is 5 μm or more, the adhesive sheet attached to the adherend can be easily peeled off from the adherend, resulting in good workability (handling properties, controllability). When the thickness of the base material is 1000 μm or less, it can prevent the adhesive sheet from being too rigid (strong stiffness) and lowering the workability.

When a resin sheet is used as the base material, the base material can be produced by appropriately using conventionally known general sheet forming methods (such as extrusion molding, T-die molding, inflation molding, uniaxial or biaxial stretching, etc.).

Surface treatment can also be performed on the surface of the side of the substrate that is in contact with the adhesive layer to improve the adhesion between the substrate and the adhesive layer.

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

The adhesive layer of the adhesive sheet according to one embodiment includes a hardened product of the adhesive composition described below.

The thickness of the adhesive layer is preferably 1~1000 μm, more preferably 5~750 μm, and more preferably 10~500 μm. When the thickness of the adhesive layer is 1 μm or more, the thickness uniformity of the adhesive layer is good. When the thickness of the adhesive layer is 1000 μm or less, the adhesive layer can fully adhere to the unevenness of the surface without any ridges.

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

The thickness of the release sheet can be appropriately selected depending on the use of the adhesive sheet, the material of the release sheet, etc. When a resin sheet is used as the 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.

The peeling surface of the peeling sheet (the surface arranged in contact with the adhesive layer) can be peeled off using conventionally known release agents such as silicone type, long chain alkyl type, fluorine type, etc., if necessary.

[Production method of adhesive sheet] The adhesive sheet of one embodiment can be produced by the method shown below, for example.

First, an adhesive solution is prepared in which the adhesive composition described below is dissolved or dispersed in a solvent. The above adhesive composition can be used directly as an adhesive solution.

Secondly, the adhesive solution is coated on the substrate, and when it contains a solvent, it is heated and dried to remove the solvent to form an adhesive layer. Subsequently, a release sheet is attached to the adhesive layer as necessary. Furthermore, if necessary, the obtained sheet is cured in an oven for a certain period of time to form a cross-linked structure, whereby an adhesive sheet can be obtained.

As another method of manufacturing an adhesive sheet, for example, the above-mentioned adhesive solution is coated on a peelable sheet, and when a solvent is contained, the solution is heated and dried to remove the solvent to form an adhesive layer. Then, place the peeling sheet with the adhesive layer on the base material with the side of the adhesive layer facing the base material, transfer the adhesive layer to the base material, and cure it in an oven for a certain period of time as needed. , a method of forming a cross-linked structure.

As a method of applying the adhesive solution to the base material (or the release sheet), a conventional method can be used. Specifically, a conventional coater is used, such as a gravure roll coater, a reverse roll coater, a contact roll coater, a dip roll coater, a rod coater, a knife coater, and a spray coater. Coating methods such as notch wheel applicator and direct applicator.

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

(Adhesive composition) An adhesive composition according to one embodiment includes a resin (A) and a photopolymerization initiator (B).

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

(In formula (1-1), k, l, m and n represent the molar composition ratio when k+l+m+n=100, k is more than 0~92 or less, l is 0~50, m It is more than 0 to less than 90, the total of k, l and m is 65 to 95, n is 5 to 35, R ¹ ~ R ⁴ is -H or -CH ₃ , R ⁵ is an alkyl group with 1 to 16 carbon atoms. , R ⁶ is an alicyclic hydrocarbon group with 3 to 30 carbon atoms or an aromatic hydrocarbon group with 6 to 20 carbon atoms, R ⁷ is -H or -(CH ₂ ) _j -COOH (j in the formula is 1 or 2 ), R ⁸ is a group represented by the above general formula (1-2) or (1-3). In formulas (1-2) and (1-3), p and q are selected from 0, 1 and 2. In either case, when p is 0, s represents 0, when p is 1 or 2, s represents 1, and R ⁹ represents -H or -CH ₃ ).

In the formula (1-1), k, l, m and n represent the molar composition ratio when k+l+m+n=100. k series exceeds 0~92 or less. l ranges from 0 to 50. m series exceeds 0~90 or less. The total of k, l and m is 65~95. When the total of k, l and m is 65 or more, an adhesive layer with sufficient adhesion to the adherend before ultraviolet irradiation can be formed. The total of k, l and m is preferably 70 to 94, more preferably 75 to 90.

In formula (1-1), the repeating unit shown in the parentheses enclosed by k (hereinafter also referred to as "repeating unit k") is an essential repeating unit. The repeating unit k contributes to the adhesion of the adhesive composition before UV irradiation. The repeat number k of the repeating unit k is from more than 0 to 92 or less, preferably from 45 to 90, more preferably from 60 to 88.

In formula (1-1), the repeating unit shown in parentheses enclosed by l (hereinafter also referred to as "repeating unit l") may not be present. In other words, the repeat number l of the repeating unit l may be 0. The repeating unit l contributes to the heat resistance of the adhesive composition. The repeat number l of the repeating unit l is 0 to 50, preferably 4 to 40, more preferably 5 to 30.

In formula (1-1), the repeating unit shown in parentheses enclosed by m (hereinafter also referred to as "repeating unit m") is an essential repeating unit. The repeating unit m contributes to the adhesion and heat resistance of the adhesive composition before UV irradiation. When the adhesive composition contains a cross-linking agent having a functional group that reacts with a carboxyl group, the repeating unit m imparts cohesive force to the adhesive layer by reacting with the cross-linking agent. The repeat number m of the repeating unit m is from more than 0 to less than 90, preferably from 1 to 20, more preferably from 1 to 10.

In formula (1-1), the repeating unit shown in parentheses enclosed by n (hereinafter also 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 repeat number n of the repeating unit n is 5 to 35, preferably 7 to 33, and more preferably 10 to 30. When the repeating unit n is 35 or less, the unsaturated bonds in the resin (A) are hardened by UV irradiation to form a three-dimensional cross-linked structure, thereby forming an adhesive layer with an adhesive force reduced to an appropriate range. When n is 5 or more, the heat resistance improvement effect due to the structure derived from the alicyclic compound can be obtained.

Through the multiplication effect of the functions contributed by these repeating units, the adhesive composition including the resin (A) has a better balance between the adhesive force before ultraviolet (UV) irradiation and the adhesive force after UV irradiation. As a result, sufficient adhesion can be obtained before UV irradiation, and an adhesive composition can be obtained that has excellent peelability with reduced adhesion after UV irradiation. Moreover, even if the adhesive composition returns to room temperature from a high temperature state before UV irradiation, the adhesive force will not be too high, and it can obtain excellent peelability after UV irradiation, and it is difficult to produce residue on the adherend after peeling off. paste.

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

The repeating unit k may be a plurality of repeating units with different R ¹ and/or R ₅ . When the repeating unit k includes a plurality of repeating units, the repeating number k of the repeating unit k represents the total repeating number of the plurality of repeating units. For example, when the repeating unit k includes repeating units A and B with different R ¹ and/or R ⁵ , including 2 repeating units A and 3 repeating units B, the repeating number k is the sum of the number of A and the number of B. 「5」.

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

The repeating unit 1 can be a plurality of repeating units with different R ² and/or R ⁶ . When the repeating unit 1 includes a plurality of repeating units, the repeating number l of the repeating unit 1 represents the total repeating number of the plurality of repeating units.

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

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

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

The repeating unit n may be a plurality of repeating units with different R ⁴ and/or R ⁸ . When the repeating unit n includes a plurality of repeating units, the repeat number n of the repeating unit n represents the total number of repeats of the plurality of repeating units.

The resin (A) represented by formula (1-1) may be any of a random copolymer, a block copolymer, and an alternating copolymer composed of repeating units k, repeating units l, repeating units m, and repeating units n. By. The resin (A) represented by the formula (1-1) may not include the repeating unit l, but may be any random copolymer, block copolymer, or alternating copolymer composed of the repeating unit k, the repeating unit m, and the repeating unit n. One.

The weight average molecular weight of the resin (A) is 50,000 to 550,000, preferably 100,000 to 500,000, more preferably 260,000 to 450,000. When the weight average molecular weight of the resin (A) is 50,000 or more, it is more difficult for the adhesive layer to remain on the adherend when the adhesive sheet having an adhesive layer containing a hardened substance of the adhesive composition is attached to the adherend and then peeled off. physically. When the weight average molecular weight of the resin (A) is 550,000 or less, the adhesive layer is fully adhered to the surface irregularities of bumps and the like without gaps. The weight average molecular weight of the resin (A) is a value measured by the method described in the Examples.

The glass transition temperature (Tg) of the resin (A) is preferably -80~0°C, more preferably -60~-10°C, still more preferably -50~-10°C. When the glass transition temperature of resin (A) is in the range of -80°C to 0°C, the adhesive composition before UV irradiation has good adhesion. 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 over 0 to 25 mg KOH/g, more preferably 3 to 20 mg KOH/g. When the acid value of the resin (A) exceeds the range of 0~25mgKOH/g, it can reduce the contamination (residual paste) of the adherend after heating. When the adhesive composition contains a cross-linking agent and the acid value of the resin (A) is within the above range, the resin (A) reacts with the cross-linking agent to effectively increase the cohesive force of the adhesive composition, thereby reducing the The adherend is contaminated (residual paste). The acid value of the resin (A) is a value measured by the method described in the Examples.

(Manufacturing method of resin (A)) Resin (A) can be produced by the method shown below, for example.

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

Next, the resin (A) can be produced by the addition reaction of the carboxyl group-containing resin (b) and the 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 forms the skeleton of the repeating unit m by polymerization. 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, (meth)acrylic acid and/or (meth)acrylic acid β-carboxyethyl ester is preferably used as the carboxyl group-containing ethylenically unsaturated monomer (a) from the viewpoint of reactivity.

In this disclosure, (meth)acrylic acid refers to “acrylic acid” or “methacrylic acid”. (Meth)acrylate refers to "acrylate" or "methacrylate". The so-called (meth)acrylyl group refers to "acrylyl group" or "methacrylyl group".

(Carboxyl-containing resin (b)) The carboxyl group-containing resin (b) contains at least a carboxyl group-containing ethylenically unsaturated monomer (a) and an ethylenically unsaturated monomer (d) copolymerizable with the carboxyl group-containing ethylenically unsaturated monomer (a). The raw material monomers are copolymerized.

The carboxyl group-containing resin (b) is a component that forms the skeleton of the resin (A) represented by the formula (1-1). The repeating unit k, the repeating unit 1 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 monomers that form the skeleton of the repeating unit k by polymerization are used. As the ethylenically unsaturated monomer (d), one or more monomers that form the skeleton of the repeating unit k by polymerization may be used together with the monomer that forms the skeleton of the repeating unit k by polymerization.

The ethylenically unsaturated monomer (d) that forms the skeleton of the repeating unit k by polymerization is an alkyl ester of (meth)acrylic acid having 1 to 16 carbon atoms. From the perspective of adjusting the peel strength of the adhesive composition, Preferably, it contains an alkyl ester of (meth)acrylic acid having 2 to 16 carbon atoms, and more preferably, it contains an alkyl ester of (meth)acrylic acid having 4 to 12 carbon atoms. Specific examples of alkyl esters of (meth)acrylic acid having 1 to 16 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and (meth)acrylate. n-Butyl acrylate, tert-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, (meth)acrylic acid n-Hexyl ester, isooctyl (meth)acrylate and lauryl (meth)acrylate. Among these, preferred are methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and iso(meth)acrylate. Octyl ester. In this disclosure, the number of carbon atoms used with respect to (meth)acrylate refers to the number of carbon atoms of the residue excluding the (meth)acryloxy group.

Examples of the ethylenically unsaturated monomer (d) that forms the skeleton of the repeating unit l by polymerization include (meth)acrylate containing a cyclic alkyl group having 3 to 30 carbon atoms, and (meth)acrylate containing a cyclic alkyl group having 6 to 30 carbon atoms. 20 Aromatic (meth)acrylate.

Examples of the (meth)acrylate containing a cyclic alkyl group having 3 to 30 carbon atoms used as the ethylenically unsaturated monomer (d) used to form the skeleton of the repeating unit 1 by polymerization include (methyl) Cyclohexyl acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicycloalkenyloxyethyl (meth)acrylate, (meth)acrylate ) dicyclopentyl acrylate and dicyclopentyloxyethyl (meth)acrylate. Among these, isobornyl (meth)acrylate is particularly preferably used. When the raw material monomer of the carboxyl group-containing resin (b) contains a cyclic alkyl group-containing (meth)acrylate, the adhesive composition containing the resin (A) produced using the carboxyl group-containing resin (b) can be improved. Heat resistance.

Examples of the (meth)acrylate containing an aromatic group having 6 to 20 carbon atoms used as the ethylenically unsaturated monomer (d) that forms the skeleton of the repeating unit 1 by polymerization include (meth)acrylic acid. Benzyl ester, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, phenoxypropyl (meth)acrylate and phenoxypolypropylene glycol (meth)acrylate . Among these, benzyl (meth)acrylate is particularly preferably used. When the raw material monomer of the carboxyl group-containing resin (b) contains an aromatic group-containing (meth)acrylate, the heat resistance of the adhesive composition containing the resin (A) produced using the carboxyl group-containing resin (b) can be improved. sex.

The raw material monomers of the carboxyl group-containing resin (b) may include not only the above-mentioned carboxyl group-containing ethylenically unsaturated monomer (a) and the above-mentioned ethylenically unsaturated monomer (d), but also the above-mentioned ethylenically unsaturated monomer. Monomers other than monomer (d) that can be copolymerized with the carboxyl group-containing ethylenically unsaturated monomer (a).

Examples of the ethylenically unsaturated monomer other than the above-mentioned ethylenically unsaturated monomer (d) that can be copolymerized with the carboxyl group-containing ethylenically unsaturated monomer (a) include (meth)acrylic acid alkoxyalkyl ester. , alkoxy (poly)alkylene glycol (meth)acrylate, hydroxyl-containing (meth)acrylate, fluorinated alkyl (meth)acrylate, dialkylaminoalkyl (meth)acrylate and ( Meth)acrylamide compound.

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

Examples of the alkoxy (poly)alkylene glycol (meth)acrylate include methoxy diethylene glycol (meth)acrylate, ethoxy diethylene glycol (meth)acrylate, and methoxy diethylene glycol (meth)acrylate. Oxydipropylene glycol (meth)acrylate.

Examples of the hydroxyl-containing (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,3-butanediol (meth)acrylate, 1,4-butanediol (meth)acrylate, 1,6-hexanediol (meth)acrylate and 3-methyl (meth)acrylate Pentylene glycol ester.

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

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

Examples of the (meth)acrylamide compound include (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, and N-propyl (meth)acrylamide, N-isopropyl(meth)acrylamide, N-hexyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N -Diethyl(meth)acrylamide, (meth)acrylamide and diacetoneacrylamide.

Specific examples of monomers other than the ethylenically unsaturated monomer (d) that can be copolymerized with the carboxyl group-containing ethylenically unsaturated monomer (a) other than the above include acrylonitrile, methacrylonitrile, and styrene. , α-methylstyrene, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl toluene, N-vinylpyridine, N-vinyl Pyrrolidone, dialkyl itaconate, dialkyl fumarate, allyl alcohol, hydroxybutyl vinyl ether, hydroxyethyl vinyl ether, 4-hydroxymethylcyclohexylmethyl vinyl ether, triethylene glycol Alcohol monovinyl ether, diethylene glycol monovinyl ether, methyl vinyl ketone, allyltrimethylammonium chloride and dimethylallyl vinyl ketone.

The method for producing the carboxyl group-containing resin (b) is not particularly limited. For example, by polymerizing the raw material monomers including the carboxyl group-containing ethylenically unsaturated monomer (a) and the ethylenically unsaturated monomer (d) that constitute the carboxyl group-containing resin (b), by conventional polymerization. Through copolymerization, carboxyl-containing resin (b) can be obtained. Specifically, as the polymerization method, solution polymerization, emulsion polymerization, block polymerization, suspension polymerization, alternating copolymerization, etc. can be used. Among these polymerization methods, considering the addition reaction between the carboxyl group-containing resin (b) obtained after polymerization and the alicyclic epoxy group-containing ethylenically unsaturated compound (c), it is preferably used from the viewpoint of ease of reaction. solution polymerization method.

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

The radical polymerization initiator is not particularly limited and can be appropriately selected and used by those skilled in the art.

Examples of the radical polymerization initiator include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) ), 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2-methylbutyronitrile), 1,1'-Azobis(cyclohexane) alkane-1-carbonitrile), 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropionate)dimethyl ester, etc. azo polymerization initiator; and benzoyl peroxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, dicumyl peroxide, Peroxidation of 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclododecane, etc. It is an oil-soluble polymerization initiator such as polymerization initiator.

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

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

As the polymerization solvent used when producing the carboxyl group-containing resin (b), various general solvents can be used. Examples of the solvent 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; and cyclohexane. Alicyclic hydrocarbons such as alkanes and methylcyclohexane; ketones such as methyl ethyl ketone and methyl isobutyl ketone; glycols such as ethylene glycol, propylene glycol and dipropylene glycol; methyl cellosolve, propylene glycol Glycol ethers such as monomethyl ether and dipropylene glycol monomethyl ether; and glycol esters such as ethylene glycol diacetate and propylene glycol monomethyl ether acetate.

These solvents can be used alone or in combination of two or more.

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

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

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

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

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

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

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

The alicyclic epoxy group-containing ethylenically unsaturated compound (c) can be used alone or in combination of two or more kinds.

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

The resin (A) is preferably an alicyclic epoxy group-containing epoxy group by additionally reacting 0.2 to 0.99 mol for 1 mol of the carboxyl group of the carboxyl group-containing resin (b), more preferably 0.3 to 0.95 mol, and even more preferably 0.6 to 0.95 mol. Manufactured from ethylenically unsaturated compound (c). 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 the adherend before UV irradiation. Sufficient adhesion, after UV irradiation, the adhesion is reduced to obtain better peelability. Moreover, the adhesive composition does not easily become high even if it returns from a high temperature state to room temperature before UV irradiation, and obtains excellent peelability after UV irradiation, and can effectively prevent residues on the adherend after peeling. paste.

The temperature of the addition reaction when producing the resin (A) is preferably 80 to 130°C, particularly preferably 90 to 120°C. When the temperature of the addition reaction is above 80°C, sufficient reaction speed can be obtained. When the temperature of the addition reaction is 130°C or lower, it is possible to prevent the double bond portion from being cross-linked by thermal radical polymerization to produce a gel.

In the additional reaction when producing the resin (A), a conventional catalyst can be used if necessary. Examples of the catalyst include primary amines such as n-butylamine, n-hexylamine, and benzylamine; triethylamine, tributylamine, dimethylbenzylamine, and 1,8-diaza Bicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,4-diazabicyclo[2.2.2]octane, etc. 3rd grade amines; aromatic amines such as aniline, toluidine, phenylenediamine, 1,8-diaminonaphthalene, etc.; pyridine, 2,6-dimethylpyridine, 4-N,N-dimethylaminopyridine Pyridine compounds such as tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, etc.; 4-grade ammonium salts such as tetramethylurea; alkyl ureas such as tetramethylurea; tetramethylguanidine, etc. Guanidine; and triphenylphosphine, dimethylphenylphosphine, tricyclohexylphosphine, tributylphosphine, tris(4-methylphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris( 2,6-dimethylphenyl)phosphine, tris(2,6-dimethoxyphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,4,6 -Phosphine compounds such as trimethoxyphenyl)phosphine.

As a catalyst for the addition reaction, among the above, a tertiary amine, a pyridine compound or a phosphine compound is preferably used in terms of reactivity.

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

Furthermore, 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. By introducing a gas with a polymerization inhibitory effect into the reaction system or adding a polymerization inhibitor, gelation during the addition reaction can be prevented.

An example of a gas having a polymerization inhibitory effect is a gas containing oxygen to an extent that does not fall within the explosion range of the substances contained in the system, such as air.

As the polymerization inhibitor, those known in the art can be used without particular limitation. Examples include 4-methoxyphenol, hydroquinone, methoxyhydroquinone, 2,6-di-tert-butylphenol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol) and phenothiazine. These polymerization inhibitors may be used alone or in combination of two or more types.

The usage amount of the polymerization inhibitor is preferably 0.005 to 5 parts by mass, more preferably 0.005 to 5 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin (b) and the alicyclic epoxy group-containing ethylenically unsaturated compound (c). It is 0.03~3 parts by mass, and the optimum is 0.05~1.5 parts by mass. When the amount of the polymerization inhibitor is too small, the polymerization inhibitory effect may be insufficient. On the other hand, when the amount of the polymerization inhibitor is too large, the exposure sensitivity of the resin (A) during UV irradiation may decrease.

When a gas having a polymerization inhibitory effect and a polymerization inhibitor are used in combination, it is more preferable because the amount of the polymerization inhibitor used can be reduced or the polymerization inhibitory effect can be improved.

<Photopolymerization initiator (B)> Examples of the photopolymerization initiator (B) contained in the adhesive composition include benzophenone, biphenyl, benzoin, ω-bromoacetophenone, chloroacetone, acetophenone, 2 ,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, p-dimethylaminoacetophenone, p-dimethylaminoacetophenone, 2-chloro Benzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone, benzoin methyl ether, benzoin isobutyl ether, benzene Coin n-butyl ether, benzyl methyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-(4-isopropyl Phenyl)-2-hydroxy-2-methylpropan-1-one, methylbenzoylcarboxylate, 2,2-diethoxyacetophenone, 4-N,N'-dimethyl Carbonyl-based photopolymerization initiators such as acetophenone and 2-methyl-1-[4-(methylthio)phenyl]-2-malinylpropan-1-one.

As the photopolymerization initiator (B), sulfide photopolymers such as diphenyl disulfide, dibenzyl disulfide, tetraethylthiuram disulfide, and tetramethylammonium monosulfide can also be used. Polymerization initiator; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, etc. ; Quinone photopolymerization initiators such as benzoquinone and anthraquinone; sulfonyl chloride photopolymerization initiators; or thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, etc. It is a photopolymerization initiator.

Among these photopolymerization initiators (B), based on the solubility of the adhesive composition, 1-hydroxycyclohexyl phenyl ketone and/or 2,4,6-trimethylbenzoyl ketone are preferably used. diphenylphosphine oxide.

These photopolymerization initiators (B) can be used alone or 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, and more preferably 0.5 to 2.0 parts by mass relative to 100 parts by mass of the resin (A). When the content of the photopolymerization initiator (B) is 0.1 parts by mass or more based on 100 parts by mass of the resin (A), the adhesive composition can be hardened by UV irradiation at a sufficiently rapid curing speed, thereby allowing the UV irradiation to Afterwards, the adhesive force of the adhesive composition is sufficiently reduced. When the content of the photopolymerization initiator (B) is 5.0 parts by mass or less based on 100 parts by mass of the resin (A), the adhesive sheet having an adhesive layer containing the adhesive composition is adhered to the adherend. When peeling off, the adhesive layer will not easily remain on the adherend. Even if the content of the photopolymerization initiator (B) exceeds 5.0 parts by mass relative to 100 parts by mass of the resin (A), an effect consistent with the content of the photopolymerization initiator (B) is not seen, so by adding this When the content is 5.0 parts by mass or less, the adhesive composition can be produced economically.

＜Cross-linking agent (C)＞ The adhesive composition not only contains resin (A) and photopolymerization initiator (B), but may also contain a cross-linking agent (C). By containing the cross-linking agent (C), an adhesive composition with a better balance between the adhesive force before UV irradiation and the adhesive force after UV irradiation can be obtained.

The cross-linking agent (C) is not particularly limited, but is preferably 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.

Examples of the cross-linking agent (C) include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hydrogenated toluene diisocyanate, 1,3-xylene diisocyanate, and 1,4-xylene diisocyanate. , diphenylmethane-4,4-diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, isocyanurate body of hexamethylene diisocyanate, tetra Methyl xylene diisocyanate, 1,5-naphthalene diisocyanate, toluene diisocyanate adduct of trimethylolpropane, xylene diisocyanate adduct of trimethylolpropane, triphenylmethane triisocyanate, Isocyanate compounds such as methyl bis(4-phenylmethane)triisocyanate; 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane, bisphenol A epichlorohydrin type Epoxy resin, N,N'-[1,3-phenylenebis(methylene)]bis[bis(ethylene oxide-2-ylmethyl)amine], ethylene glycol diglycidyl ether , polyethylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether , polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether and other epoxy compounds; tetramethylolmethane-tri-β-aziridinyl propionate, trimethylolpropane -Tri-β-ethylenepropionylpropionate, N,N'-diphenylmethane-4,4'-bis(1-ethylenepropinylcarboxamide), N,N'-hexamethylene -Eminedine compounds such as 1,6-bis(1-ethylenecarboxamide); and hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexapropoxymethylmelamine, Melamine compounds such as butoxymethylmelamine, hexapentyloxymethylmelamine, and hexahexyloxymethylmelamine.

Among these cross-linking agents (C), epoxy compounds and/or isocyanate compounds are preferably used because of their good reactivity with the resin (A).

These cross-linking agents (C) can be used alone or in combination of two or more kinds.

The cross-linking 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 relative to 100 parts by mass of the resin (A). parts by mass. When the content of the cross-linking agent (C) is 0.05 parts by mass or more relative to 100 parts by mass of the resin (A), a three-dimensional cross-linked structure is fully formed in the adhesive composition. As a result, the adhesive force of the adhesive composition after UV irradiation can be sufficiently reduced. When the content of the cross-linking agent (C) is 10 parts by mass or less based on 100 parts by mass of the resin (A), the adhesive force of the adhesive composition before UV irradiation is good.

＜Other ingredients＞ If necessary, the adhesive composition may contain other components besides the above-mentioned resin (A), photopolymerization initiator (B), and cross-linking agent (C). Examples of other components include tackifiers, solvents, and various additives.

(Tackiness imparting agent) The adhesive imparting agent can be used by those known in the art without particular restrictions. Examples of the tackifier include terpene-based tackifier resin, phenol-based tackifier resin, rosin-based tackifier resin, aliphatic petroleum resin, aromatic petroleum resin, copolymer petroleum resin, and alicyclic petroleum resin. Resin, xylene resin, epoxy adhesive resin, polyamide adhesive resin, ketone adhesive resin and elastic system adhesive resin. These adhesive imparting agents can be used alone or in combination of two or more types.

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

(solvent) 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 that can be used include methyl ethyl ketone, methyl isobutyl ketone, acetone, ethyl acetate, n-propyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, and n-propanol. , isopropyl alcohol and other organic solvents. These solvents can be used individually or in mixture of 2 or more types.

(additive) Examples of additives include plasticizers, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, benzotriazole and other light stabilizers, Phosphate esters and other flame retardants, surfactants and antistatic agents.

[Production method of adhesive composition] The adhesive composition can be produced by conventionally known methods.

For example, the above-mentioned resin (A), photopolymerization initiator (B), cross-linking agent (C) if necessary, adhesion-imparting agent, solvent, various additives and other other components can be prepared by using conventional methods. Made by mixing and stirring.

The adhesive composition of one embodiment is suitable as a material for forming an adhesive layer of an adhesive sheet, and particularly preferably as a material for forming an adhesive layer of a releasable adhesive sheet.

Since the adhesive composition of one embodiment contains the resin (A) represented by the formula (1-1) and the photopolymerization initiator (B), it can be obtained by using the material as the adhesive layer forming the adhesive sheet. An adhesive sheet with sufficient adhesion to the adherend. Moreover, the adhesive sheet can be peeled off when the adherend to which the adhesive sheet is attached returns from a high-temperature state to room temperature. It can also obtain excellent peelability after UV irradiation and is less likely to cause residue.

[Processing steps] The manufacturing method of a semiconductor device may have a processing step between the above-mentioned protection step and the later-described stripping step.

As the processing steps, conventionally known processing steps used for manufacturing semiconductor devices can be applied without particular limitation. For example, when the adhesive sheet used in the protection step is used as a wafer dicing tape, after the adhesive sheet is attached to the wafer with multiple parts formed in the protection step, the wafer is cut as a processing step, and the wafer is cut into individual parts. A single part (cutting) becomes a cutting step for component chips (wafers). When the lamination step of semiconductor wafers is implemented as a processing step, only the non-mounting surface of the bonded surface with the bump is protected in the protection step, and the mounting surfaces without the adhesive sheet are brought into contact with each other for lamination, while electrical connection is made.

[Heating step] The manufacturing method of a semiconductor device may include a heating step between the above-mentioned protection step and the later-described stripping step. When the manufacturing method of a semiconductor device has a processing step after the protection step, the order of the aforementioned processing steps and heating steps is not limited, but it is preferable based on the protective function and temporary fixing function of the adhesive sheet, that is, from the perspective of maximizing the adhesion performance. The processing step may be performed simultaneously with the heating step, or may be performed before the heating step.

As the heating step, a conventionally known heating step used in the production of semiconductor devices can be applied without particular limitation. Examples of the heating step include a post-hardening step for a PCB with bumps, a sputtering step for a semiconductor wafer, and a reflow step after stacking the semiconductor wafer.

The conditions of the heating step are not particularly limited. By performing the aforementioned protection step before the heating step, the bonded surface with the bumps can be well protected even when a high temperature treatment is performed, for example, above 150°C, above 180°C, or above 200°C. The upper limit temperature of the heating step is not particularly limited, but from the viewpoint of heat resistance of the adhesive sheet, it is preferably 300°C or lower, more preferably 270°C or lower. The heating time is not particularly limited, but may be, for example, 1 minute to 180 minutes, preferably 1 minute to 120 minutes, more preferably 1 minute to 60 minutes.

[UV irradiation step] In the UV irradiation step, UV is usually irradiated from the base material side of the adhesive sheet. When the adherend is translucent, UV can be irradiated from the side of the adherend to the adhesive sheet. UV irradiation can cross-link and harden the adhesive layer, improve the heat resistance of the adhesive sheet, or impart light peeling properties to the adhesive sheet. The UV irradiation step may be performed between the aforementioned protection step and the subsequent peeling step, and the order of the aforementioned processing step and the aforementioned heating step is not limited.

Examples of light sources used for UV irradiation of the adhesive sheet attached to the adherend before peeling off include LED lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, xenon lamps, metal halide lamps, chemical lamps and black lights. It is better to use LED lamps, high-pressure mercury lamps or metal halide lamps for UV irradiation.

The amount of UV irradiation irradiated to the adhesive sheet is preferably 50~3000mJ/cm ² , more preferably 100~600mJ/cm ² . If the amount of UV irradiation irradiated to the adhesive sheet is 50mJ/cm2 or ^more , the adhesive layer can be hardened by UV irradiation at a sufficiently fast curing speed, thereby fully reducing the adhesive force of the adhesive layer after UV irradiation. Small. Even if the UV irradiation dose to the adhesive sheet exceeds 3000mJ/cm ² , corresponding effects are not obtained. Therefore, by setting the UV irradiation dose to the adhesive sheet to 3000mJ/cm ² or less, the impact of UV irradiation on the adherend can be reduced. The impact of the adhesive film can be peeled off economically.

[Peel-off step] In the peeling step, UV irradiation is performed to harden the adhesive layer, and then the adhesive sheet is peeled off from the bonded surface of the attached bump. Through UV irradiation, the unsaturated bonds in the adhesive form a three-dimensional cross-linked structure and harden. As a result, the adhesive force of the adhesive layer is reduced. Subsequently, the adhesive sheet is peeled off from the semiconductor device.

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

According to the method of manufacturing a semiconductor device according to one embodiment, even when the heating step is performed, outgassing is not generated, and the semiconductor device is obtained in a state where there is no residue on the surface of the body to which the bumps are attached, so that it can be achieved without any problem. The resulting semiconductor device is then subjected to subsequent mounting steps. [Example]

Hereinafter, the present invention will be explained more specifically through Examples and Comparative Examples. In addition, the present invention is not limited to the following examples.

[Manufacture Example 1: Production of Resin (A)] <Preparation of the first mixed solution> A first mixed solution was prepared, as shown in Table 1, containing: raw material monomers containing 23.9 parts by mass of acrylic acid of the carboxyl group-containing ethylenically unsaturated monomer (a) as a component that can be combined with the above (a) The polymerized ethylenically unsaturated monomer (d) is 71.8 parts by mass of n-butyl acrylate and 143.6 parts by mass of 2-ethylhexyl acrylate; and a total of 100 parts by mass of the raw material monomers of the carboxyl group-containing resin (b) It was 2.39 parts by mass of 2,2'-azobis(isobutyronitrile) as the polymerization initiator.

<Preparation of the second mixed solution> A second mixed solution was prepared, as shown in Table 1, containing: 59.8 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate of the alicyclic epoxy group-containing ethylenically unsaturated compound (c), relative to A total of 100 parts by mass of the carboxyl group-containing resin (b) and the alicyclic epoxy group-containing ethylenically unsaturated compound (c) obtained by using the first mixed solution was 1.5 parts by mass of tris(4-) as a catalyst. Methylphenyl)phosphine (TPTP), 100.0 parts by mass of n-butyl acetate and 91.1 parts by mass of toluene as solvents.

In a four-necked flask equipped with a stirrer, a dropping pipe, a cooling pipe and a nitrogen introduction pipe, 175.6 parts by mass of n-butyl acetate as a solvent was fed, and the temperature was raised to 80°C in a nitrogen atmosphere. Then, while maintaining the reaction temperature at 80°C ± 2°C, the above-mentioned first mixed solution was evenly added dropwise into the above-mentioned four-necked flask over 4 hours. After the dropwise addition was completed, stirring was continued for 6 hours at a temperature of 80°C ± 2°C. The polymerization is carried out for 1 hour to obtain carboxyl group-containing resin (b). Subsequently, to the reaction system, 0.15 parts by mass of a polymerization inhibitor was added to the total of 100 parts by mass of the carboxyl group-containing resin (b) and the alicyclic epoxy group-containing ethylenically unsaturated compound (c). 4-Methoxyphenol.

The temperature of the reaction system after adding 4-methoxyphenol was raised to 100°C, and the above-mentioned second mixed solution was added dropwise over 0.5 hours, and then stirred at a temperature of 100°C for 8 hours to synthesize resin (A-1) and cool to room temperature. temperature (23℃).

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

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

Regarding the resin (A-1), the weight average molecular weight and glass transition temperature were investigated by the method shown below. The acid value of the resin (A-1) was measured in accordance with JIS K 0070: 1992.

<Weight average molecular weight (Mw)> Using a gel permeation chromatography (Shodex (registered trademark) GPC-101, manufactured by Showa Denko Co., Ltd.), it was measured under the following conditions at room temperature and calculated in terms of polystyrene. Pipe string: Manufactured by Showa Denko Co., Ltd., Shodex (registered trademark) LF-804 Tube string temperature: 40℃ Sample: 0.2 mass% tetrahydrofuran solution of resin (A) Flow: 1mL/min Eluate: Tetrahydrofuran Detector: RI detector

<Glass transition temperature (Tg)> A 10 mg sample was collected from the resin (A-1). Using a differential scanning calorimeter (DSC), the sample temperature was changed from -100°C to 200°C at a heating rate of 10°C/min for differential scanning calorimetry. The starting temperature of the endotherm caused by the observed glass transfer was set to Tg. When more than 2 endothermic onset temperatures are observed, Tg is the simple average of the 2 or more endothermic onset temperatures.

[Manufacturing Examples 2~12] It was prepared in the same manner as in Production Example 1, except that the carboxyl group-containing ethylenically unsaturated monomer (a), the ethylenically unsaturated monomer (d), and the polymerization initiator were used in the contents (parts by mass) shown in Table 1. 1st mixed solution.

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 the catalyst were used in the contents (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 above-mentioned first mixed solution and the above-mentioned second mixed solution were used.

Resins (A-2) to (A-12) were individually identified in the same manner as in Production Example 1 and found to be compounds represented by general formulas (2-2) to (2-12). The repeating unit k of the compound represented by ^the general formulas (2-2) to ( ^2-7 ) and ( ^2-10 ) is two types of repeating units (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 following 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 formula (2-2), k-1 is 31.9, k-2 is 47.6, m is 1.8, and the total of k-1, k-2 and m is 81.3. n is 18.7).

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

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

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

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

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

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

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

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

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

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

Regarding the resins (A-2) to (A-12), the weight average molecular weight, glass transition temperature, and acid value were investigated in the same manner as the resin (A-1). The results are shown in Table 2.

Table 1 shows the carboxyl group-containing ethylenically unsaturated monomer (a) used to produce resins (A-1) to (A-12) and the ethylenically unsaturated monomer (d) copolymerizable with the above (a). ), polymerization initiator, alicyclic epoxy group-containing ethylenically unsaturated compound (c), catalyst, polymerization inhibitor and solvent type and usage amount (mass parts).

[Examples 1 to 11, Comparative Examples 1 to 6] To the reaction solutions of the resins (A-1) to (A-12) synthesized in Production Examples 1 to 12, add ethyl acetate as a diluting solvent, and adjust the contents of the resins (A-1) to (A-12) respectively. is 30% by mass. Using a resin (A-1) ~ (A-12) solution containing 30% by mass of resin (A-1) ~ (A-12), an adhesive composition was obtained by the method shown below.

In a plastic container in a room where active lines are blocked, add the resin (A) and photopolymerization initiator (B) shown in Table 3 and Table 4 at the contents (parts by mass) shown in Table 3 and Table 4 respectively. and cross-linking agent (C) and stirred to obtain the adhesive compositions of Examples 1 to 11 and Comparative Examples 1 to 6.

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

"TETRAD-C", "TETRAD-X", "HX" and "TPO" in Table 3 and Table 4 are respectively represented as follows. “TETRAD-C”: 1,3-bis(N,N’-diglycidylaminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: TETRAD-C) "TETRAD-X": N,N'-[1,3-phenylenebis(methylene)]bis[bis(oxirane-2-ylmethyl)amine] (Mitsubishi Gas Chemical Co., Ltd. Made, trade name: TETRAD-X) "HX": Isocyanurate body of hexamethylene diisocyanate (manufactured by TOSOH Co., Ltd., trade name: CORONATE (registered trademark) HX) "TPO": 2,4,6-trimethylbenzyldiphenylphosphine oxide (manufactured by BASF, trade name: L-TPO)

[Manufacturing of adhesive sheets for measuring adhesive force] The adhesive compositions of Examples 1 to 11 and Comparative Examples 1 to 6 were directly coated on the substrate such that the dried film thickness was 20 μm, and heated and dried at 100° C. for 2 minutes to form an adhesive layer. Subsequently, by laminating the release sheet on the adhesive layer, the adhesive sheets of Examples 1 to 11 and Comparative Examples 1 to 6 were obtained. As the base material, a polyamide (PA) film with a thickness of 25 μm was used. As the release sheet, a polyethylene terephthalate (PET) film with a thickness of 25 μm was used.

[Manufacturing of adhesive sheets for bump protection] The adhesive compositions of Examples 1 to 11 and Comparative Examples 1 to 6 were directly coated on the substrate such that the film thickness after drying was 100 μm, and heated and dried at 100° C. for 2 minutes to form an adhesive layer. Subsequently, the peeled sheet was attached to the adhesive layer and cured in an oven at 40° C. for 3 days to cross-link and harden the adhesive layer, thereby obtaining the adhesive sheets of Examples 1 to 11 and Comparative Examples 1 to 6. As the base material, a polyamide (PA) film with a thickness of 25 μm was used. As the release sheet, a polyethylene terephthalate (PET) film with a thickness of 25 μm was used.

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

[Peel strength before UV irradiation] Cut out the adhesive sheet for measuring adhesion into a size of 25mm long and 100mm wide, and peel off the peeling sheet to expose the adhesive layer. Next, attach the adhesive sheet to the glass plate in such a way that the exposed adhesive layer (measurement surface) is in contact with the glass plate, and use a 2kg rubber roller (width: about 50mm) to go back and forth once to obtain the peel strength before UV irradiation. Samples for measurement.

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

[Peel strength after UV irradiation] Prepare the same sample for measuring the peel strength before UV irradiation, and irradiate ultraviolet (UV) from the adhesive sheet side at an irradiation dose of 1000 mJ/cm ² to obtain the peel strength after UV irradiation. Sample. For the UV irradiation system, a conveyor type ultraviolet irradiation device (manufactured by EYE GRAPHIC, 2KW lamp, 80W/cm) was used.

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

[Residue after heating test] Peel off the bump protection adhesive sheet to expose the adhesive layer. Next, the exposed adhesive layer and the PCB with bumps (bump diameter φ = 20 μm, distance between bumps 30 μm, bump height 45 μm) were processed using a mounter (HS7800 manufactured by Hugle Electronics Co., Ltd.) at 40°C for 10 minutes to attach. Next, heat treatment is performed at 200°C for 2 hours, and after cooling, ultraviolet (UV) is irradiated from the base material side of the adhesive sheet at an irradiation dose of 1000 mJ/cm ² . For the UV irradiation system, a conveyor type ultraviolet irradiation device (manufactured by EYE GRAPHIC, 2KW lamp, 80W/cm) was used. Then, peel off the adhesive sheet and observe the PCB with bumps using an optical microscope. If the residual paste area is less than 5% of the entire PCB with bumps, the residual paste is evaluated as "A". If it is greater than 5% and less than 20%, the evaluation is "A". It is "B", and when it is 20% or more, it is evaluated as "C".

[Step embeddability 1] The peeling sheet of the bump protecting adhesive sheet exposes the adhesive layer. Next, the exposed adhesive layer and the PCB with bumps (bump diameter φ = 20 μm, distance between bumps 30 μm, bump height 45 μm) were processed using a mounter (HS7800 manufactured by Hugle Electronics Co., Ltd.) at 40°C for 5 minutes to attach. When observed with an optical microscope from the side of the bump protection adhesive sheet, if the area where air bubbles are mixed is less than 1% of the entire PCB with bumps, the step embedding property 1 is evaluated as "A"; if it is greater than 1% and less than 10% The evaluation is "B", and when it is 10% or more, the evaluation is "C".

[Step embeddability 2] For the PCB with bumps and the adhesive sheet for bump protection that is obtained by the operation of step embedability 1, use a blade ("SDC200 R100NMR" manufactured by Tokyo Seiko Co., Ltd., curve width: 0.3mm, blade rotation speed: 28000rpm, cutting speed: 30mm/sec, cutting depth: 100μm) for cutting. The bump-attached PCB cut into small pieces was observed with an optical microscope from the bump protection adhesive sheet side. When the area where air bubbles are mixed is less than 1% of the entire bump-attached PCB, the step embedding property 2 is evaluated. It is "A", when it is greater than 1% and less than 10%, it is evaluated as "B", and when it is 10% or more, it is evaluated as "C".

[Step embeddability 3] The PCB with bumps and the adhesive sheet for bump protection that has been cut into small pieces by the operation of step embedding property 2 is heat treated at 200°C for 2 hours. After the PCB with bumps is allowed to cool, observe it with an optical microscope from the bump protection adhesive sheet side. If the area where bubbles are mixed is less than 1% of the entire PCB with bumps, the step embedding property is evaluated as "3" A", when it is greater than 1% and less than 10%, it is evaluated as "B", and when it is more than 10%, it is evaluated as "C".

As shown in Table 3, the "residual paste after heating test" of the adhesive sheets of Examples 1 to 11 are all A or B. Moreover, these adhesive sheets were rated A in any of the evaluations of "Step Embedding Properties 1", "Step Embedding Properties 2", and "Step Difference Embedding Properties 3", and the sealing of the PCB with bumps was Good adhesion.

On the other hand, as shown in Table 4, for the adhesive sheets of Comparative Examples 1 to 6 in which the molecular weight of the resin (A) exceeds 550,000, the "residual paste after the heating test" is all A, but the "step difference embedding" is "Property 1", "Step Embedding Property 2", and "Step Embedding Property 3" are B or C, indicating insufficient adhesion to PCBs with bumps.

Claims (12)

A manufacturing method of a semiconductor device, which includes the following steps: a step of protecting an adhesive sheet having a sheet-like base material and an adhesive layer formed on the base material on the bonded surface of the bump attached to the semiconductor device, UV irradiation of the adhesive sheet to harden the adhesive layer, and a peeling step of peeling and removing the adhesive sheet from the bonded surface with the bumps. The adhesive layer is the hardening of the adhesive composition. The aforementioned adhesive composition includes a resin (A) represented by the following general formula (1-1) and a photopolymerization initiator (B). The weight average molecular weight of the aforementioned resin (A) is 50,000 to 550,000. (In formula (1-1), k, l, m and n represent the molar composition ratio when k+l+m+n=100, k is more than 0~92 or less, l is 0~50, m It is more than 0 to less than 90, the total of k, l and m is 65 to 95, n is 5 to 35, R ¹ ~ R ⁴ is -H or -CH ₃ , R ⁵ is an alkyl group with 1 to 16 carbon atoms. , R ⁶ is an alicyclic hydrocarbon group with 3 to 30 carbon atoms or an aromatic hydrocarbon group with 6 to 20 carbon atoms, R ⁷ is -H or -(CH ₂ ) _j -COOH (j in the formula is 1 or 2 ), R ⁸ is a group represented by the above general formula (1-2) or (1-3). In formulas (1-2) and (1-3), p and q are selected from 0, 1 and 2. In either case, when p is 0, s represents 0, when p is 1 or 2, s represents 1, and R ⁹ represents -H or -CH ₃ ). For example, the manufacturing method of a semiconductor device according to claim 1, wherein n in the aforementioned formula (1-1) is 7 to 33. For example, the manufacturing method of a semiconductor device according to claim 1 or 2, wherein k in the aforementioned formula (1-1) is 45 to 90, l is 4 to 40, and m is 1 to 20. The method for manufacturing a semiconductor device according to claim 1 or 2, wherein the adhesive composition further contains a cross-linking agent (C). The method for manufacturing a semiconductor device according to claim 1 or 2, wherein the glass transition temperature of the resin (A) is -80~0°C. The method for manufacturing a semiconductor device according to claim 1 or 2, wherein there is a heating step of 150° C. or above between the protection step and the stripping step. The manufacturing method of a semiconductor device as claimed in claim 1 or 2, wherein there is a processing step between the aforementioned protection step and the aforementioned stripping step. The manufacturing method of a semiconductor device according to claim 1 or 2, wherein there is a heating step of 150°C or above between the aforementioned protection step and the aforementioned UV irradiation step. The manufacturing method of a semiconductor device according to claim 1 or 2, wherein there is a processing step between the aforementioned protection step and the aforementioned UV irradiation step. The method for manufacturing a semiconductor device according to claim 1 or 2, wherein there is a heating step of 150° C. or above between the UV irradiation step and the peeling step. The method for manufacturing a semiconductor device according to claim 1 or 2, wherein there is a processing step between the UV irradiation step and the peeling step. A semiconductor device manufactured by the method for manufacturing a semiconductor device according to any one of claims 1 to 11.