Method for manufacturing semiconductor device, adhesive sheet for manufacturing semiconductor device, and wound body

Abstract

The purpose of the present invention is to provide a method for manufacturing a semiconductor device that makes it possible to suppress any decrease in yield in a rewiring process or the like and to improve yield in semiconductor device manufacturing or the like. In addition, the purpose of the present invention is to provide an adhesive sheet for manufacturing a semiconductor device that makes it possible to suppress any decrease in yield in a rewiring process or the like. Furthermore, the purpose of the present invention is to provide a wound body in which the aforementioned adhesive sheet for manufacturing a semiconductor device is wound. The present invention is a method for manufacturing a semiconductor device, the method having the following first step, second step, and third step. First step: a step for laminating, onto a support substrate, an adhesive sheet having a metal layer and an adhesive layer that contains a resin. Second step: a step for forming a semiconductor rewiring layer on the metal layer. Third step: a step for removing the support substrate and the adhesive layer.

Description

Method for manufacturing semiconductor device, adhesive sheet for manufacturing semiconductor device, and roll

[0001] The present invention relates to a method for producing a semiconductor device, an adhesive sheet for use in producing a semiconductor device, and a roll of the adhesive sheet for use in producing a semiconductor device.

[0002] During the processing of electronic components such as semiconductors, in order to facilitate the handling of the electronic components and prevent them from being damaged, the electronic components are fixed to a support substrate via a temporary fixing material made of an adhesive resin composition, or an adhesive sheet having an adhesive layer is attached to the electronic components to protect them. For example, when a thick film wafer cut from a high-purity silicon single crystal or the like is ground to a predetermined thickness to obtain a thin film wafer, the thick film wafer is adhered to a support substrate via an adhesive resin composition.

[0003] Thus, adhesive resin compositions and adhesive sheets used for electronic components are required to have high enough adhesion to firmly fix the electronic components during processing, as well as the ability to peel the electronic components off without damaging them after processing is complete (hereinafter also referred to as "high adhesion and easy peeling"). As a means of achieving high adhesion and easy peeling, for example, Patent Document 1 discloses a pressure-sensitive adhesive sheet using a pressure-sensitive adhesive layer containing an adhesive polymer in which a polyfunctional monomer or oligomer having a radiation-polymerizable functional group is bonded to the side chain or main chain of the polymer. By utilizing the fact that the polymer has a radiation-polymerizable functional group, which hardens when irradiated with ultraviolet light, the adhesive strength is reduced by irradiating ultraviolet light during peeling, allowing the sheet to be peeled off without leaving any adhesive residue.

[0004] Japanese Patent Application Publication No. 5-32946

[0005] The manufacturing of semiconductor devices involves a rewiring process for mounting semiconductors. The most advanced technology in the rewiring process is, for example, Fan Out-Wafer Level Package (FO-WLP).

[0006] Typically, the rewiring process is performed by stacking process materials on a support substrate, forming a metal seed layer such as copper plating by sputtering, etc., and then forming a semiconductor rewiring layer on the metal seed layer, etc. However, when the size of the semiconductor device to be manufactured is large, outgassing from the insulating material can cause problems when performing sputtering or the like to form the metal seed layer during the rewiring process, making it impossible to form the metal seed layer with sufficient strength, which can result in a decrease in yield during the rewiring process due to a decrease in heat resistance, a decrease in chemical resistance, etc.

[0007] Furthermore, one way to overcome the problems that arise when performing sputtering or the like to form a metal seed layer during the rewiring process is to increase the exhaust capacity of the sputtering equipment, etc. However, from a cost perspective, there are only a limited number of equipment with high exhaust capacity that can be used to form a metal seed layer after the processing material has been stacked on the support substrate, making it difficult to introduce sputtering equipment with high exhaust capacity.

[0008] An object of the present invention is to provide a method for manufacturing a semiconductor device that can suppress a decrease in yield during a rewiring process, etc., and improve the yield in the manufacture of semiconductor devices. Another object of the present invention is to provide an adhesive sheet for manufacturing a semiconductor device that can suppress a decrease in yield during a rewiring process, etc. A further object of the present invention is to provide a roll in which the adhesive sheet for manufacturing a semiconductor device is wound.

[0009] Disclosure 1 is a method for manufacturing a semiconductor device, including the following first, second, and third steps: First step: a step of laminating an adhesive sheet having a resin-containing adhesive layer and a metal layer on a support substrate; Second step: a step of forming a semiconductor redistribution layer on the metal layer; and Third step: a step of removing the support substrate and the adhesive layer. Disclosure 2 is a method for manufacturing a semiconductor device according to Disclosure 1, wherein in the third step, at least the support substrate is irradiated with light. Disclosure 3 is a method for manufacturing a semiconductor device according to Disclosure 2, wherein the light is laser light. Disclosure 4 is a method for manufacturing a semiconductor device according to Disclosure 1, 2, or 3, wherein the metal layer has a layer composed of copper. Disclosure 5 is a method for manufacturing a semiconductor device according to Disclosure 1, 2, 3, or 4, wherein the metal layer does not have a layer composed of titanium, or has a layer composed of titanium, and if the metal layer has a layer composed of titanium, the thickness of the layer composed of titanium is 1.0 μm or less. Disclosure 6 is the method for producing a semiconductor device according to Disclosures 1, 2, 3, 4, or 5, wherein the adhesive sheet has the metal layer on its outermost surface. Disclosure 7 is the method for producing a semiconductor device according to Disclosures 1, 2, 3, 4, 5, or 6, wherein the metal layer comprises at least one layer selected from the group consisting of a vapor deposition layer, a sputtering layer, and an ion plating layer. Disclosure 8 is an adhesive sheet for producing a semiconductor device having a metal layer and an adhesive layer containing a resin. Disclosure 9 is the adhesive sheet for producing a semiconductor device according to Disclosure 8, wherein the resin comprises at least one selected from the group consisting of a (meth)acrylic copolymer and a resin having an imide skeleton in the main chain repeating unit. Disclosure 10 is the adhesive sheet for producing a semiconductor device according to Disclosures 8 or 9, wherein the adhesive layer has an ultraviolet transmittance of 5% or less at a wavelength of 355 nm. Disclosure 11 is the adhesive sheet for producing a semiconductor device according to Disclosures 8 or 9, wherein the adhesive layer has an ultraviolet transmittance of 50% or more at a wavelength of 355 nm. The present disclosure 12 is the adhesive sheet for producing a semiconductor device according to the present disclosure 8, 9, 10, or 11, wherein the metal layer is used as a metal seed layer. The present disclosure 13 is the adhesive sheet for producing a semiconductor device according to the present disclosure 8, 9, 10, 11, or 12, wherein the metal layer has a layer made of copper.Disclosure 14 is the adhesive sheet for producing a semiconductor device according to Disclosure 13, wherein the copper layer has a thickness of 1.0 μm or less. Disclosure 15 is the adhesive sheet for producing a semiconductor device according to Disclosures 8, 9, 10, 11, 12, 13, or 14, wherein the metal layer does not have a layer made of titanium, or has a layer made of titanium, and if the metal layer has a layer made of titanium, the thickness of the layer made of titanium is 1.0 μm or less. Disclosure 16 is the adhesive sheet for producing a semiconductor device according to Disclosures 8, 9, 10, 11, 12, 13, 14, or 15, wherein the metal layer is on the outermost surface. Disclosure 17 is the adhesive sheet for producing a semiconductor device according to Disclosures 8, 9, 10, 11, 12, 13, 14, 15, or 16, wherein the metal layer includes at least one layer selected from the group consisting of a vapor deposition layer, a sputtering layer, and an ion plating layer. Disclosure 18 is the adhesive sheet for production of semiconductor device according to Disclosure 8, 9, 10, 11, 12, 13, 14, 15, 16, or 17, in which the adhesive layer and the metal layer are directly laminated together. Disclosure 19 is the adhesive sheet for production of semiconductor device according to Disclosure 8, 9, 10, 11, 12, 13, 14, 15, 16, or 17, in which the adhesive layer, substrate, and metal layer are arranged in this order. Disclosure 20 is the adhesive sheet for production of semiconductor device according to Disclosure 19, in which the substrate includes at least one film selected from the group consisting of a PET film, a PEN film, and a PEEK film. Disclosure 21 is an adhesive sheet for manufacturing a semiconductor device according to Disclosures 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20, having a non-metallic layer and the metal layer, the metal layer being laminated on one side of the non-metallic layer, the non-metallic layer including the adhesive layer, and the non-metallic layer having a light transmittance at a wavelength of 500 nm of 5% or more.

[0023] Disclosure 22 is the adhesive sheet for producing a semiconductor device according to Disclosures 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, or 21, which has a non-metallic layer and the metal layer, the metal layer being laminated on one side of the non-metallic layer, the non-metallic layer including the adhesive layer, the adhesive layer including a base polymer, the base polymer including at least one selected from the group consisting of a (meth)acrylic copolymer and a resin having an imide skeleton in its main chain repeating unit, and the adhesive layer does not include a black pigment or contains more than 0% by mass and not more than 1% by mass of black pigment. Disclosure 23 is the adhesive sheet for producing a semiconductor device according to Disclosures 21 or 22, wherein the non-metallic layer has a light transmittance of 5% or more at a wavelength of 355 nm. Disclosure 24 is the adhesive sheet for producing a semiconductor device according to Disclosures 21, 22, or 23, wherein the non-metallic layer has a thickness of 1 μm or more and 200 μm or less. Disclosure 25 is an adhesive sheet for producing a semiconductor device according to Disclosure 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, or 24, which is used as a light-peelable adhesive sheet. Disclosure 26 is an adhesive sheet for producing a semiconductor device according to Disclosure 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25, which is used as a laser-peelable adhesive sheet. Disclosure 27 is an adhesive sheet for producing a semiconductor device according to Disclosure 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, or 26, which is used to form a semiconductor rewiring layer. The present disclosure 28 is a roll formed by rolling up the adhesive sheet for production of semiconductor device according to the present disclosure 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, or 27.Disclosure 29 provides a method for manufacturing a semiconductor device, comprising the steps of (i) attaching an adhesive sheet to a support substrate and (ii) irradiating the support substrate with light having a wavelength of λ nm to peel off the adhesive sheet, wherein the adhesive sheet has a non-metallic layer and a metal layer, and the metal layer is laminated on one side of the non-metallic layer; in step (i), the non-metallic layer is attached to the support substrate so as to be in contact with the support substrate; and in step (ii), the light having a wavelength of λ nm satisfies a light transmittance of 5% or more through the non-metallic layer. The present invention will be described in detail below. The semiconductor device manufacturing method according to Disclosure 1 is also referred to as the "semiconductor device manufacturing method of Invention 1," and the semiconductor device manufacturing method according to Disclosure 29 is also referred to as the "semiconductor device manufacturing method of Invention 2." Furthermore, matters common to the semiconductor device manufacturing method of Invention 1 and the semiconductor device manufacturing method of Invention 2 are either not specifically specified or are described as the "semiconductor device manufacturing method of the present invention."

[0010] The present inventors have noted that when an adhesive sheet having a resin-containing adhesive layer and a metal layer is used, the metal layer can be used as a metal seed layer during the rewiring process, and as a result of investigating a method for manufacturing a semiconductor device having specific steps, they have found a method for manufacturing a semiconductor device that can suppress a decrease in yield during the rewiring process, etc., and have completed the method for manufacturing a semiconductor device and the adhesive sheet for manufacturing a semiconductor device of the present invention 1. Furthermore, the present inventors have investigated a method for manufacturing a semiconductor device having specific steps using an adhesive sheet having a non-metallic layer including an adhesive layer and a metal layer, and have found a method for manufacturing a semiconductor device that can improve the yield in semiconductor device manufacturing, and have completed the method for manufacturing a semiconductor device of the present invention 2.

[0011] <Method for manufacturing a semiconductor device and adhesive sheet for manufacturing a semiconductor device according to invention 1> The method for manufacturing a semiconductor device according to invention 1 comprises the following first, second, and third steps: First step: a step of laminating an adhesive sheet having a resin-containing adhesive layer and a metal layer on a support substrate; Second step: a step of forming a semiconductor rewiring layer on the metal layer; Third step: a step of removing the support substrate and the adhesive layer. Since the method for manufacturing a semiconductor device according to invention 1 comprises the first, second, and third steps, it is possible to form a rewiring layer without forming a metal seed layer of copper or the like on a processing material such as an adhesive sheet during the rewiring step. This eliminates problems that may occur when performing sputtering or the like to form a metal seed layer during the rewiring step, improves yield during the rewiring step, and improves the manufacturing efficiency of semiconductor devices.

[0012] The present invention also provides an adhesive sheet for semiconductor device production, which has a resin-containing adhesive layer and a metal layer. Because the adhesive sheet for semiconductor device production of the present invention has a metal layer, the metal layer can be used as a metal seed layer during the rewiring process, eliminating the need to form a metal seed layer during the rewiring process. As a result, there are no problems with sputtering or other processes for forming a metal seed layer during the rewiring process, improving yields during the rewiring process and improving semiconductor device production efficiency. Furthermore, the metal layer in the adhesive sheet is laminated during the adhesive sheet production process, allowing for the use of equipment with high exhaust capacity during the adhesive sheet production process. This allows for the easy production of large adhesive sheets with large metal layers without the problems of sputtering or other processes. Therefore, even in the production of large semiconductor devices, using the metal layer of the large adhesive sheet as a metal seed layer during the rewiring process can suppress yield declines during the rewiring process and other processes. Examples of adhesive sheets for semiconductor device production of the present invention include adhesive sheets used in the semiconductor device production method of Invention 1 described below.

[0013] The semiconductor device manufacturing method of the present invention 1 includes a first step of laminating an adhesive sheet having a resin-containing adhesive layer and a metal layer onto a support substrate. The adhesive sheet used in the first step includes a resin-containing adhesive layer and a metal layer. Since the adhesive sheet includes a metal layer, it is not necessary to form a metal seed layer during the rewiring process. This eliminates problems when performing sputtering or other processes to form a metal seed layer during the rewiring process, thereby improving yield during the rewiring process and improving semiconductor device manufacturing efficiency. Furthermore, since the metal layer in the adhesive sheet is laminated during the manufacturing of the adhesive sheet, equipment with large exhaust capacity can be easily used during the manufacturing of the adhesive sheet, making it easy to manufacture large adhesive sheets having large metal layers without problems such as sputtering. Therefore, even in the manufacture of large semiconductor devices, by using the metal layer of the large adhesive sheet as a metal seed layer during the rewiring process, it is possible to suppress a decrease in yield during the rewiring process.

[0014] The adhesive sheet has an adhesive layer containing a resin. The resin may or may not be curable, but is preferably curable from the viewpoint of facilitating removal of the adhesive layer. From the viewpoint of facilitating removal of the adhesive layer, the resin preferably contains at least one selected from the group consisting of (meth)acrylic copolymers and resins having an imide skeleton in the repeating unit of the main chain. In this specification, "(meth)acrylic" means acrylic or methacrylic.

[0015] When the resin contains a (meth)acrylic copolymer, the adhesive layer has better flexibility and can be more easily removed.

[0016] The (meth)acrylic copolymer preferably has a structural unit derived from an alkyl(meth)acrylate. Examples of the alkyl(meth)acrylate include methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, n-butyl(meth)acrylate, tert-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, n-heptyl(meth)acrylate, n-octyl(meth)acrylate, isooctyl(meth)acrylate, n-nonyl(meth)acrylate, isononyl(meth)acrylate, decyl(meth)acrylate, and isodecyl(meth)acrylate. Examples of suitable alkyl (meth)acrylates include acrylate, lauryl (meth)acrylate, myristyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, esters of 5,7,7-trimethyl-2-(1,3,3-trimethylbutyl)-1-octanol and (meth)acrylic acid, esters of alcohols having a total of 18 carbon atoms and one or two methyl groups in the linear main chain and (meth)acrylic acid, behenyl (meth)acrylate, and arachidyl (meth)acrylate. Of these, 2-ethylhexyl (meth)acrylate is preferred. These alkyl (meth)acrylates may be used alone or in combination of two or more. In this specification, the term "(meth)acrylate" refers to acrylate or methacrylate.

[0017] The (meth)acrylic copolymer preferably has a carbon-carbon double bond in its side chain. When the (meth)acrylic copolymer has a carbon-carbon double bond in its side chain, the adhesive strength of the adhesive layer can be significantly reduced by curing the copolymer by heating, irradiating with light, or the like, thereby making it easier to remove the adhesive layer. In this specification, the term "side chain" refers to a branched structure extending from the main chain, where the longest chain in the (meth)acrylic copolymer is the main chain. In this specification, the carbon-carbon double bond in the side chain of the acrylic copolymer does not include a carbon-carbon double bond constituting an aromatic ring.

[0018] Examples of methods for introducing a carbon-carbon double bond into the side chain of the (meth)acrylic copolymer include a method in which a (meth)acrylic polymer having no carbon-carbon double bond introduced therein, obtained by copolymerizing the alkyl (meth)acrylate, a polar functional group-containing monomer described below, or another monomer described below, is reacted with a compound having a functional group reactive with the functional group contained in the (meth)acrylic polymer having no carbon-carbon double bond introduced therein and a functional group having a carbon-carbon double bond (hereinafter also referred to as a "functional group-containing unsaturated compound (a)")

[0019] Examples of the functional group-containing unsaturated compound (a) used in the production of the (meth)acrylic copolymer include the same polar functional group-containing monomers described below, depending on the functional group in the (meth)acrylic polymer without carbon-carbon double bonds. When the functional group in the (meth)acrylic polymer without carbon-carbon double bonds is a carboxy group, for example, an epoxy group-containing monomer or an isocyanate group-containing monomer is used as the functional group-containing unsaturated compound (a). When the functional group in the (meth)acrylic polymer without carbon-carbon double bonds is a hydroxyl group, for example, an isocyanate group-containing monomer is used as the functional group-containing unsaturated compound (a). When the functional group in the (meth)acrylic polymer without carbon-carbon double bonds is an epoxy group, for example, a carboxy group-containing monomer or an amide group-containing monomer such as acrylamide is used as the functional group-containing unsaturated compound (a). When the functional group in the (meth)acrylic polymer without introduced carbon-carbon double bonds is an amino group, for example, an epoxy group-containing monomer is used as the functional group-containing unsaturated compound (a). Specific examples of the functional group-containing unsaturated compound (a) include 2-methacryloyloxyethyl isocyanate (MOI), 2-acryloyloxyethyl isocyanate (AOI), and 1,1-(bisacryloyloxymethyl)ethyl isocyanate (BEI).

[0020] The preferred lower limit of the content of the structural unit derived from the functional group-containing unsaturated compound (a) in the (meth)acrylic copolymer is 0.005% by mass, and the preferred upper limit is 80% by mass. When the content of the structural unit derived from the functional group-containing unsaturated compound (a) is 0.005% by mass or more, the adhesive layer can be sufficiently cured during curing, thereby suppressing the occurrence of adhesive residue and making it easier to remove. When the content of the structural unit derived from the functional group-containing unsaturated compound (a) is 80% by mass or less, the adhesive layer can maintain appropriate flexibility even after curing, suppressing the occurrence of adhesive residue and making it easier to remove. The more preferred lower limit of the content of the structural unit derived from the functional group-containing unsaturated compound (a) is 0.01% by mass, and the more preferred upper limit is 75% by mass.

[0021] The (meth)acrylic copolymer preferably further contains a structural unit derived from a polar functional group-containing monomer. The (meth)acrylic copolymer contains a structural unit derived from a polar functional group-containing monomer, which increases the cohesive strength of the adhesive layer, making it easier to remove the adhesive layer. Furthermore, when the adhesive layer contains a crosslinking agent (described below), the adhesive strength of the adhesive sheet can be reduced by reacting the functional group derived from the structural unit derived from the polar functional group-containing monomer with the crosslinking agent through light irradiation, heating, or the like, thereby making it easier to remove the adhesive layer.

[0022] Examples of the structural unit derived from the polar functional group-containing monomer include a structural unit derived from a carboxy group-containing monomer, a structural unit derived from a hydroxyl group-containing monomer, a structural unit derived from an epoxy group-containing monomer, a structural unit derived from an isocyanate group-containing monomer, and a structural unit derived from an amino group-containing monomer. In particular, from the viewpoint of further improving the cohesive strength of the adhesive layer, it is preferable that the (meth)acrylic copolymer has at least one structural unit selected from the group consisting of a structural unit derived from a carboxy group-containing monomer and a structural unit derived from a hydroxyl group-containing monomer. The polar functional group-containing monomer may be used alone or in combination of two or more.

[0023] Examples of the carboxy group-containing monomer include acrylic acid and methacrylic acid. Examples of the hydroxy group-containing monomer include hydroxyethyl acrylate and hydroxyethyl methacrylate. Examples of the epoxy group-containing monomer include glycidyl acrylate and glycidyl methacrylate. Examples of the isocyanate group-containing monomer include isocyanatoethyl acrylate and isocyanatoethyl methacrylate. Examples of the amino group-containing monomer include aminoethyl acrylate and aminoethyl methacrylate.

[0024] The preferred lower limit of the total content of the structural units derived from the polar functional group-containing monomer in the (meth)acrylic copolymer is 0.01% by mass, and the preferred upper limit is 30% by mass. When the total content of the structural units derived from the polar functional group-containing monomer is 0.01% by mass or more, the cohesive strength of the adhesive layer is increased, thereby reducing the occurrence of adhesive residue and making the adhesive layer easier to remove. Furthermore, when the adhesive layer contains a crosslinking agent (described below), the adhesive strength of the adhesive sheet can be reduced by reacting the functional groups derived from the structural units derived from the polar functional group-containing monomer with the crosslinking agent through light irradiation, heating, or the like, thereby making it easier to remove the adhesive layer. When the total content of the structural units derived from the polar functional group-containing monomer is 30% by mass or less, the adhesive layer has appropriate flexibility, resulting in sufficient initial adhesive strength for the adhesive sheet. A more preferred lower limit of the total content of the structural units derived from the polar functional group-containing monomer is 0.1% by mass, a more preferred upper limit is 25% by mass, and an even more preferred lower limit is 1% by mass.

[0025] The (meth)acrylic copolymer may have structural units derived from other monomers in addition to the structural units derived from the alkyl (meth)acrylate, the structural units derived from the functional group-containing unsaturated compound, and the structural units derived from the polar functional group-containing monomer. Examples of the other monomers include benzyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and polypropylene glycol mono(meth)acrylate. Furthermore, examples of the other monomers that can be used include various monomers commonly used in acrylic polymers, such as vinyl carboxylates such as vinyl acetate and styrene. The other monomers may be used alone or in combination of two or more.

[0026] Examples of methods for producing the (meth)acrylic copolymer include a method in which a monomer mixture containing the alkyl(meth)acrylate and the polar functional group-containing monomer or the like is copolymerized by radical reaction in the presence of a polymerization initiator, and then the resulting (meth)acrylic polymer into which no carbon-carbon double bond has been introduced is reacted with the functional group-containing unsaturated compound (a). As the method for radically reacting the monomer mixture, i.e., the polymerization method, a conventionally known method is used, and examples thereof include solution polymerization (boiling point polymerization or constant temperature polymerization), emulsion polymerization, suspension polymerization, and bulk polymerization.

[0027] Examples of polymerization initiators used to produce the (meth)acrylic copolymer include organic peroxides and azo compounds. Examples of organic peroxides include 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, t-hexylperoxypivalate, t-butylperoxypivalate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate, and t-butylperoxylaurate. Examples of azo compounds include azobisisobutyronitrile and azobiscyclohexanecarbonitrile. The polymerization initiators may be used alone or in combination of two or more. Furthermore, when the radical reaction method is living radical polymerization, examples of the polymerization initiator include organic tellurium polymerization initiators. The organic tellurium polymerization initiator is not particularly limited as long as it is one that is generally used in living radical polymerization, and examples thereof include organic tellurium compounds, organic telluride compounds, etc. Note that, in living radical polymerization, in addition to the organic tellurium polymerization initiator, the azo compound may also be used as a polymerization initiator used to produce the (meth)acrylic copolymer in order to accelerate the polymerization rate.

[0028] The preferred lower limit of the carbon-carbon double bond equivalent of the (meth)acrylic copolymer is 0.05 meq / g. When the carbon-carbon double bond equivalent of the (meth)acrylic copolymer is 0.05 meq / g or more, the adhesive layer can be more easily removed. A more preferred lower limit of the carbon-carbon double bond equivalent of the (meth)acrylic copolymer is 0.06 meq / g, and an even more preferred lower limit is 0.75 meq / g. Furthermore, a preferred upper limit of the carbon-carbon double bond equivalent of the (meth)acrylic copolymer is 2.0 meq / g. When the carbon-carbon double bond equivalent of the (meth)acrylic copolymer is 2.0 meq / g or less, the adhesive layer can maintain appropriate flexibility even after curing, and the adhesive layer can be more easily removed while suppressing the generation of adhesive residue. In this specification, the term "carbon-carbon double bond equivalent of the (meth)acrylic copolymer" refers to the milliequivalent (meq / g) of carbon-carbon double bonds per 1 g of the (meth)acrylic copolymer.

[0029] The weight-average molecular weight (Mw) of the (meth)acrylic copolymer preferably has a lower limit of 200,000 and an upper limit of 2,000,000. When the weight-average molecular weight (Mw) of the (meth)acrylic copolymer is 200,000 or more, the adhesive layer has sufficient initial adhesive strength. When the weight-average molecular weight (Mw) of the (meth)acrylic copolymer is 2,000,000 or less, the adhesive layer has superior flexibility, and the adhesive layer can be more easily removed while suppressing the generation of adhesive residue. The weight-average molecular weight (Mw) of the (meth)acrylic copolymer is more preferably 250,000 and more preferably 1,800,000, with an upper limit of 1,500,000 being even more preferable. In this specification, the weight-average molecular weight is measured as a polystyrene-equivalent molecular weight by gel permeation chromatography (GPC). Specifically, for example, the measurement can be performed using an APC system (manufactured by Waters Corporation) with an RI-PDA detector under the following conditions: a mobile phase of THF, a flow rate of 1.0 mL / min, a column temperature of 40°C, and a sample concentration of 0.2% by mass. The column that can be used is, for example, an HR-MB-M 6.0 x 150 mm (manufactured by Waters Corporation).

[0030] The glass transition temperature (Tg) of the (meth)acrylic copolymer is not particularly limited, but a preferred upper limit is -20°C. When the glass transition temperature (Tg) of the (meth)acrylic copolymer is -20°C or lower, the adhesive layer's ability to conform to the adherend is further improved. A more preferred upper limit of the glass transition temperature (Tg) of the (meth)acrylic copolymer is -30°C, an even more preferred upper limit is -40°C, and an even more preferred upper limit is -50°C. Furthermore, the lower limit of the glass transition temperature (Tg) of the acrylic copolymer is not particularly limited, and is usually -90°C or higher, but from the viewpoint of preventing adhesive residue, a preferred lower limit is -80°C. The glass transition temperature (Tg) of the (meth)acrylic copolymer can be determined, for example, by differential scanning calorimetry.

[0031] The preferred lower limit of the content of the (meth)acrylic copolymer per 100 parts by mass of the resin is 20 parts by mass. A (meth)acrylic copolymer content of 20 parts by mass or more makes it possible to more easily remove the adhesive layer. A more preferred lower limit of the content of the (meth)acrylic copolymer is 23 parts by mass, and an even more preferred lower limit is 25 parts by mass. The upper limit of the content of the (meth)acrylic copolymer is 100 parts by mass, i.e., the resin may be composed solely of the (meth)acrylic copolymer, but from the viewpoint of making it possible to more easily remove the adhesive layer while suppressing the generation of adhesive residue, a preferred upper limit is 98 parts by mass, and a more preferred upper limit is 95 parts by mass.

[0032] Resins having the imide skeleton in the repeating unit of their main chain have extremely excellent heat resistance due to the imide skeleton, and decomposition of the main chain is unlikely to occur even when subjected to high-temperature processing at 300°C or higher. Therefore, by including a resin having the imide skeleton in the repeating unit of the main chain, the resulting adhesive sheet has excellent heat resistance and can further suppress outgassing during high-temperature processing, voids between the adhesive sheet and the support substrate or other adherend, and lifting. Furthermore, since the adhesive layer can be prevented from increasing its adhesion to the adherend or the support substrate, the adhesive layer can be more easily removed without leaving any adhesive residue.

[0033] The resin having the imide skeleton in the repeating unit of the main chain preferably has a constitutional unit represented by the following formula (1).

[0034]

[0035] In formula (1), P １ represents an aromatic group; １ represents a substituted or unsubstituted, linear, branched, or cyclic aliphatic group.

[0036] In the above formula (1), P １ is preferably an aromatic group having 5 to 50 carbon atoms. １ is an aromatic group having from 5 to 50 carbon atoms, the resulting adhesive sheet has better heat resistance. That is, outgassing during high-temperature processing and the occurrence of voids and lifting between the adhesive layer and the adherend such as a support substrate can be further suppressed, and the adhesive layer can be further prevented from increasing its adhesion to the adherend such as a support substrate, making it easier to remove the adhesive layer while suppressing the occurrence of adhesive residue.

[0037] In the above formula (1), Q １ is preferably a substituted or unsubstituted linear, branched or cyclic aliphatic group having from 2 to 100 carbon atoms. １ When Q is a substituted or unsubstituted linear, branched or cyclic aliphatic group having from 2 to 100 carbon atoms, the resulting adhesive sheet has better optical transparency. In addition, the adhesive layer has better flexibility, can exhibit high conformability to the adherend such as a support substrate, and can be more easily removed. １ is preferably an aliphatic group derived from a diamine compound. In particular, from the viewpoints of light transparency, flexibility, and compatibility with solvents and other components of the resin having the imide skeleton in the main chain repeating unit, the Q １is more preferably an aliphatic group derived from a dimer diamine. The dimer diamine is a diamine compound obtained by reducing and amminating cyclic and acyclic dimer acids obtained as dimers of unsaturated fatty acids, and examples thereof include linear, monocyclic, and polycyclic dimer diamines. The dimer diamine may contain a carbon-carbon double bond or may be a hydrogenated product to which hydrogen has been added.

[0038] The aliphatic group derived from the dimer diamine is preferably at least one group selected from the group consisting of a group represented by the following formula (2-1), a group represented by the following formula (2-2), a group represented by the following formula (2-3), and a group represented by the following formula (2-4). Among these, the group represented by the following formula (2-2) is more preferred.

[0039]

[0040] In formulas (2-1) to (2-4), R １ ~R １６ are each independently a linear or branched hydrocarbon group, and * represents a bond, which bonds to N in the above formula (1).

[0041] In the above formulas (2-1) to (2-4), R １ ~R １６ The hydrocarbon group represented by R may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. １ and R ２ , R ３ and R ４ , R ５ and R ６ , R ７ and R ８ , R ９ and R １０ , R １１ and R １２ , R １３ and R １４ , and R １５ and R １６The preferred lower limit of the total number of carbon atoms is 7, and the preferred upper limit is 50. When the total number of carbon atoms is within the above range, the resulting adhesive sheet will have excellent light transparency, flexibility, and compatibility with solvents and other components of the resin having the imide skeleton in the main chain repeating unit. The more preferred lower limit of the total number of carbon atoms is 9, and the more preferred upper limit is 25, and the even more preferred lower limit is 12, 18, and 14, respectively.

[0042] In the group represented by the formula (2-1), the group represented by the formula (2-2), the group represented by the formula (2-3), and the group represented by the formula (2-4), the optical isomerism is not particularly limited, and any optical isomerism is included.

[0043] The resin having an imide skeleton in the repeating unit of the main chain preferably includes a resin having no maleimide group and having an imide skeleton in the repeating unit of the main chain, and more preferably includes a resin having no polymerizable functional group having a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain.

[0044] The resin having no maleimide groups and an imide skeleton in its main chain repeating unit preferably has a weight-average molecular weight of 20,000 (lower limit) and 2,000,000 (upper limit). Having a weight-average molecular weight of 20,000 or more for the resin having no maleimide groups and an imide skeleton in its main chain repeating unit results in the resulting adhesive sheet having superior heat resistance. This effectively prevents outgassing during high-temperature processing, voids between the adhesive layer and the support substrate, and lifting. This effectively prevents the adhesive layer from becoming too tightly attached to the support substrate or other adherend, making it easier to remove the adhesive layer without leaving any adhesive residue. Having a weight-average molecular weight of 2,000,000 or less for the resin having no maleimide groups and an imide skeleton in its main chain repeating unit results in the resin having superior compatibility with solvents and other components. The weight average molecular weight of the resin having no maleimide group and having an imide skeleton in the repeating unit of the main chain is more preferably 40,000 in lower limit and 600,000 in upper limit, still more preferably 50,000 in lower limit and still more preferably 300,000 in upper limit.

[0045] Specific examples of the resin that does not have a maleimide group and has an imide skeleton in the repeating unit of the main chain include resins that have a constitutional unit represented by the above formula (1) and have functional groups at both ends that do not have maleimide groups.

[0046] The resin having a structural unit represented by the above formula (1) and a functional group having no maleimide group at both ends may have a structural unit represented by the following formula (3).

[0047]

[0048] In formula (3), P ２ represents an aromatic group; ２ represents a group having a substituted or unsubstituted aromatic structure.

[0049] In the above formula (3), P ２ is preferably an aromatic group having 5 to 50 carbon atoms. ２is an aromatic group having from 5 to 50 carbon atoms, the resulting adhesive sheet has better heat resistance. That is, outgassing during high-temperature processing and the occurrence of voids and lifting between the adhesive layer and the adherend such as a support substrate can be further suppressed, and the adhesive layer can be further prevented from increasing its adhesion to the adherend such as a support substrate, making it easier to remove the adhesive layer while suppressing the occurrence of adhesive residue.

[0050] In the above formula (3), Q ２ is preferably a substituted or unsubstituted group having an aromatic structure having 5 to 50 carbon atoms. ２ is a substituted or unsubstituted group having an aromatic structure having from 5 to 50 carbon atoms, the resulting adhesive sheet has better heat resistance. That is, it is possible to further suppress outgassing during high-temperature processing, the formation of voids between the adhesive layer and the adherend such as a support substrate, and the occurrence of lifting, and it is also possible to further prevent the adhesive layer from becoming more strongly bonded to the adherend such as a support substrate, and it becomes possible to more easily remove the adhesive layer while suppressing the occurrence of adhesive residue.

[0051] Examples of the functional group not having a maleimide group include an aliphatic group, an alicyclic group, an aromatic group, an acid anhydride group, and an amino group. Specific examples include an unreacted terminal group of an acid anhydride or diamine compound that serves as a raw material for a resin not having a maleimide group and having an imide skeleton in the repeating unit of its main chain. In a resin having a structural unit represented by formula (1) and functional groups not having a maleimide group at both ends, the functional groups not having a maleimide group at both ends may be the same or different.

[0052] The content of the structural unit represented by the formula (1) in a resin having a structural unit represented by the formula (1) and functional groups at both ends that do not have maleimide groups is preferably 30 mol%, more preferably 50 mol%, and preferably 90 mol%, and more preferably 80 mol%. When a resin having a structural unit represented by the formula (1) and functional groups at both ends that do not have maleimide groups has a structural unit represented by the formula (3), the content of the structural unit represented by the formula (3) is preferably 5 mol%, more preferably 10 mol%, and even more preferably 20 mol%, and preferably 50 mol%, and more preferably 30 mol%. When the contents of the structural units represented by the formula (1) and the structural units represented by the formula (3) are within the above ranges, the resulting adhesive sheet can be more effectively prevented from outgassing during high-temperature processing, from forming voids between the adhesive sheet and the support substrate or other adherend, and from lifting, making it easier to remove the adhesive layer. The structural unit represented by the formula (1) and the structural unit represented by the formula (3) may have a block structure consisting of block components in which the respective structural units are arranged consecutively, or may have a random structure in which the respective structural units are arranged randomly.

[0053] Examples of a method for producing the resin having no maleimide group and an imide skeleton in the repeating unit of the main chain include a method of reacting a diamine compound with an aromatic acid anhydride.

[0054] As the diamine compound, either an aliphatic diamine compound or an aromatic diamine compound can be used. By using an aliphatic diamine compound as the diamine compound, the resulting adhesive sheet has better light transmittance. In addition, the adhesive layer has better flexibility, can exhibit high conformability to an adherend such as a support substrate, and can be more easily removed. In addition, by using an aromatic diamine compound as the diamine compound, the resulting adhesive sheet has better heat resistance. The diamine compounds may be used alone or in combination of two or more.

[0055] Examples of the aliphatic diamine compound include 1,10-diaminodecane, 1,12-diaminododecane, dimer diamine, 1,2-diamino-2-methylpropane, 1,2-diaminocyclohexane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,7-diaminoheptane, 1,8-diaminomenthane, 1,8-diaminooctane, 1,9-diaminononane, 3,3'-diamino-N-methyldipropylamine, diaminomaleonitrile, 1,3-diaminopentane, bis(4-amino-3-methylcyclohexyl)methane, 1,2-bis(2-aminoethoxy)ethane, and 3(4),8(9)-bis(aminomethyl)tricyclo(5.2.1.02,6)decane.

[0056] Among the aliphatic diamine compounds, dimer diamine is preferred from the viewpoints of light transparency, flexibility, and compatibility with solvents and other components of the resin that does not have a maleimide group and has an imide skeleton as a repeating unit in the main chain. Specific examples of the dimer diamine include dimer diamines that can constitute at least one group selected from the group consisting of the group represented by the above formula (2-1), the group represented by formula (2-2), the group represented by formula (2-3), and the group represented by formula (2-4).

[0057] Examples of the aromatic diamine compound include 9,10-diaminophenanthrene, 4,4'-diaminooctafluorobiphenyl, 3,7-diamino-2-methoxyfluorene, 4,4'-diaminobenzophenone, 3,4-diaminobenzophenone, 3,4-diaminotoluene, 2,6-diaminoanthraquinone, 2,6-diaminotoluene, 2,3-diaminotoluene, 1,8-diaminonaphthalene, 2,4-diaminotoluene, 2,5-diaminotoluene, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 1,5-diaminonaphthalene, 1,2-diaminoanthraquinone, 2,4-cumenediamine, 1,3-bisaminomethylbenzene, 1,3-bisaminomethylcyclohexane, 2-chloro-1,4-diaminobenzene, 1,4-diamino-2,5-dichlorobenzene, 1,4-diamino-2,5-dimethylbenzene, 4,4'-diamino-2,2'-bistrifluoromethylbiphenyl, bis(amino-3-chlorophenyl)ethane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3,5-diethylphenyl) phenyl)methane, 9,9'-bis(4-amino-3-ethylphenyl)fluorene, 2,3-diaminonaphthalene, 2,3-diaminophenol, bis(4-amino-5-methylphenyl)methane, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3-ethylphenyl)methane, 4,4'-diaminophenylsulfone, 3,3'-diaminophenylsulfone, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, 4,4'-oxydianiline, 4,4' -diaminodiphenyl sulfide, 3,4'-oxydianiline, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diamino-3,3'-dimethoxybiphenyl, 1,3-bis(2-(4-aminophenyl)-2-propyl)benzene (manufactured by Mitsui Fine Chemicals, Inc., "Bisaniline M", etc.), 1,4-bis(2-(4-aminophenyl)-2-propyl)benzene (Mitsui Fine Chemicals, Inc., "Bisaniline P"), 9,9-bis(4-aminophenyl)fluorene, o-tolidine sulfone, 5,5'-methylenebis(anthranilic acid), 1,3-bis(4-aminophenoxy)-2,2-dimethylpropane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)butane, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3,3',5,5'-tetramethylbenzidine, 4,4'-diaminobenzanilide, 2,2-bis(4-aminophenyl)hexafluoropropane, polyoxyalkylenediamines (for example, Jeffamine P manufactured by Huntsman), D-230, D-400, D-2000, and D-4000), 1,3-cyclohexanebis(methylamine), m-xylylenediamine, p-xylylenediamine, etc.

[0058] Examples of the aromatic acid anhydride include pyromellitic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,4,5-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 3,3',4,4'-biphenylethertetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 4,4'-sulfonyldiphthalic acid, 1-trifluoromethyl-2,3,5,6-benzenetetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, 1,1-bis(2,3-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(3,4-dicarboxyphenyl)ethane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)ether, benzene-1,2,3,4-tetracarboxylic acid, 2,3,2',3'-benzophenonetetracarboxylic acid, 2,3,3',4'-benzophenonetetracarboxylic acid, phenanthrene-1,8,9,10-tetracarboxylic acid, pyrazine-2,3,5,6-tetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide, 4,4'-(4,4'-isopropylidenediphenoxy)-bis(phthalic acid), and other carboxylic acid anhydrides.

[0059] The preferred lower limit of the content of the resin that does not have a maleimide group and has an imide skeleton in its main chain repeating unit per 100 parts by mass of the resin is 10 parts by mass, and the preferred upper limit is 90 parts by mass. When the content of the resin that does not have a maleimide group and has an imide skeleton in its main chain repeating unit is within this range, the adhesive layer can be more easily removed. From the viewpoint of making the adhesive layer even more easily removable, the more preferred lower limit of the content of the resin that does not have a maleimide group and has an imide skeleton in its main chain repeating unit is 20 parts by mass, and the more preferred upper limit is 80 parts by mass.

[0060] The resin having an imide skeleton in its main chain repeating unit preferably includes a resin having a functional group with a carbon-carbon double bond and an imide skeleton in its main chain repeating unit. By including a resin having a functional group with a carbon-carbon double bond and an imide skeleton in its main chain repeating unit, the adhesive layer undergoes uniform and rapid polymerization and crosslinking throughout upon irradiation with light, etc., resulting in an increase in elastic modulus and a significant decrease in adhesive strength. This further prevents adhesion enhancement, making it easier to remove the adhesive layer while suppressing the occurrence of adhesive residue. When the resin having an imide skeleton in its main chain repeating unit includes a resin that does not include the maleimide group and has an imide skeleton in its main chain repeating unit, it is preferable that the resin further includes a resin that has a functional group with a carbon-carbon double bond and has an imide skeleton in its main chain repeating unit, in addition to the resin that does not include the maleimide group and has an imide skeleton in its main chain repeating unit.

[0061] Examples of the functional group having a carbon-carbon double bond include an optionally substituted maleimide group, a citraconic group, a vinyl ether group, an allyl group, and a (meth)acryloyl group. Among these, an optionally substituted maleimide group is preferred because it provides higher heat resistance. In this specification, "(meth)acryloyl" means acryloyl or methacryloyl.

[0062] In the resin having a functional group having a carbon-carbon double bond and an imide skeleton in the repeating unit of the main chain, the functional group having a carbon-carbon double bond preferably has a functional group equivalent (weight average molecular weight / number of functional groups having a carbon-carbon double bond) of 4000 or less. When the functional group equivalent of the functional group having a carbon-carbon double bond is 4000 or less, the resulting adhesive sheet has superior heat resistance. This is thought to be because the presence of functional groups having a carbon-carbon double bond at a density above a certain level in the resin molecule shortens the inter-crosslink distance, thereby further suppressing adhesion enhancement. The functional group equivalent of the functional group having a carbon-carbon double bond is more preferably 3000 or less, and even more preferably 2000 or less. Furthermore, there is no particular preferred lower limit for the functional group equivalent of the functional group having a carbon-carbon double bond, but the practical lower limit is approximately 600.

[0063] The resin having a functional group with a carbon-carbon double bond and an imide skeleton in the repeating unit of its main chain preferably has a weight-average molecular weight of 1,000 or less and 100,000 or less. When the resin having a functional group with a carbon-carbon double bond and an imide skeleton in the repeating unit of its main chain has a weight-average molecular weight of 1,000 or more, the adhesive layer can be easily formed, and the adhesive layer can exhibit a certain degree of flexibility, thereby exhibiting high conformability to an adherend such as a support substrate and making the adhesive layer more easily removable. When the resin having a functional group with a carbon-carbon double bond and an imide skeleton in the repeating unit of its main chain has a weight-average molecular weight of 100,000 or less, the solubility of the resin having a functional group with a carbon-carbon double bond and an imide skeleton in the repeating unit of its main chain in a solvent can be prevented from becoming too low. The weight average molecular weight of the resin having a functional group with a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain is more preferably 1,500 in lower limit and 50,000 in upper limit, still more preferably 2,000 in lower limit and still more preferably 20,000 in upper limit.

[0064] In the resin having the functional group having a carbon-carbon double bond and an imide skeleton in the repeating unit of the main chain, the functional group having a carbon-carbon double bond may be located either in a side chain or at a terminal, but is preferably located at both terminals, and more preferably located in both terminals and also in a side chain. The functional groups having a carbon-carbon double bond at both terminals of the resin having the functional group having a carbon-carbon double bond and an imide skeleton in the repeating unit of the main chain are highly reactive, allowing the adhesive layer to be cured more sufficiently by irradiation with light, etc. As a result, adhesion enhancement can be more effectively prevented, and the adhesive layer can be more easily removed while suppressing the occurrence of adhesive residue. Furthermore, the presence of a functional group having a carbon-carbon double bond in the side chain of the resin having the functional group having a carbon-carbon double bond and an imide skeleton in the repeating unit of the main chain results in the resulting adhesive sheet having superior heat resistance. This is thought to be due to the shorter inter-crosslink distance, which further suppresses adhesion enhancement. Furthermore, by having the functional group having a carbon-carbon double bond and by having a functional group having a carbon-carbon double bond in a side chain of a resin having an imide skeleton in the repeating unit of its main chain, it becomes easy to adjust the functional group equivalent to 4000 or less while setting the weight average molecular weight to 1000 or more. This makes it possible to provide the adhesive layer with sufficient initial adhesive strength and to further prevent adhesion enhancement, and to make it easier to remove the adhesive layer while suppressing the generation of adhesive residue.

[0065] As described above, in a resin having a functional group having a carbon-carbon double bond and an imide skeleton in the repeating unit of its main chain, the functional group having a carbon-carbon double bond may be located either in a side chain or at a terminal. When either the side chain or the terminal has a functional group other than a functional group having a carbon-carbon double bond (a functional group not having a carbon-carbon double bond), examples of the functional group not having a carbon-carbon double bond include aliphatic groups, alicyclic groups, aromatic groups, acid anhydride groups, and amino groups. Specific examples include unreacted terminal groups of acid anhydrides and diamine compounds that are raw materials for resins having the functional group having a carbon-carbon double bond and an imide skeleton in the repeating unit of their main chain. When a resin having a functional group having a carbon-carbon double bond and an imide skeleton in the repeating unit of its main chain has two or more functional groups not having a carbon-carbon double bond in a side chain or at a terminal, the functional groups not having a carbon-carbon double bond may be the same or different.

[0066] Specific examples of the resin having a functional group having a carbon-carbon double bond and an imide skeleton in the repeating unit of the main chain include resins having a constitutional unit represented by the above formula (1) and having a functional group having a carbon-carbon double bond at least in either the terminal or the side chain.

[0067] The resin having a structural unit represented by the above formula (1) and a functional group having a carbon-carbon double bond at least at either the terminal or the side chain may have at least one structural unit selected from the group consisting of a structural unit represented by the following formula (4-1) and a structural unit represented by the following formula (4-2):

[0068]

[0069] In the above formula (4-1), P ３ represents an aromatic group; Q ３ represents a group having a substituted or unsubstituted aromatic structure, and in the above formula (4-2), P ４ represents an aromatic group, R represents a substituted or unsubstituted branched aliphatic group or aromatic group, and X represents a functional group having a carbon-carbon double bond.

[0070] P in the above formula (4-1) ３ and P in the above formula (4-2) ４ is preferably an aromatic group having 5 to 50 carbon atoms. ３ and P ４ is an aromatic group having 5 to 50 carbon atoms, the resulting adhesive sheet has better heat resistance. That is, outgassing during high-temperature processing and the occurrence of voids and lifting between the adhesive layer and the adherend such as a support substrate can be further suppressed, and the adhesive layer can be further prevented from increasing its adhesion to the adherend such as a support substrate, making it easier to remove the adhesive layer while suppressing the occurrence of adhesive residue.

[0071] In the above formula (4-1), Q ３ is preferably a substituted or unsubstituted group having an aromatic structure having 5 to 50 carbon atoms. ３ is a substituted or unsubstituted group having an aromatic structure of 5 to 50 carbon atoms, the resulting adhesive sheet has better heat resistance. That is, it is possible to further suppress outgassing during high-temperature processing, the formation of voids between the adhesive layer and the adherend, such as a support substrate, and the occurrence of lifting, and it is also possible to further prevent the adhesive layer from becoming more strongly bonded to the adherend, such as a support substrate, and it becomes easier to remove the adhesive layer while suppressing the occurrence of adhesive residue.

[0072] In the above formula (4-2), R is preferably a substituted or unsubstituted branched aliphatic or aromatic group having 2 to 100 carbon atoms. When R is a substituted or unsubstituted branched aliphatic or aromatic group having 2 to 100 carbon atoms, the adhesive layer has better flexibility, can exhibit high conformability to an adherend such as a support substrate, and can be more easily removed.

[0073] In the above formula (4-2), R is an aromatic group having an aromatic ester group or an aromatic ether group, and the aromatic ester group or aromatic ether group in R is preferably bonded to X. Here, "aromatic ester group" refers to a group in which an ester group is directly bonded to an aromatic ring, and "aromatic ether group" refers to a group in which an ether group is directly bonded to an aromatic ring. By having the aromatic group have a moiety that is bonded to an ester group or an ether group, the resulting adhesive sheet has superior heat resistance. This means that outgassing during high-temperature processing, voids between the adhesive and the support substrate, and lifting can be further suppressed. Furthermore, increased adhesion of the adhesive layer to the support substrate or other adherend can be further prevented, making the adhesive layer more easily removable. Meanwhile, by bonding X to R via an aromatic ester group or an aromatic ether group, the carbon-carbon double bond in X is not conjugated with R, and therefore polymerization and crosslinking upon heating or light irradiation are not hindered.

[0074] The content of the structural unit represented by the formula (1) in a resin having a functional group having a carbon-carbon double bond at at least one of the terminal and the side chain is preferably 30 mol% or more, more preferably 50 mol% or less, and preferably 90 mol% or less, and more preferably 80 mol% or less. When a resin having a structural unit represented by the formula (1) and a functional group having a carbon-carbon double bond at at least one of the terminal and the side chain has a structural unit represented by the formula (4-1), the content of the structural unit represented by the formula (4-1) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or less, and preferably 50 mol% or less, and more preferably 30 mol% or less. When a resin having a structural unit represented by formula (1) and a functional group having a carbon-carbon double bond at at least one of the terminal and the side chain has a structural unit represented by formula (4-2), the content of the structural unit represented by formula (4-2) is preferably 10 mol% at the lower limit, more preferably 20 mol%, and preferably 50 mol% at the upper limit, more preferably 30 mol%. When the content of each structural unit in the structural unit represented by formula (1), the structural unit represented by formula (4-1), and the structural unit represented by formula (4-2) is within the above range, the resulting adhesive sheet can be more effectively prevented from outgassing during high-temperature processing, from forming voids between the adhesive sheet and the adherend, such as a support substrate, and from lifting, and the adhesive layer can be more easily removed. The structural unit represented by the formula (1), the structural unit represented by the formula (4-1), and the structural unit represented by the formula (4-2) may have a block structure consisting of block components in which the respective structural units are arranged consecutively, or may have a random structure in which the respective structural units are arranged randomly.

[0075] Examples of methods for producing a resin having the above-mentioned functional group having a carbon-carbon double bond and an imide skeleton in the repeating unit of its main chain include the following. Specifically, first, a diamine compound is reacted with an aromatic acid anhydride to prepare an imide compound. Next, a compound having a functional group reactive with the functional group of the imide compound and a functional group having a carbon-carbon double bond (hereinafter also referred to as a "functional group-containing unsaturated compound (b)") is reacted with the functional group of the imide compound to obtain a resin having the above-mentioned functional group having a carbon-carbon double bond and an imide skeleton in the repeating unit of its main chain. Alternatively, a resin having the above-mentioned functional group having a carbon-carbon double bond and an imide skeleton in the repeating unit of its main chain can also be obtained by reacting a diamine compound with an aromatic acid anhydride to prepare an imide compound, and then reacting the terminal of the imide compound with, for example, maleic anhydride.

[0076] The diamine compound and aromatic acid anhydride used in the method for producing a resin having a functional group with a carbon-carbon double bond and an imide skeleton in the repeating unit of the main chain may be the same as those used in the method for producing a resin having no maleimide group and an imide skeleton in the repeating unit of the main chain.

[0077] The functional group-containing unsaturated compound (b) is selected and used depending on the functional group at the terminal or side chain of the imide compound. For example, when the functional group at the terminal or side chain of the imide compound is a hydroxyl group, examples of the functional group-containing unsaturated compound (b) include maleimide compounds having a carboxyl group, vinyl compounds having an ether group, allyl compounds having a glycidyl group, allyl ether compounds having a glycidyl group, vinyl ether compounds having a glycidyl group, allyl compounds having an isocyanate group, (meth)acryloyl compounds having an isocyanate group, and allyl compounds having a hydroxyl group. Examples of the maleimide compounds having a carboxyl group include maleimide acetate, maleimidopropionic acid, maleimidobutyric acid, maleimidohexanoic acid, trans-4-(N-maleimidomethyl)cyclohexane-1-carboxylic acid, and 19-maleimido-17-oxo-4,7,10,13-tetraoxa-16-azanonadecanoic acid. Examples of vinyl compounds having an ether group include butyl vinyl ether. Examples of allyl compounds having a glycidyl group include diallyl monoglycidyl isocyanurate. Examples of allyl ether compounds having a glycidyl group include allyl glycidyl ether and glycerin diallyl monoglycidyl ether. Examples of vinyl ether compounds having a glycidyl group include glycidyloxyethyl vinyl ether, glycidyloxybutyl vinyl ether, glycidyloxyhexyl vinyl ether, glycidyl diethylene glycol vinyl ether, and glycidyl cyclohexanedimethanol monovinyl ether. Examples of allyl compounds having an isocyanate group include allyl isocyanate. Examples of (meth)acryloyl compounds having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate. Examples of allyl compounds having a hydroxyl group include trimethylolpropane diallyl ether and pentaerythritol triallyl ether.Furthermore, for example, when the functional group at the end or side chain of the imide compound is a carboxy group, examples of the functional group-containing unsaturated compound (b) include an allyl compound having a hydroxyl group, an allyl compound having a glycidyl group, an allyl ether compound having a glycidyl group, and a vinyl ether compound having a glycidyl group.

[0078] The preferred lower limit of the content of the resin having a functional group with a carbon-carbon double bond and having an imide skeleton in the repeating unit of its main chain per 100 parts by mass of the resin is 10 parts by mass, and the preferred upper limit is 100 parts by mass. When the content of the resin having a functional group with a carbon-carbon double bond and having an imide skeleton in the repeating unit of its main chain per 100 parts by mass of the resin is within this range, the adhesive layer can be more easily removed. From the viewpoint of making the adhesive layer even easier to remove, the preferred lower limit of the content of the resin having a functional group with a carbon-carbon double bond and having an imide skeleton in the repeating unit of its main chain per 100 parts by mass of the resin is 20 parts by mass, even more preferably 30 parts by mass, and even more preferably 90 parts by mass, even more preferably 80 parts by mass, and even more preferably 70 parts by mass.

[0079] When the resin having an imide skeleton in its main chain repeating unit does not have the maleimide group and includes a resin having an imide skeleton in its main chain repeating unit, it is preferable that the resin further includes a compound having two or more functional groups having a carbon-carbon double bond in the molecule and having a molecular weight of 5,000 or less (hereinafter simply referred to as a "polyfunctional reactive carbon-carbon double bond-containing compound"). Furthermore, when the resin having an imide skeleton in its main chain repeating unit includes a resin having the functional group having a carbon-carbon double bond and also includes a resin having an imide skeleton in its main chain repeating unit, the resin may further include the polyfunctional reactive carbon-carbon double bond-containing compound. By including the polyfunctional reactive carbon-carbon double bond-containing compound, the adhesive sheet is more efficiently three-dimensionally reticulated by irradiation with light or the like, which can more effectively prevent adhesion enhancement and make the adhesive layer more easily removable.

[0080] In addition, when the resin having the imide skeleton in the repeating unit of the main chain is not reactive itself, the resin must further contain another component having a reactive functional group to make the resin reactive as a whole. As such another component having a reactive functional group, it is preferable to use the polyfunctional reactive carbon-carbon double bond-containing compound. An example of a case in which the resin having the imide skeleton in the repeating unit of the main chain is not reactive itself is when the resin having the imide skeleton in the repeating unit of the main chain does not have the maleimide group and only contains a resin having the imide skeleton in the repeating unit of the main chain.

[0081] Examples of the functional group having a carbon-carbon double bond in the polyfunctional reactive carbon-carbon double bond-containing compound include an optionally substituted maleimide group, a citraconic imide group, a vinyl ether group, an allyl group, and a (meth)acryloyl group. Among these, an optionally substituted maleimide group is preferred because it provides higher heat resistance. In particular, the polyfunctional reactive carbon-carbon double bond-containing compound is preferably a bismaleimide compound.

[0082] The polyfunctional reactive carbon-carbon double bond-containing compound preferably has a group derived from a diamine compound. As the diamine compound, either an aliphatic diamine compound or an aromatic diamine compound can be used, but an aliphatic diamine compound is preferred. That is, the polyfunctional reactive carbon-carbon double bond-containing compound more preferably has an aliphatic group derived from a diamine compound. By using an aliphatic diamine compound as the diamine compound, the resulting adhesive sheet has superior optical transparency. Furthermore, the adhesive layer has superior flexibility, exhibiting high conformability to an adherend such as a supporting substrate, and allowing the adhesive layer to be more easily removed.

[0083] Among the above aliphatic diamine compounds, the above-mentioned dimer diamines are preferred from the viewpoints of light transparency, flexibility, and compatibility with the solvent of the polyfunctional reactive carbon-carbon double bond-containing compound and other components.

[0084] The preferred lower limit of the content of the polyfunctional reactive carbon-carbon double bond-containing compound per 100 parts by mass of the resin is 5 parts by mass, and the preferred upper limit is 90 parts by mass. When the content of the polyfunctional reactive carbon-carbon double bond-containing compound is within this range, the adhesive layer can be more easily removed. From the viewpoint of making the adhesive layer even more easily removable, the more preferred lower limit of the content of the polyfunctional reactive carbon-carbon double bond-containing compound is 10 parts by mass, and the more preferred upper limit is 50 parts by mass.

[0085] When the resin contains a resin having a functional group having a carbon-carbon double bond and having an imide skeleton in the repeating unit of its main chain, and the polyfunctional reactive carbon-carbon double bond-containing compound, the preferred lower limit for the total content of the resin having a functional group having a carbon-carbon double bond and having an imide skeleton in the repeating unit of its main chain, and the polyfunctional reactive carbon-carbon double bond-containing compound, per 100 parts by mass of the resin, is 20 parts by mass, and the preferred upper limit is 80 parts by mass. When the total content of the resin having a functional group having a carbon-carbon double bond and having an imide skeleton in the repeating unit of its main chain, and the polyfunctional reactive carbon-carbon double bond-containing compound is within this range, the adhesive layer can be more easily removed. From the viewpoint of making it possible to more easily remove the adhesive layer, the lower limit of the total content of the resin having a functional group having a carbon-carbon double bond and having an imide skeleton in a repeating unit of its main chain, and the polyfunctional reactive carbon-carbon double bond-containing compound is more preferably 30 parts by mass, even more preferably 40 parts by mass, still more preferably 50 parts by mass, and more preferably 70 parts by mass.

[0086] The resin preferably contains a compound having a maleimide group. By including the compound having a maleimide group, the resulting adhesive sheet has superior heat resistance. The compound having a maleimide group is preferably a bismaleimide compound, or a resin having a maleimide group and an imide skeleton in the repeating unit of its main chain. That is, the resin preferably contains the bismaleimide compound as the polyfunctional reactive carbon-carbon double bond-containing compound, or the compound having the imide bond has the functional group having the carbon-carbon double bond, and the resin having an imide skeleton in the repeating unit of its main chain has a maleimide group as the functional group having the carbon-carbon double bond.

[0087] The upper limit of the resin content in the adhesive layer is preferably 99% by mass. A resin content of 99% by mass or less makes it easier to remove the adhesive layer. A more preferred upper limit of the resin content is 98% by mass, an even more preferred upper limit is 96% by mass, and an even more preferred upper limit is 90% by mass. Furthermore, a preferred lower limit of the resin content is 5% by mass. A resin content of 5% by mass or more can further suppress adhesion enhancement during high-temperature processing. A more preferred lower limit of the resin content is 10% by mass, and an even more preferred lower limit is 20% by mass.

[0088] The adhesive layer preferably further contains a polymerization initiator. By containing the polymerization initiator in the adhesive layer, the resin becomes more easily cured, and increased adhesion of the adhesive layer to an adherend such as a support substrate during high-temperature processing can be more effectively suppressed. As a result, the adhesive layer can be more easily removed. The polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator, but a photopolymerization initiator is preferred from the viewpoint of easier process control of the curing of the adhesive layer.

[0089] Examples of the photopolymerization initiator include those that are activated by irradiation with light having a wavelength of 250 nm or more and 800 nm or less. Among them, the photopolymerization initiator is preferred to have a molar absorption coefficient at 405 nm of 10 mL / (g cm), more preferably 200 mL / (g cm), and even more preferably 405 mL / (g cm), since it is unlikely to overlap with the absorption wavelength of the resin and is sufficiently activated when the adhesive sheet is irradiated with light. In addition, there is no particular upper limit for the molar absorption coefficient at 405 nm, but it is preferred to have a molar absorption coefficient of 1.0 x 10 ６ The practical upper limit is about mL / (g cm).

[0090] Examples of the photopolymerization initiator include acetophenone derivatives, benzoin ether compounds, ketal derivatives, phosphine oxide derivatives, and oxime ester compounds. Examples of the acetophenone derivatives include methoxyacetophenone, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)butan-1-one. Examples of the benzoin ether compounds include benzoin propyl ether and benzoin isobutyl ether. Examples of the ketal derivatives include benzyl dimethyl ketal and acetophenone diethyl ketal. Examples of the phosphine oxide derivatives include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. Examples of the oxime ester compound include 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone and 1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime)-1,2-octadione. Examples of the photopolymerization initiator include bis(η5-cyclopentadienyl)titanocene derivative compounds, benzophenone, Michler's ketone, chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, α-hydroxycyclohexylphenyl ketone, and 2-hydroxymethylphenylpropane. These photopolymerization initiators may be used alone or in combination of two or more.

[0091] The content of the polymerization initiator is preferably 0.1 parts by mass or less and 10 parts by mass or less per 100 parts by mass of the resin. By using the polymerization initiator in this range, the adhesive layer is uniformly and quickly polymerized and crosslinked throughout, and the elastic modulus is increased, which can prevent a significant decrease in adhesive strength and increased adhesion, making it easier to remove the adhesive layer. The more preferred lower limit of the polymerization initiator content is 0.3 parts by mass, and the more preferred upper limit is 5 parts by mass.

[0092] When the resin contains the (meth)acrylic copolymer and the (meth)acrylic copolymer contains a structural unit derived from the polar functional group-containing monomer, the adhesive layer preferably contains a crosslinking agent. By containing the crosslinking agent in the adhesive layer, the polar functional groups derived from the structural unit derived from the polar functional group-containing monomer react with the crosslinking agent, forming a crosslinked structure in the (meth)acrylic copolymer, significantly reducing the adhesive strength of the non-metallic layer. As a result, the non-metallic layer can be more easily removed.

[0093] Examples of the crosslinking agent include an isocyanate-based crosslinking agent, an aziridine-based crosslinking agent, an epoxy-based crosslinking agent, a metal chelate-based crosslinking agent, etc. Among these, an isocyanate-based crosslinking agent is preferred because it has a fast reaction rate and further increases the cohesive strength of the adhesive layer.

[0094] The preferred lower limit of the content of the crosslinking agent relative to 100 parts by mass of the (meth)acrylic copolymer is 0.005 parts by mass, and the preferred upper limit is 30 parts by mass. By having the content of the crosslinking agent within this range, the non-metallic layer can be more easily removed. The more preferred lower limit of the content of the crosslinking agent is 0.008 parts by mass, and the more preferred upper limit is 28 parts by mass, and the even more preferred lower limit is 0.01 parts by mass, and the even more preferred upper limit is 25 parts by mass.

[0095] The adhesive layer preferably further contains an ultraviolet absorber, which makes it possible to more easily remove the support substrate and the adhesive layer by irradiation with light (laser light, etc.).

[0096] Examples of the ultraviolet absorber include triazine-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, etc. Among these, from the viewpoint of further improving the heat resistance of the adhesive sheet, it is preferable that the ultraviolet absorber include a triazine-based ultraviolet absorber.

[0097] Examples of the triazine-based ultraviolet absorber include Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 477, Tinuvin 479, Tinuvin 1577ED, and Tinuvin 1600 (all manufactured by BASF Corporation), and Adekastab LA46 and Adekastab LA-F70 (all manufactured by ADEKA Corporation). Of these, Tinuvin 400, Tinuvin 479, and Tinuvin 1600 are preferred.

[0098] The preferred lower limit of the content of the ultraviolet absorber relative to 100 parts by mass of the resin is 1 part by mass, and the preferred upper limit is 30 parts by mass. When the content of the ultraviolet absorber is within the above range, the support substrate and the adhesive layer can be more easily removed when irradiated with light (laser light, etc.). The more preferred lower limit of the ultraviolet absorber is 5 parts by mass, and even more preferred lower limit is 7 parts by mass, and the more preferred upper limit is 20 parts by mass, and even more preferred upper limit is 15 parts by mass.

[0099] The adhesive layer preferably further contains an inorganic filler, which can prevent the adhesive layer from decreasing in elastic modulus at high temperatures and can further prevent peeling during high-temperature processing even when the adhesive layer is subjected to high-temperature processing at 300°C or higher.

[0100] Examples of the inorganic filler include inorganic fillers consisting of at least one selected from the group consisting of oxides of silicon, titanium, aluminum, calcium, boron, magnesium, and zirconia, and composites thereof. Among these, silica and talc are preferred because they are commercially available at low cost and easily available.

[0101] The inorganic filler may be surface-modified. Examples of the functional group that may be used to modify the surface of the inorganic filler include an alkylsilane group, a methacryloyl group, and a dimethylsiloxane group. Among these, a dimethylsiloxane group is preferred because it has appropriate hydrophobicity.

[0102] The preferred lower limit of the average particle size of the inorganic filler is 5 nm. When the average particle size of the inorganic filler is 5 nm or more, peeling of the adhesive layer during high-temperature processing can be more effectively prevented, and the adhesive layer can be more easily removed. A more preferred lower limit of the average particle size of the inorganic filler is 10 nm, and an even more preferred lower limit is 15 nm. Furthermore, the average particle size of the inorganic filler is preferably equal to or less than the thickness of the adhesive layer. When the average particle size of the inorganic filler is equal to or less than the thickness of the adhesive layer, peeling of the resulting adhesive sheet during high-temperature processing can be more effectively prevented, and the adhesive layer can be more easily removed. The average particle size of the inorganic filler is more preferably equal to or less than 70% of the thickness of the adhesive layer, and even more preferably equal to or less than 50% of the thickness of the adhesive layer. The average particle size can be determined, for example, by observing 50 random inorganic fillers using an electron microscope or optical microscope and calculating the average particle size of each inorganic filler, or by performing laser diffraction particle size distribution measurement.

[0103] The content of the inorganic filler is preferably 1 part by mass or less and 20 parts by mass or less per 100 parts by mass of the resin. By having the content of the inorganic filler within this range, peeling of the adhesive layer during high-temperature processing can be more effectively prevented, and the adhesive layer can be more easily removed. The content of the inorganic filler is more preferably 3 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 5 parts by mass or less, and even more preferably 10 parts by mass or less.

[0104] It is preferable that the adhesive layer does not contain a black pigment, or that the black pigment content is more than 0% by mass and not more than 1% by mass. When the adhesive layer does not contain a black pigment, or that the black pigment content is more than 0% by mass and not more than 1% by mass, the adhesive layer and the metal layer can be more easily peeled off. As a result, a step of removing the adhesive layer from the metal layer is not required. In the adhesive sheet, it is most preferable that the adhesive layer does not contain a black pigment.

[0105] The adhesive layer may contain known additives such as photosensitizers, heat stabilizers, antioxidants, antistatic agents, plasticizers, surfactants, waxes, etc., as long as the effects of the present invention are not impaired.

[0106] The adhesive layer preferably has a light transmittance of 5% or less at a wavelength of 355 nm, or 10% or more at a wavelength of 355 nm. When the adhesive layer has a light transmittance of 355 nm in the above range, the support substrate and the adhesive layer can be more easily removed by irradiation with light (laser light, etc.).

[0107] When the adhesive layer has a light transmittance of 5% or less at a wavelength of 355 nm, the support substrate and the adhesive sheet can be irradiated with light (e.g., laser light) at a wavelength of 355 nm to cause peeling at the interface between the support substrate and the adhesive layer, thereby making it easier to remove the support substrate. After peeling the support substrate, dry etching (e.g., plasma etching) can be performed on the adhesive layer, making it easier to remove the support substrate and the adhesive layer. When the adhesive layer has a UV transmittance of 5% or less at a wavelength of 355 nm, the adhesive layer's light transmittance at a wavelength of 355 nm is more preferably 3%, and even more preferably 1%. When the adhesive layer has a light transmittance of 5% or less at a wavelength of 355 nm, there is no particular lower limit to the adhesive layer's light transmittance at a wavelength of 355 nm, but the practical lower limit is 0.01%.

[0108] When the adhesive layer has a light transmittance of 355 nm greater than 5%, typically, irradiating a laminate comprising a support substrate and the adhesive sheet with light (e.g., laser light) at a wavelength of 355 nm from the support substrate side causes peeling at the interface between the adhesive layer and the metal layer. When the adhesive layer has a UV transmittance of 10% or greater at a wavelength of 355 nm, peeling occurs more easily at the interface between the adhesive layer and the metal layer when irradiated with light (e.g., laser light) at a wavelength of 355 nm, making it easier to remove the support substrate and the adhesive layer. Therefore, even when irradiating with UV light (e.g., laser light) with low irradiation energy, the support substrate and the adhesive layer can be easily removed, thereby reducing the impact of UV irradiation on the metal layer and improving the quality of the semiconductor redistribution layer obtained using the adhesive sheet. When the adhesive layer has a light transmittance of 10% or greater at a wavelength of 355 nm, the lower limit of the adhesive layer's light transmittance at a wavelength of 355 nm is more preferably 50%, even more preferably 60%, and even more preferably 80%. Furthermore, when the adhesive layer has a light transmittance of 10% or more for a light beam having a wavelength of 355 nm, there is no particular preferred upper limit for the light transmittance of the adhesive layer for a light beam having a wavelength of 355 nm, but the practical upper limit is 95%. Note that when the adhesive sheet has a configuration having the adhesive layer, the substrate, and the metal layer in this order, as described below, and the adhesive layer or the substrate remains on the metal layer after the support substrate is peeled off, the adhesive layer or the substrate can be further dry-etched to more easily remove the adhesive layer or the substrate.

[0109] The adhesive layer in the adhesive sheet has a preferred lower limit of 10% for the light transmittance at a wavelength of 500 nm. When the adhesive layer has a light transmittance at a wavelength of 10% or more, the adhesive layer can be more easily peeled from the metal layer described below by irradiating a laminate comprising a support substrate and the adhesive sheet with light (e.g., a green laser) having a wavelength of 500 nm or more from the support substrate side. As a result, the process of removing the adhesive layer from the metal layer is unnecessary. The adhesive layer's more preferred lower limit for the light transmittance at a wavelength of 500 nm is 70%. Furthermore, there is no particular preferred upper limit for the light transmittance at a wavelength of 500 nm of the adhesive layer in the adhesive sheet, but the practical upper limit is 95%.

[0110] The light transmittances in this specification can be measured using a spectrophotometer, such as Spectrophotometer U-3900 (manufactured by Hitachi High-Tech Science Corporation).

[0111] Methods for adjusting the light transmittance of each adhesive layer in the adhesive sheet within the above range include adjusting the thickness of the adhesive layer, changing the composition of the adhesive layer (for example, adjusting the type of resin, reducing the content of black pigment, etc.), and the like.

[0112] The adhesive layer preferably has a thickness of 1 μm at its lower limit and 100 μm at its upper limit. By ensuring sufficient adhesion between the support substrate and the adhesive sheet to firmly secure the electronic components during processing, the nonmetallic layer can be more easily peeled from the metal layer described below by irradiating light (laser light, etc.) from the support substrate side. When peeling occurs at the interface between the support substrate and the adhesive layer by irradiating light (laser light, etc.), the remaining adhesive layer can be efficiently removed by etching. The adhesive layer's thickness is more preferably 3 μm at its lower limit, 50 μm at its upper limit, 4 μm at its even more preferred limit, 30 μm at its even more preferred limit, 5 μm at its even more preferred limit, and 20 μm at its even more preferred limit. When the adhesive layer contains the inorganic filler, the adhesive layer's thickness is 5 μm or more.

[0113] The adhesive sheet has a metal layer. The metal layer is preferably used as a metal seed layer. By using the metal layer as a metal seed layer, it is not necessary to form a metal seed layer during a rewiring process, etc. As a result, there are no problems when performing sputtering or the like to form a metal seed layer during the rewiring process, and the yield during the rewiring process, etc. is further improved, thereby further improving the manufacturing efficiency of semiconductor devices. Furthermore, the metal layer in the adhesive sheet is laminated during the manufacturing of the adhesive sheet, and since equipment with large exhaust capacity can be easily used during the manufacturing of the adhesive sheet, large adhesive sheets having large metal layers can be manufactured more easily without problems such as sputtering. Therefore, even in the manufacturing of large semiconductor devices, by using the metal layer of a large adhesive sheet as a metal seed layer during the rewiring process, it is possible to further suppress a decrease in yield during the rewiring process, etc.

[0114] Examples of the metal layer include a layer made of copper, a layer made of titanium, and a layer made of stainless steel. Among these, a layer made of copper is preferred from the viewpoint of electrical conductivity. The metal layer may be a single layer or may be composed of two or more layers.

[0115] When the metal layer has a layer made of copper, the preferred upper limit of the thickness of the copper layer is 1.0 μm. By having a thickness of the copper layer of 1.0 μm or less, etching of the metal layer remaining after separating the support substrate and the adhesive layer can be performed more efficiently. A more preferred upper limit of the thickness of the copper layer is 0.8 μm, and an even more preferred upper limit is 0.6 μm. Furthermore, when the metal layer has a layer made of copper, the lower limit of the thickness of the copper layer is not particularly limited, but a preferred lower limit is 0.1 μm.

[0116] The metal layer does not have a layer composed of titanium, or has a layer composed of titanium. If the metal layer has the layer composed of titanium, the preferred upper limit of the thickness of the layer composed of titanium is 1.0 μm. If the metal layer does not have a layer composed of titanium, or has a layer composed of titanium and has a layer composed of titanium, the thickness of the layer composed of titanium being 1.0 μm or less makes it easier to remove the adhesive layer. If the metal layer has the layer composed of titanium, the more preferred upper limit of the thickness of the layer composed of titanium is 0.8 μm, and even more preferred upper limit is 0.6 μm. It is most preferred that the metal layer does not have a layer composed of titanium. Note that if the metal layer has the layer composed of titanium, the lower limit of the thickness of the layer composed of titanium is not particularly limited, but the preferred lower limit is 0.05 μm.

[0117] The preferred upper limit of the thickness of the entire metal layer is 2.0 μm. When the thickness of the entire metal layer is 2.0 μm or less, etching of the metal layer remaining after separating the support substrate and the adhesive layer can be carried out more efficiently. The more preferred upper limit of the thickness of the entire metal layer is 1.5 μm, and even more preferred upper limit is 1.0 μm. Furthermore, from the viewpoint of film formability, the preferred lower limit of the thickness of the entire metal layer is 0.1 μm, more preferably 0.2 μm, and even more preferably 0.3 μm. In addition, in the optically peelable adhesive sheet of the present invention, when the metal layer is composed of two or more layers, the "thickness of the metal layer" means the thickness of the entire metal layer.

[0118] The metal layer preferably includes a dry process layer from the viewpoint of suppressing chemical effects on the non-metal layer (such as effects on adhesive strength). The dry process layer preferably includes one layer selected from the group consisting of a vapor deposition layer, a sputtering layer, and an ion plating layer, from the viewpoint of forming a more uniform metal layer, and more preferably includes a sputtering layer.

[0119] The surface roughness (Ra) of the metal layer is preferably 500 nm or less. In the rewiring process using the metal layer, copper is plated on the metal layer as needed, and then a lithography process is performed to produce wiring. In this case, if the film quality of the metal layer formed (filmed) on the adhesive sheet is poor, high-performance wiring such as high-resolution wiring may not be formed. By having the surface roughness of the metal layer be 500 nm or less, the film quality of the metal layer is improved, and high-performance wiring can be easily formed. The surface roughness (Ra) of the metal layer is more preferably less than 500 nm, and even more preferably 100 μm or less. There is no particular lower limit for the surface roughness (Ra) of the metal layer, and 0 μm is most preferred.

[0120] The adhesive sheet preferably has the metal layer on the outermost surface thereof. By having the metal layer on the outermost surface of the adhesive sheet, the metal layer can be used as a metal seed layer without any additional steps.

[0121] From the viewpoint of facilitating the removal of the adhesive layer and further suppressing peeling between the adhesive layer and the metal layer during the rewiring process, it is preferable that the adhesive layer and the metal layer are directly laminated on each other in the adhesive sheet. By directly laminating the adhesive layer and the metal layer, the metal layer and the adhesive layer have mutual adhesion, which can further suppress peeling between the adhesive layer and the metal layer during the rewiring process. Furthermore, by directly laminating the adhesive layer and the metal layer, the adhesive layer can be easily removed by plasma etching.

[0122] The adhesive sheet may have layers other than the adhesive layer and the metal layer as long as the effects of the present invention are not impaired. Therefore, if necessary, the adhesive sheet may have another layer between the adhesive layer and the substrate or between the substrate and the metal layer for the purpose of improving adhesion between layers. In this case, the thickness of the other layer inserted between the layers is preferably 10 μm or less, more preferably 5 μm or less, even more preferably 3 μm or less, and particularly preferably 1 μm or less.

[0123] The adhesive sheet preferably further comprises a substrate, which makes it easier to laminate the resulting adhesive sheet onto an adherend such as a supporting substrate.

[0124] From the viewpoint of making it easier to laminate the adhesive sheet on the support substrate, it is preferable that the adhesive sheet have the adhesive layer, the substrate, and the metal layer in this order. When the adhesive sheet has such a structure, the rigidity of the substrate improves handleability, making it easier to laminate the adhesive sheet on the support substrate. Although other layers may be present between the adhesive layer and the substrate or between the substrate and the metal layer, it is more preferable that the adhesive layer is directly laminated on one side of the substrate and the metal layer is directly laminated on the other side of the substrate. By directly laminating the adhesive layer on the substrate, the adhesion between the adhesive layer and the substrate is increased, reducing problems such as peeling of the adhesive sheet during processing. By directly laminating the metal layer on the substrate, a metal layer with excellent film formation quality can be formed, making it possible to form higher-performance wiring (such as wiring with high resolution).

[0125] The substrate is not particularly limited, and examples thereof include polyethylene terephthalate (PET) film, polyethylene naphthalate (PEN) film, polyether ether ketone (PEEK) film, polycarbonate (PC) film, acrylic resin (PMMA) film, polyamide (PA) film, etc. Among these, from the viewpoint of excellent heat resistance, it is preferable that the substrate includes at least one selected from the group consisting of PET film, PEN film, and PEEK film.

[0126] The substrate preferably has a lower limit of 10% for the transmittance of light at a wavelength of 500 nm. When the substrate has a transmittance of 10% or more for light at a wavelength of 500 nm, the non-metallic layer described below and the metal layer described below can be more easily peeled off by irradiating a laminate obtained by laminating a support substrate and the adhesive sheet with light (e.g., a green laser) having a wavelength of 500 nm or more from the support substrate side. As a result, the step of removing the non-metallic layer described below from the metal layer is unnecessary. The substrate more preferably has a lower limit of 25% for the transmittance of light at a wavelength of 500 nm. Furthermore, there is no particular upper limit for the transmittance of light at a wavelength of 500 nm of the substrate in the adhesive sheet, but the practical upper limit is 95%.

[0127] The substrate preferably has a lower limit of 10% for the transmittance of light at a wavelength of 355 nm. When the substrate has a transmittance of 10% or more for light at a wavelength of 355 nm, the non-metallic layer described below and the metal layer can be more easily peeled off by irradiating a laminate obtained by laminating a support substrate and the adhesive sheet with light (laser light, etc.) at a wavelength of 355 nm from the support substrate side. As a result, the step of removing the non-metallic layer described below from the metal layer is unnecessary. The substrate more preferably has a lower limit of 15% for the transmittance of light at a wavelength of 355 nm. Furthermore, there is no particular upper limit for the transmittance of light at a wavelength of 355 nm of the substrate in the adhesive sheet, but the practical upper limit is 95%.

[0128] The preferred lower limit of the thickness of the substrate is 5 μm, and the preferred upper limit is 100 μm. By having a thickness of 5 μm or more, it is possible to ensure ease of handling during production. By having a thickness of 100 μm or less, it is possible to further prevent problems during use due to curling of the substrate when handling the product. Furthermore, by having a thickness of the substrate within this range, the resulting adhesive sheet has excellent handleability and is easier to laminate on an adherend such as a support substrate. The more preferred lower limit of the thickness of the substrate is 10 μm, the more preferred upper limit is 75 μm, and the even more preferred upper limit is 25 μm.

[0129] The adhesive sheet for semiconductor device manufacturing has a non-metallic layer and the metal layer, the metal layer is laminated on one side of the non-metallic layer, the non-metallic layer includes the adhesive layer, and it is preferable that the non-metallic layer has a light transmittance of 5% or more at a wavelength of 500 nm (hereinafter, this may be simply referred to as the "first configuration").

[0130] When the adhesive sheet is peeled from the support substrate by irradiation with light (laser light, etc.), the light (laser light, etc.) irradiation may cause resin components, etc. contained in the non-metallic layer to scatter, contaminating the substrate, etc., or peeling occurs at the interface between the non-metallic layer of the adhesive sheet and the support substrate, making it necessary to perform a step of removing the non-metallic layer remaining on the metal layer after peeling by plasma etching, etc. When the adhesive sheet satisfies the first configuration, the adhesive sheet can easily photo-peel the non-metallic layer from the metal layer, making it more suitable for use as a photo-peelable adhesive sheet, as described below, and further improving the yield in the manufacture of semiconductor devices.

[0131] From a similar viewpoint, it is also preferable that the adhesive sheet has a non-metallic layer and the metal layer, the metal layer is laminated on one side of the non-metallic layer, the non-metallic layer includes the adhesive layer, the adhesive layer includes a base polymer, the base polymer includes at least one selected from the group consisting of (meth)acrylic copolymers and resins having an imide skeleton in the main chain repeating unit, and the adhesive layer does not include a black pigment or the content of the black pigment is more than 0% by mass and not more than 1% by mass (hereinafter, this may be simply referred to as the "second configuration").

[0132] In the first and second configurations, examples of the non-metallic layer include layers other than the metallic layer, such as an adhesive layer and a substrate.

[0133] The adhesive layer and substrate of the non-metallic layer can be, for example, the adhesive layer and substrate of the adhesive sheet described above. When the non-metallic layer has the adhesive layer of the adhesive sheet described above, the non-metallic layer can be more easily removed. Furthermore, when the non-metallic layer has the substrate of the adhesive sheet described above, the non-metallic layer can be more easily peeled from the metal layer by irradiating a laminate comprising a support substrate and the adhesive sheet with light (green laser) having a wavelength of 500 nm or more from the support substrate side.

[0134] When the adhesive sheet satisfies the first configuration, the non-metallic layer preferably has a lower limit of 5% for light transmittance at a wavelength of 500 nm. When the non-metallic layer in the adhesive sheet has a light transmittance at a wavelength of 500 nm of 5% or more, the non-metallic layer can be more easily peeled from the metal layer described below by irradiating a laminate comprising a support substrate and the adhesive sheet for semiconductor device production with light having a wavelength of 500 nm or more (e.g., a green laser) from the support substrate side. As a result, the process of removing the non-metallic layer from the metal layer is unnecessary. The non-metallic layer in the adhesive sheet more preferably has a lower limit of 10%, even more preferably 15%, even more preferably 20%, and especially preferably 50% for light transmittance at a wavelength of 500 nm. When the adhesive sheet satisfies the second configuration, the non-metallic layer preferably has a lower limit of 5% for light transmittance at a wavelength of 500 nm. When the non-metallic layer in the adhesive sheet has a light transmittance of 5% or more at a wavelength of 500 nm, the non-metallic layer can be more easily peeled from the metal layer described below by irradiating a laminate comprising a support substrate and the adhesive sheet for semiconductor device production with light (e.g., a green laser) having a wavelength of 500 nm or more from the support substrate side. As a result, the process of removing the non-metallic layer from the metal layer is unnecessary. The more preferred lower limit of the light transmittance at a wavelength of 500 nm of the non-metallic layer in the adhesive sheet is 10%, an even more preferred lower limit is 15%, an even more preferred lower limit is 20%, and an especially preferred lower limit is 50%. Furthermore, there is no particular preferred upper limit for the light transmittance at a wavelength of 500 nm of the non-metallic layer in the adhesive sheet, but the practical upper limit is 95%.

[0135] Methods for adjusting the light transmittance of the non-metallic layer within the above range include adjusting the thickness of the non-metallic layer, the adhesive layer, and the substrate, adjusting the light transmittance of the adhesive layer and the substrate, changing the composition of the adhesive layer (for example, adjusting the type of base polymer, reducing the pigment content, etc.), and changing the type of the substrate.

[0136] In the adhesive sheet, the non-metallic layer may have a light transmittance of 5% or more at a wavelength of 355 nm, or less than 5%. When the non-metallic layer has a light transmittance of 5% or more at a wavelength of 355 nm, the non-metallic layer can be easily peeled from the metal layer described below by irradiating a laminate comprising a support substrate and the adhesive sheet with light (e.g., laser light) at a wavelength of 355 nm from the support substrate side. As a result, the step of removing the non-metallic layer from the metal layer is unnecessary. When the non-metallic layer has a light transmittance of 5% or more at a wavelength of 355 nm, the non-metallic layer preferably has a light transmittance of 10% or more at a wavelength of 355 nm, and more preferably has a light transmittance of 50% or more at a wavelength of 355 nm. Furthermore, when the non-metallic layer has a light transmittance of 5% or more at a wavelength of 355 nm, there is no particular upper limit to the preferred light transmittance of the non-metallic layer at a wavelength of 355 nm, but the practical upper limit is 95%.

[0137] On the other hand, when the light transmittance of the non-metallic layer at a wavelength of 355 nm is less than 5%, it can be peeled at the interface between the support substrate and the non-metallic layer by irradiating it with light (e.g., laser) at a wavelength of 355 nm. Therefore, after the non-metallic layer and the metal layer described below are peeled by irradiating them with light (e.g., green laser), the non-metallic layer can be easily removed from the support substrate by irradiating them with light (e.g., laser light) at a wavelength of 355 nm. Furthermore, when a laminate formed by laminating a support substrate and the adhesive sheet is irradiated with light (e.g., laser light) at a wavelength of 355 nm from the support substrate side to peel the support substrate and the non-metallic layer, if necessary, the non-metallic layer remaining on the metal layer can also be removed by dry etching (e.g., plasma etching). Furthermore, when the light transmittance of the non-metallic layer at a wavelength of 355 nm is less than 5%, the non-metallic layer has better heat resistance. Although the reason for this excellent heat resistance is unclear, it is speculated that the non-metallic layer contains a material that absorbs 355 nm light, such as a material containing an aromatic ring, and therefore the heat resistance is improved. If the non-metallic layer has a light transmittance of less than 5% at 355 nm, the non-metallic layer preferably has a light transmittance of less than 3%, and more preferably less than 1%. Furthermore, if the non-metallic layer has a light transmittance of less than 5% at 355 nm, there is no particular preferred lower limit for the light transmittance of the non-metallic layer at 355 nm, but the practical lower limit is 0.01%.

[0138] In the first configuration, the adhesive layer preferably includes a base polymer, and the base polymer preferably includes at least one selected from the group consisting of (meth)acrylic copolymers and resins having an imide skeleton in their main chain repeating units. By including at least one selected from the group consisting of the (meth)acrylic copolymers and resins having an imide skeleton in their main chain repeating units, the adhesive sheet allows for easier removal of the non-metallic layer. In the second configuration, the adhesive layer preferably includes a base polymer, and the base polymer preferably includes at least one selected from the group consisting of (meth)acrylic copolymers and resins having an imide skeleton in their main chain repeating units. By including at least one selected from the group consisting of the (meth)acrylic copolymers and resins having an imide skeleton in their main chain repeating units, the adhesive sheet allows for easier removal of the non-metallic layer.

[0139] The (meth)acrylic copolymer and the resin having an imide skeleton in the repeating unit of the main chain in the base polymer may be, for example, the (meth)acrylic copolymer and the resin having an imide skeleton in the repeating unit of the main chain used as the resin in the adhesive sheet described above.

[0140] When the adhesive sheet satisfies the first configuration, it is preferable that the adhesive layer does not contain a black pigment, or that the black pigment content is more than 0% by mass and not more than 1% by mass. When the adhesive layer of the adhesive sheet does not contain a black pigment, or that the black pigment content is more than 0% by mass and not more than 1% by mass, it becomes easier to adjust the light transmittance of the non-metallic layer in the adhesive sheet at a wavelength of 500 nm to 5% or more. It is most preferable that the adhesive layer of the adhesive sheet does not contain a black pigment. When the adhesive sheet satisfies the second configuration, the adhesive layer does not contain a black pigment, or that the black pigment content is more than 0% by mass and not more than 1% by mass. When the adhesive layer of the adhesive sheet does not contain a black pigment, or that the black pigment content is more than 0% by mass and not more than 1% by mass, it becomes easier to peel the non-metallic layer from the metal layer described below by irradiating a laminate obtained by laminating a support substrate and the adhesive sheet with light (e.g., a green laser) with a wavelength of 500 nm or more from the support substrate side. As a result, the step of removing the non-metallic layer from the metallic layer is not necessary.In the adhesive sheet, it is most preferable that the adhesive layer does not contain a black pigment.

[0141] In the first and second configurations, the metal layer is preferably laminated on one side of the non-metallic layer. Furthermore, when the non-metallic layer has the adhesive layer and the substrate as described above, the adhesive sheet preferably has the adhesive layer, the substrate, and the metal layer in this order, and more preferably the adhesive layer is laminated directly on one side of the substrate, and the metal layer is laminated directly on the other side of the substrate. In particular, in the first and second configurations, the adhesive sheet preferably has the metal layer on its outermost surface. By having the metal layer on its outermost surface, the metal layer can be used as a metal seed layer without any additional steps.

[0142] When the adhesive sheet satisfies the first or second configuration, the preferred lower limit of the thickness of the non-metallic layer is 1 μm, and the preferred upper limit is 200 μm. By ensuring that the thickness of the non-metallic layer is within this range, the resulting adhesive sheet does not impede light transmission, and light (laser light, etc.) irradiated from the support substrate side of the laminate comprising the support substrate and the adhesive sheet can reach the metal layer described below, making it easy to peel the non-metallic layer from the metal layer. The more preferred lower limit of the thickness of the non-metallic layer is 3 μm, and the more preferred upper limit is 80 μm.

[0143] The method for producing the adhesive sheet is not particularly limited, and it can be produced using a conventionally known method. Specifically, for example, the resin and optional additives are first mixed using a bead mill, ultrasonic dispersion, homogenizer, high-power disperser, roll mill, or the like to prepare an adhesive solution. The resulting adhesive solution is then applied to a release PET film and dried at 130°C for 10 minutes to form an adhesive layer. The adhesive sheet can then be produced by forming a metal layer on the adhesive layer. When the metal layer is a multilayer structure, the adhesive sheet can be produced by forming a multilayer metal layer on the layer composed of a metal formed on the adhesive layer, followed by forming a layer composed of another metal.

[0144] Alternatively, an adhesive sheet having an adhesive layer, a substrate, and a metal layer in this order can be produced by applying the adhesive solution obtained by the method described above to one side of a substrate, drying at 130°C for 10 minutes, and then laminating a metal layer by sputtering or the like on the side of the substrate that does not have an adhesive layer on one side.

[0145] Methods for forming the metal layer on the adhesive layer include, for example, dry processes and wet processes. A dry process is preferred from the viewpoint of suppressing chemical effects on the adhesive layer (such as effects on adhesive strength). The dry process preferably includes at least one selected from the group consisting of vapor deposition, sputtering, and dry plating, and more preferably includes sputtering, from the viewpoint of forming a more uniform metal layer. In addition, when the metal layer is a multi-layer structure, a similar method can be used when a layer made of another metal is formed on a layer made of a metal formed on the adhesive layer to form a multi-layer metal layer.

[0146] The adhesive sheet is suitably used as a photo-releasable adhesive sheet. By using the adhesive sheet as a photo-releasable adhesive sheet, when the desired process of applying the adhesive sheet is completed, the adhesive sheet can be easily peeled off by the simple operation of irradiating light, making it possible to easily move on to other processes in the manufacturing process of a semiconductor device. Note that, in this specification, photo-releasability means peeling the adhesive sheet from the adherend by irradiating light, and includes peeling the adhesive sheet from the adherend while irradiating light, as well as peeling the adhesive sheet from the adherend after irradiating light.

[0147] The light used in the photo-peeling is not particularly limited. Examples of the light include light from an LED, an ultra-high pressure mercury lamp, a laser, a metal halide lamp, a xenon lamp, etc. Among these, the adhesive sheet is more preferably used as a laser-peeling adhesive sheet that can be peeled from an adherend by irradiation with laser light, from the viewpoint that the energy is appropriately strong and the peeling of the adhesive sheet by light irradiation can be made easier.

[0148] The adhesive sheet has an area of ​​2500 cm ２ It is preferable that the area of ​​the adhesive sheet is 2500 cm or more. ２For these reasons, the adhesive sheet can be suitably used in the manufacture of large-scale semiconductor devices. In particular, the adhesive sheet is suitably used for forming a semiconductor rewiring layer.

[0149] The adhesive sheet for semiconductor device production can be used without problems even when stored as a wound body (roll-shaped body). By forming the adhesive sheet for semiconductor device production into a wound body, the handleability of the adhesive sheet for semiconductor device production is further improved. A wound body formed by winding the adhesive sheet for semiconductor device production of the present invention also constitutes one aspect of the present disclosure.

[0150] The thickness of the adhesive sheet portion for semiconductor device production in the wound body ((diameter of wound body - diameter of winding core) / 2) is not particularly limited, but a preferred lower limit is 5 mm and a preferred upper limit is 1250 mm. When the thickness of the adhesive sheet portion for semiconductor device production in the wound body is within the above range, the handleability of the wound body is further improved. A more preferred lower limit for the thickness of the adhesive sheet portion for semiconductor device production in the wound body is 8 mm, a more preferred upper limit is 200 mm, an even more preferred lower limit is 10 mm, and an even more preferred upper limit is 150 mm.

[0151] The diameter of the winding core of the wound body is not particularly limited, but a preferred lower limit is 10 mm and a preferred upper limit is 400 mm. When the diameter of the winding core of the wound body is within the above range, the handleability of the wound body is further improved. A more preferred lower limit of the diameter of the winding core of the wound body is 30 mm, a more preferred upper limit is 250 mm, an even more preferred lower limit is 50 mm, and an even more preferred upper limit is 150 mm. In particular, from the viewpoint of making the apparatus used to manufacture the wound body widely versatile, the diameter of the winding core of the wound body is preferably 75 mm (3-inch core) or 150 mm (6-inch core), and more preferably 75 mm.

[0152] The length of the adhesive sheet for semiconductor device production in the roll in the winding direction can be the same as that of a roll of a conventional adhesive film, but can be, for example, 1 m or more and 1000 m or less. The length of the adhesive sheet for semiconductor device production in the roll in the winding direction can be adjusted by changing the size of the manufacturing device for the roll.

[0153] The width of the roll (the length in the stretching direction of the roll) is adjusted appropriately depending on the size of the adherend, and may be, for example, 300 mm or more and 750 mm or less. The width of the adhesive film in the roll (the length in the direction perpendicular to the winding direction) is not particularly limited, and is used, for example, in a width that is about 5 mm to 20 mm shorter than the width of the roll.

[0154] In the first step of the semiconductor device manufacturing method of the present invention 1, the adhesive sheet is laminated on a support substrate. Examples of the support substrate include a glass plate and a sapphire plate. Among these, a glass plate is preferred because it is a transparent support substrate and can be easily removed by irradiation with light (laser light, etc.).

[0155] In the method for manufacturing a semiconductor device according to the first invention, examples of the method for laminating the adhesive sheet onto the support substrate include lamination using a laminator in the atmosphere, vacuum lamination using a vacuum laminator in a vacuum, etc. Among these, vacuum lamination using a vacuum laminator is preferred from the viewpoint of in-plane uniformity and suppressing the occurrence of voids due to problems during lamination.

[0156] The vacuum lamination method using the vacuum laminator is as follows: －２ For example, lamination is performed under conditions of 100 Pa.

[0157] The semiconductor device manufacturing method of the present invention 1 includes a second step of forming a semiconductor rewiring layer on the metal layer. In the second step, the metal layer of the adhesive sheet is used as a metal seed layer to be used in the rewiring step, thereby eliminating the need to form a metal seed layer during the rewiring step, and eliminating problems when performing sputtering or the like of the metal seed layer. As a result, the semiconductor device manufacturing method of the present invention 1 improves yield during the rewiring step and improves the manufacturing efficiency of semiconductor devices.

[0158] The method for forming the semiconductor redistribution layer on the metal layer in the semiconductor device manufacturing method of the first invention is not particularly limited, but examples thereof include the following method. That is, first, a resist is applied to the metal layer, and the resist is hardened by exposure or heating, and then the layer is immersed in a developer such as cyclopentanone to form a wiring pattern for the semiconductor redistribution layer. Next, the formed wiring pattern is plated with metal to form the semiconductor redistribution layer.

[0159] The method for manufacturing a semiconductor device according to the first aspect of the present invention includes a third step of removing the support substrate and the adhesive layer. Note that the phrase "removing the support substrate and the adhesive layer" in the third step may refer to removing the support substrate and the adhesive layer separately, or may refer to removing both the support substrate and the adhesive layer simultaneously.

[0160] The method for removing the support substrate and the adhesive layer in the semiconductor device manufacturing method of the present invention 1 is not particularly limited, but a method of irradiating light onto at least the support substrate is preferred from the viewpoint of simplicity of the process and, since it is a dry process, being able to suppress the influence on the semiconductor redistribution layer caused by immersion in chemical solutions in a wet process.

[0161] In the method for manufacturing a semiconductor device according to the first aspect of the present invention, when the support substrate is irradiated with light, the light to be irradiated is not particularly limited. Examples of the light include light from an LED, an ultra-high pressure mercury lamp, a laser, a metal halide lamp, a xenon lamp, etc. Among these, laser light is preferred from the viewpoint of peelability of the non-metal layer by light irradiation.

[0162] Specific examples of the method for irradiating at least the support substrate with light in the semiconductor device manufacturing method of the present invention 1 include a method in which a laser peeling device (manufactured by Quark Corporation, "QLA-355-2D-2GNNC3") is used to irradiate a laser having a wavelength of 355 nm from the support substrate side.

[0163] After the semiconductor device manufacturing method of the present invention 1 is performed, the metal layer can be removed to obtain a semiconductor redistribution layer. The method for removing the metal layer is not particularly limited, and a conventionally known method can be used. Specific examples include etching using a chemical solution (such as an acid or alkaline solution) and etching using a dry process such as plasma.

[0164] <Method for manufacturing a semiconductor device according to present invention 2> The present disclosure also provides a method for manufacturing a semiconductor device, comprising: a step (i) of attaching an adhesive sheet to a support substrate; and a step (ii) of irradiating the support substrate, to which the adhesive sheet has been attached, with light having a wavelength of λ nm, and peeling off the adhesive sheet, wherein the adhesive sheet has a non-metallic layer and a metallic layer, and the metallic layer is laminated on one side of the non-metallic layer, and in the step (i), the non-metallic layer is attached so as to be in contact with the support substrate, and in the step (ii), the light having a wavelength of λ nm satisfies a light transmittance of 5% or more through the non-metallic layer.

[0165] In the semiconductor device manufacturing method of the second aspect of the present invention, the adhesive sheet has a non-metallic layer and a metal layer. Since equipment with a large exhaust capacity can be easily used during the manufacturing of the adhesive sheet, a large adhesive sheet having a large-area metal layer can be easily manufactured without problems such as sputtering. In the semiconductor device manufacturing method of the second aspect of the present invention using such an adhesive sheet, there is no need to perform sputtering or the like to form a metal seed layer after step (i), so problems caused by sputtering or the like do not occur, and yield can be improved. Furthermore, in step (ii), the non-metallic layer can be removed together with the support substrate by photo-peeling the non-metallic layer and the metal layer in the adhesive sheet, eliminating the need for a step of removing the non-metallic layer remaining on the metal layer, thereby improving the manufacturing efficiency and yield of semiconductor devices.

[0166] In the method for manufacturing a semiconductor device according to the second aspect of the present invention, the metal layer in the adhesive sheet is laminated on one surface of the non-metallic layer. When the non-metallic layer has an adhesive layer and a base material, as described below, the adhesive sheet preferably has the adhesive layer, base material, and metal layer in this order, and more preferably the adhesive layer is laminated directly on one surface of the base material, and the metal layer is laminated directly on the other surface of the base material.

[0167] In the method for manufacturing a semiconductor device of the present invention 2, the non-metallic layer may be, for example, a layer other than a metal layer, such as an adhesive layer, a substrate, etc. The adhesive layer, substrate, and metal layer are not particularly limited, and may be, for example, the same as the adhesive layer and metal layer of the adhesive sheet described above.

[0168] In the step (i) of the method for manufacturing a semiconductor device according to the second aspect of the present invention, the non-metallic layer of the adhesive sheet is attached to the support substrate so as to be in contact with the support substrate. By attaching the non-metallic layer to the support substrate so as to be in contact with the support substrate, the semiconductor device can be easily handled during manufacturing.

[0169] In the method for manufacturing a semiconductor device according to the second aspect of the present invention, examples of the support substrate include a glass plate and a sapphire plate. Among these, a glass plate is preferred because it is a transparent support substrate and can be easily removed by light irradiation.

[0170] In the step (i) of the semiconductor device manufacturing method of the present invention 2, examples of the method for attaching the non-metallic layer of the adhesive sheet to the support substrate include lamination using a laminator in the atmosphere, vacuum lamination using a vacuum laminator in a vacuum, etc. Among these, vacuum lamination using a vacuum laminator is preferred from the viewpoint of in-plane uniformity and suppressing the generation of voids due to problems during attachment.

[0171] The vacuum lamination using the vacuum laminator is, for example, 10 －２ For example, lamination is performed under conditions of 100 Pa.

[0172] In the step (ii) of the method for manufacturing a semiconductor device of the present invention 2, the support substrate to which the adhesive sheet (non-metallic layer) is attached is irradiated with light having a wavelength of λ nm to peel off the adhesive sheet (the non-metallic layer and the metal layer).

[0173] In the semiconductor device manufacturing method of the second aspect of the present invention, the lower limit of the light transmittance of the non-metallic layer for the light with the wavelength λ nm in step (ii) is 5%. In step (ii), the light transmittance of the non-metallic layer for the light with the wavelength λ nm is 5% or more, so that the non-metallic layer and the metal layer can be easily peeled off by irradiating light in step (ii). As a result, the step of removing the non-metallic layer from the metal layer is unnecessary, improving the manufacturing efficiency and yield of semiconductor devices. In step (ii), the lower limit of the light transmittance of the non-metallic layer for the light with the wavelength λ nm in step (ii) is preferably 10%, and more preferably 50%. Furthermore, there is no particular upper limit of the preferred light transmittance of the non-metallic layer for the light with the wavelength λ nm in step (ii), but a practical upper limit is 95%.

[0174] In the step (ii) of the method for manufacturing a semiconductor device according to the second aspect of the present invention, the wavelength of the irradiated light is not particularly limited as long as it satisfies the light transmittance of 5% or more for the non-metallic layer, but the wavelength of the light irradiated onto the support substrate is preferably 200 nm or more and 600 nm or less, and more preferably 500 nm or more and 600 nm or less. Note that, in the step (ii), as long as the wavelength of the irradiated light is a wavelength that satisfies the light transmittance of 5% or more for the non-metallic layer, only one type of light may be irradiated, or two or more types of light having different wavelengths may be irradiated.

[0175] The light used in step (ii) of the semiconductor device manufacturing method of the present invention 2 is not particularly limited. Examples of the light include light from an LED, an ultra-high pressure mercury lamp, a laser, a metal halide lamp, a xenon lamp, etc. Among these, laser light is more preferable from the viewpoint of decomposing and peeling off the non-metallic layer. As the laser light irradiated onto the support substrate, a green laser with a wavelength of 515 nm or a green laser with a wavelength of 532 nm is preferably used.

[0176] In the semiconductor device manufacturing method of the present invention 2, a processing step is usually performed between the above steps (i) and (ii). Specific examples of the processing step include a step of forming a semiconductor rewiring layer on the metal layer. In the step of forming a semiconductor rewiring layer on the metal layer, the metal layer in the adhesive sheet is used as a metal seed layer used in the rewiring step, thereby eliminating the need to form a metal seed layer during the rewiring step, and eliminating problems when performing sputtering of the metal seed layer. As a result, the semiconductor device manufacturing method of the present invention 2 improves yield during the rewiring step and the like, thereby improving the manufacturing efficiency of semiconductor devices and the yield in the manufacture of semiconductor devices.

[0177] In the semiconductor device manufacturing method of the second aspect of the present invention, examples of the method for forming a semiconductor redistribution layer on the metal layer include the following methods. That is, first, a resist is applied to the metal layer, and the resist is hardened by exposure or heating, etc., and then the substrate is immersed in a developer such as cyclopentanone to form a wiring pattern of the semiconductor redistribution layer. The formed wiring pattern is then plated with metal to form a semiconductor redistribution layer. Furthermore, the metal layer used as the metal seed layer can be removed after step (ii). Conventionally known methods can be used to remove the metal layer. Specific examples include etching using a chemical solution (such as an acid or alkaline solution) and etching by a dry process such as plasma.

[0178] According to the present invention, it is possible to provide a method for manufacturing a semiconductor device that can suppress a decrease in yield during a rewiring process, etc., and improve the yield in the manufacture of semiconductor devices, etc. Also, according to the present invention, it is possible to provide an adhesive sheet for manufacturing a semiconductor device that can suppress a decrease in yield during a rewiring process, etc. Furthermore, according to the present invention, it is possible to provide a wound body in which the adhesive sheet for manufacturing a semiconductor device is wound.

[0179] The following examples will explain the present invention in more detail, but the present invention is not limited to these examples.

[0180] (Synthesis of Acrylic Copolymer A) A reactor equipped with a thermometer, a stirrer, and a cooling tube was prepared. 94 parts by mass of 2-ethylhexyl acrylate, 6 parts by mass of hydroxyethyl methacrylate, 0.01 parts by mass of lauryl mercaptan, and 80 parts by mass of ethyl acetate were added to the reactor, and the reactor was heated to initiate reflux. Subsequently, 0.01 parts by mass of 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane was added as a polymerization initiator to initiate polymerization under reflux. Next, 0.01 parts by mass of 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane was added one hour and two hours after the start of polymerization, and then 0.05 parts by mass of t-hexylperoxypivalate was added four hours after the start of polymerization to continue the polymerization reaction. Then, 8 hours after the start of polymerization, an ethyl acetate solution containing a (meth)acrylic polymer without carbon-carbon double bonds and having a solids content of 55% by mass and a weight-average molecular weight of 500,000 was obtained. 3.5 parts by mass of 2-isocyanatoethyl methacrylate was added to 100 parts by mass of the resin solids content of the obtained ethyl acetate solution containing a (meth)acrylic polymer without carbon-carbon double bonds, and the mixture was allowed to react to obtain acrylic copolymer A. The weight-average molecular weight of acrylic copolymer A was 550,000. The weight-average molecular weight of the obtained acrylic copolymer A was measured by gel permeation chromatography (GPC, apparatus name: Acquity APC system (manufactured by Waters Corporation)) using THF as the eluent and an HR-MB-M 6.0 x 150 mm column (manufactured by Waters Corporation).

[0181] (Synthesis of Acrylic Copolymer C) A reactor equipped with a thermometer, a stirrer, and a cooling tube was prepared. 90 parts by mass of n-butyl acrylate, 8 parts by mass of 4-hydroxybutyl acrylate, 0.01 parts by mass of lauryl mercaptan, and 80 parts by mass of ethyl acetate were added to the reactor, and the reactor was heated to initiate reflux. Subsequently, 0.01 parts by mass of 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane was added as a polymerization initiator to initiate polymerization under reflux. Next, 0.01 parts by mass of 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane was added one hour and two hours after the start of polymerization, and then 0.05 parts by mass of t-hexylperoxypivalate was added four hours after the start of polymerization to continue the polymerization reaction. Then, 8 hours after the start of polymerization, an ethyl acetate solution containing a (meth)acrylic polymer without carbon-carbon double bonds and having a solids content of 50% by mass and a weight-average molecular weight of 350,000 was obtained. 4 parts by mass of 2-isocyanatoethyl methacrylate was added to 100 parts by mass of the resin solids content of the obtained ethyl acetate solution containing a (meth)acrylic polymer without carbon-carbon double bonds, and the mixture was reacted to obtain acrylic copolymer C. The weight-average molecular weight of acrylic copolymer C was 400,000. The weight-average molecular weight of the obtained acrylic copolymer C was measured by gel permeation chromatography (GPC, apparatus name: Acquity APC system (manufactured by Waters Corporation)) using THF as the eluent and an HR-MB-M 6.0 x 150 mm column (manufactured by Waters Corporation).

[0182] (Synthesis of Polyimide Resin B) 250 mL of toluene was placed in a 500 mL round-bottom flask equipped with a Teflon (registered trademark) stirrer. 31.9 g (0.06 mol) of dimer diamine (manufactured by Croda, "Priamine 1075"), 5.5 g (0.015 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, and 39.8 g (0.0765 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride were added in this order. A Dean-Stark tube and a condenser were attached to the flask, and the resulting mixture was refluxed for 6 hours and cooled to room temperature. A brown solid polyimide resin B having a structural unit represented by the following formula (5-1) and a structural unit represented by the following formula (5-2) was obtained. The weight average molecular weight of the obtained polyimide resin B was measured by gel permeation chromatography (GPC, apparatus name: Acquity APC system (manufactured by Waters Corporation)) using THF as an eluent and an HR-MB-M (manufactured by Waters Corporation) as a column, and was found to be 78,000.

[0183]

[0184] (Example 1-1) (Preparation of Adhesive Sheet) The materials listed in Table 1 were added to 150 mL of ethyl acetate and mixed to prepare an adhesive solution. The resulting adhesive solution was applied with a doctor knife to the release-treated surface of a 50 μm-thick PET film (release PET film) that had been subjected to one-side release treatment, so that the dried thickness was as listed in Table 1. The coating solution was then heated at 110°C for 10 minutes to dry, forming an adhesive layer. Furthermore, sputtering was performed using a sputtering apparatus (exhaust capacity: 2600 sccm / Pa) to form a metal layer having a thickness shown in Table 1 and comprising a copper layer on the adhesive layer. A separately prepared release PET film was then superimposed so that the release-treated surface faced the metal layer, yielding an adhesive sheet with a release PET film. In this specification, "sccm / Pa" refers to the flow rate required for exhaust when reducing the vacuum to 1 Pa.

[0185] (Measurement of UV transmittance of adhesive layer at a wavelength of 355 nm) The adhesive layer before sputtering was removed and set in a spectrophotometer to measure the UV transmittance (%) of the adhesive layer at a wavelength of 355 nm. The results are shown in Table 1. The spectrophotometer used was a Spectrophotometer U-3900 (manufactured by Hitachi High-Tech Science Corporation).

[0186] Examples 1-2 to 1-3, 1-5, and 1-7 Preparation of Adhesive Sheet Each of the materials listed in Table 1 was added to and mixed with 150 mL of toluene to prepare an adhesive solution. The resulting adhesive solution was applied with a doctor knife to the release-treated surface of a 50 μm-thick PET film (release PET film) that had been release-treated on one side, so that the dried thickness was as shown in Table 1. The coating solution was then dried at 130° C. for 10 minutes to form an adhesive layer. Further, sputtering was performed using a sputtering apparatus (exhaust capacity: 2600 sccm / Pa) to form a metal layer of the type and thickness shown in Table 1 on the adhesive layer, and a separately prepared release PET film was then superimposed so that the release-treated surface faced the metal layer, yielding an adhesive sheet with a release PET film.

[0187] (Measurement of UV Transmittance of Adhesive Layer at a Wavelength of 355 nm) The UV transmittance (%) of the adhesive layer at a wavelength of 355 nm was measured in the same manner as in Example 1-1. The results are shown in Table 1.

[0188] (Example 1-6) (Preparation of Adhesive Sheet) Each material listed in Table 1 was added to 150 mL of toluene and mixed to prepare an adhesive solution. The resulting adhesive solution was applied with a doctor knife to the release-treated surface of a 50 μm-thick PET film (release PET film) that had been release-treated on one side so that the dried thickness was as listed in Table 1. The coating solution was then heated at 130° C. for 10 minutes to dry an adhesive layer. Further, deposition was performed using a vacuum deposition apparatus (exhaust capacity: 2600 sccm / Pa) to form a metal layer having a copper layer of the thickness shown in Table 1 on the adhesive layer, and a separately prepared release PET film was then superimposed so that the release-treated surface faced the metal layer, thereby obtaining an adhesive sheet with a release PET film.

[0189] (Measurement of UV Transmittance of Adhesive Layer at a Wavelength of 355 nm) The UV transmittance (%) of the adhesive layer at a wavelength of 355 nm was measured in the same manner as in Example 1-1. The results are shown in Table 1.

[0190] (Examples 1-8, 1-11) (Preparation of Adhesive Sheet) Each material listed in Table 2 was added to 150 mL of toluene and mixed to prepare an adhesive solution. The resulting adhesive solution was applied with a doctor knife to the release-treated surface of a 50 μm-thick PET film (release PET film) that had been release-treated on one side so that the dried thickness was as listed in Table 1. An adhesive layer was then formed by heating at 130° C. for 10 minutes to dry the coating solution. Furthermore, a layer composed of copper was formed on the adhesive layer using a sputtering apparatus (exhaust capacity: 2600 sccm / Pa), and a layer composed of titanium was formed on the copper layer, thereby forming a metal layer with the thickness shown in Table 2. A separately prepared release PET film was then superimposed so that the release-treated surface faced the metal layer, and an adhesive sheet with a release PET film was obtained.

[0191] (Measurement of UV transmittance of adhesive layer at wavelength of 355 nm) The UV transmittance (%) of the adhesive layer at wavelength of 355 nm was measured in the same manner as in Example 1-1. The results are shown in Table 2.

[0192] (Examples 1-9) (Preparation of Adhesive Sheet) A 25 μm thick polyether ether ketone (PEEK) film ("EXPEEK" manufactured by Kurabo Industries, Ltd.) was sputtered with copper using a sputtering device (exhaust capacity: 2600 sccm / Pa). Separately, the materials listed in Table 2 were added to 150 mL of toluene and mixed to prepare an adhesive solution. The resulting adhesive solution was applied with a doctor knife to the release-treated surface of a 50 μm thick PET film (release PET film) that had been subjected to one-side release treatment so that the dried thickness was as listed in Table 1. The coating solution was then dried by heating at 130° C. for 10 minutes to form an adhesive layer. The resulting adhesive layer was laminated onto the non-copper-sputtered side of the copper-sputtered PEEK film by thermal lamination at a temperature of 100°C using a laminator ("HOTDOG LEON13DX" manufactured by Lamy Corporation), to obtain an adhesive sheet having an adhesive layer, a substrate, and a metal layer in this order.

[0193] (Measurement of UV transmittance of adhesive layer at a wavelength of 355 nm) Using the adhesive layer before being laminated and integrated with the substrate, the UV transmittance (%) of the adhesive layer at a wavelength of 355 nm was measured in the same manner as in Example 1-1. The results are shown in Table 2.

[0194] Examples 1-4 and 1-10 Preparation of Adhesive Sheet An adhesive sheet having an adhesive layer, a substrate, and a metal layer in this order was obtained in the same manner as in Example 1-9, except that an adhesive solution was prepared by adding and mixing the materials listed in Tables 1 and 2, and that a 25 μm thick polyethylene naphthalate (PEN) film (manufactured by Toyobo Co., Ltd., "Teonex") was used instead of a 25 μm thick polyether ether ketone (PEEK) film.

[0195] (Measurement of UV transmittance of adhesive layer at wavelength of 355 nm) The UV transmittance (%) of the adhesive layer at wavelength of 355 nm was measured in the same manner as in Example 1 to 9. The results are shown in Tables 1 and 2.

[0196] (Example 1-12) (Preparation of adhesive sheet) An adhesive sheet having an adhesive layer, a substrate, and a metal layer in this order was obtained in the same manner as in Examples 1-4 and 1-10, except that a 25 μm thick polyethylene terephthalate (PET) film (manufactured by Toray Industries, Inc., "Lumirror") was used instead of the 25 μm thick polyether ether ketone (PEEK) film.

[0197] (Measurement of UV Transmittance of Adhesive Layer at a Wavelength of 355 nm) The UV transmittance (%) of the adhesive layer at a wavelength of 355 nm was measured in the same manner as in Examples 1-4 and 1-10. The results are shown in Table 2.

[0198] Comparative Examples 1-1 and 1-2 Preparation of Adhesive Each material listed in Table 2 was added to 150 mL of toluene and mixed to prepare an adhesive solution.

[0199] (Measurement of UV transmittance of adhesive layer at a wavelength of 355 nm) The obtained adhesive solution was applied with a doctor knife to the release-treated surface of a 50 μm thick PET film (release PET film) that had been release-treated on one side, so that the dried thickness was as shown in Table 2. The coating solution was dried by heating at 130° C. for 10 minutes to form an adhesive layer composed of the adhesive of Comparative Examples 1-1 to 1-2, and the UV transmittance (%) of the adhesive layer at a wavelength of 355 nm was measured in the same manner as in Example 1-1. The results are shown in Table 2.

[0200] (Example 2-1) (Preparation of Adhesive Sheet) The materials listed in Table 3 were added to 150 mL of ethyl acetate and mixed to prepare a pressure-sensitive adhesive solution. The resulting pressure-sensitive adhesive solution was applied with a doctor knife to the release-treated surface of a 50 μm-thick polyethylene terephthalate (PET) film (release PET film) that had been subjected to one-side release treatment, so that the thickness after drying was 10 μm. An adhesive layer was then formed by heating and drying at 130 ° C. for 10 minutes. Next, the resulting adhesive layer was laminated onto one side of a 50 μm-thick PET film (Toray Industries, Inc., "Lumirror #50-S10", substrate) using a laminator (Lamy Corporation, "HOTDOG LEON13DX") at 100 ° C. to form a non-metallic layer. Copper was sputtered using a sputtering device (exhaust capacity: 2600 sccm / Pa) to laminate a copper layer (metal layer) with a thickness of 200 nm on the side of the obtained non-metal layer that did not have the adhesive layer of the substrate, thereby obtaining an adhesive sheet having an adhesive layer, a substrate, and a metal layer in that order.

[0201] (Measurement of light transmittance of adhesive layer, substrate, and non-metallic layer) For the adhesive layer before lamination with the substrate PET film, the release PET film was peeled off and the light transmittance at wavelengths of 500 nm and 355 nm was measured using a spectrophotometer. Furthermore, for the substrate before lamination with the adhesive layer and the non-metallic layer before lamination with the metal layer, the light transmittance at wavelengths of 500 nm and 355 nm was measured using a spectrophotometer. The respective results are shown in Table 3. Furthermore, a Spectrophotometer U-3900 (manufactured by Hitachi High-Tech Science Corporation) was used as the spectrophotometer.

[0202] Example 2-2 An adhesive sheet having a non-metallic layer, substrate, and metal layer in this order was obtained in the same manner as in Example 2-1, except that a 50 μm thick low-oligomer PET film ("Lumirror #50-X10S" manufactured by Toray Industries, Inc.) was used as the substrate instead of the 50 μm thick PET film, and the thickness of the copper layer (metallic layer) was changed to 500 nm. The light transmittance of the adhesive layer, substrate, and non-metallic layer was measured in the same manner as in Example 2-1. The respective results are shown in Table 3.

[0203] Example 2-3 A non-metallic layer was obtained in the same manner as in Example 1, except that a 50 μm thick polycarbonate (PC) film (manufactured by Sumika Acrylic Sales Co., Ltd., "Technoloy C000 #50") was used as the substrate instead of the 50 μm thick PET film. A 1000 nm thick copper layer (metal layer) was laminated on the side of the obtained non-metallic layer that did not have the adhesive layer of the substrate by vapor deposition of copper using a vacuum deposition apparatus (exhaust capacity: 2600 sccm / Pa), thereby obtaining an adhesive sheet having an adhesive layer, substrate, and metal layer in this order. The light transmittance of the adhesive layer, substrate, and non-metallic layer was measured in the same manner as in Example 2-1. The respective results are shown in Table 3.

[0204] (Example 2-4) Each material listed in Table 3 was added to 150 mL of toluene and mixed to prepare a pressure-sensitive adhesive solution. The obtained pressure-sensitive adhesive solution was applied to the release-treated surface of a 50 μm-thick PET film (release PET film) that had been subjected to one-side release treatment, so that the thickness after drying was 5 μm, using a doctor knife, and heated to 130 ° C. for 10 minutes to dry, thereby forming an adhesive layer. Next, the obtained adhesive layer was laminated onto one side of a 50 μm-thick PC film (manufactured by Sumika Acrylic Sales Co., Ltd., "Technoloy C000 #50", substrate) using a laminator (manufactured by Lamy Corporation, "HOTDOG LEON13DX") at 100 ° C., and integrated to obtain a non-metallic layer. Titanium was vapor-deposited using a vacuum deposition apparatus (exhaust capacity: 2600 sccm / Pa) on the surface of the obtained non-metallic layer that did not have the adhesive layer of the substrate, to form a 200 nm thick titanium layer (metal layer), thereby obtaining an adhesive sheet having an adhesive layer, a substrate, and a metal layer in this order. The light transmittance of the adhesive layer, the substrate, and the non-metallic layer was measured in the same manner as in Example 2-1. The results are shown in Table 3.

[0205] (Example 2-5) The materials listed in Table 3 were added to 150 mL of ethyl acetate and mixed to prepare a pressure-sensitive adhesive solution. The resulting pressure-sensitive adhesive solution was applied to the release-treated surface of a 50 μm-thick PET film (release PET film) that had been subjected to one-sided release treatment, with a doctor knife so that the thickness after drying was 10 μm. The adhesive layer (non-metallic layer) was formed by heating and drying at 130 ° C. for 10 minutes. Copper was sputtered onto the resulting adhesive layer (non-metallic layer) using a sputtering device (exhaust capacity: 2600 sccm / Pa), and then titanium was sputtered to form a 200 nm-thick copper layer and a 200 nm-thick titanium layer (a multi-layer metal layer), resulting in an adhesive sheet having an adhesive layer (non-metallic layer) and a metal layer. The light transmittance of the adhesive layer (non-metallic layer) was measured in the same manner as in Example 2-1. The results are shown in Table 3.

[0206] (Example 2-6) Each material listed in Table 3 was added to 150 mL of toluene and mixed to prepare a pressure-sensitive adhesive solution. The resulting pressure-sensitive adhesive solution was applied with a doctor knife to a release-treated surface of a 50 μm-thick PET film (release PET film) that had been subjected to one-side release treatment, so that the resulting thickness after drying was 5 μm. The resulting adhesive solution was then dried by heating at 130°C for 10 minutes to form an adhesive layer (non-metallic layer). Copper was sputtered onto the resulting adhesive layer (non-metallic layer) using a sputtering device (exhaust capacity: 2600 sccm / Pa) to form a 300 nm-thick copper layer (metallic layer), resulting in an adhesive sheet having an adhesive layer (non-metallic layer) and a metal layer. The light transmittance of the adhesive layer (non-metallic layer) was measured in the same manner as in Example 2-1. The results are shown in Table 3.

[0207] (Example 2-7) An adhesive sheet having a non-metallic layer, substrate, and metal layer in this order was obtained in the same manner as in Example 2-1, except that a 25 μm thick polyethylene naphthalate (PEN) film (Teonex Q83, manufactured by Toyobo Co., Ltd.) was used as the substrate instead of the 50 μm thick PET film. The light transmittance of the adhesive layer, substrate, and non-metallic layer was measured in the same manner as in Example 2-1. The respective results are shown in Table 3.

[0208] (Example 2-8) An adhesive sheet having a non-metallic layer, a substrate, and a metal layer in this order was obtained in the same manner as in Example 2-1, except that the composition of the adhesive layer was changed to that shown in Table 4 and the thickness of the copper layer (metallic layer) was changed to 300 nm. The light transmittance of the adhesive layer, the substrate, and the non-metallic layer was measured in the same manner as in Example 2-1. The respective results are shown in Table 4.

[0209] (Example 2-9) Each material listed in Table 4 was added to 150 mL of toluene and mixed to prepare a pressure-sensitive adhesive solution. The resulting pressure-sensitive adhesive solution was applied to the release-treated surface of a 50 μm-thick PET film (release PET film) that had been subjected to one-side release treatment, using a doctor knife, so that the thickness after drying was 5 μm. The adhesive layer was then heated and dried at 130 ° C. for 10 minutes to form an adhesive layer. Next, the resulting adhesive layer was thermally laminated onto one side of a 25 μm-thick PEN film (manufactured by Toyobo Co., Ltd., "Teonex Q83", substrate) using a laminator (manufactured by Lamy Corporation, "HOTDOG LEON13DX") at 100 ° C. to form an integrated non-metallic layer. Copper was sputtered using a sputtering device (exhaust capacity: 2600 sccm / Pa) onto the surface of the obtained non-metallic layer that did not have the adhesive layer of the substrate, to form a 500 nm thick copper layer (metal layer), thereby obtaining an adhesive sheet having an adhesive layer, a substrate, and a metal layer in this order. The light transmittance of the adhesive layer, the substrate, and the non-metallic layer was measured in the same manner as in Example 2-1. The results are shown in Table 4.

[0210] (Example 2-10) An adhesive sheet having a non-metallic layer, substrate, and metal layer in this order was obtained in the same manner as in Example 2-1, except that a 25 μm thick polyether ether ketone (PEEK) film ("Expeak" manufactured by Kurabo Industries, Ltd.) was used as the substrate instead of the 50 μm thick PET film. The light transmittance of the adhesive layer, substrate, and non-metallic layer was measured in the same manner as in Example 2-1. The respective results are shown in Table 4.

[0211] (Example 2-11) Each material listed in Table 4 was added to 150 mL of toluene and mixed to prepare a pressure-sensitive adhesive solution. The resulting pressure-sensitive adhesive solution was applied to the release-treated surface of a 50 μm-thick PET film (release PET film) that had been subjected to one-side release treatment, using a doctor knife, so that the thickness after drying would be 5 μm, and the adhesive layer was formed by heating and drying at 130 ° C. for 10 minutes. Next, the resulting adhesive layer was thermally laminated onto one side of a 25 μm-thick PEEK film (manufactured by Kurabo Industries, Ltd., "Xpeak", substrate) using a laminator (manufactured by Ramie Corporation, "HOTDOG LEON 13DX") at 100 ° C. to form an integrated non-metallic layer. Copper was sputtered using a sputtering device (exhaust capacity: 2600 sccm / Pa) onto the surface of the obtained non-metallic layer that did not have the adhesive layer of the substrate, to form a 200 nm thick copper layer (metal layer), thereby obtaining an adhesive sheet having an adhesive layer, a substrate, and a metal layer in this order. The light transmittance of the adhesive layer, the substrate, and the non-metallic layer was measured in the same manner as in Example 2-1. The respective results are shown in Table 4.

[0212] (Example 2-12) Each material listed in Table 4 was added to 150 mL of toluene and mixed to prepare a pressure-sensitive adhesive solution. The resulting pressure-sensitive adhesive solution was applied with a doctor knife to a release-treated surface of a 50 μm-thick PET film (release PET film) that had been subjected to one-side release treatment, so that the resulting thickness after drying was 10 μm. The resulting solution was then dried by heating at 130°C for 10 minutes to form an adhesive layer (non-metallic layer). Copper was sputtered onto the resulting adhesive layer (non-metallic layer) using a sputtering device (exhaust capacity: 2600 sccm / Pa) to form a 200 nm-thick copper layer (metallic layer), resulting in an adhesive sheet having an adhesive layer (non-metallic layer) and a metal layer. The light transmittance of the adhesive layer (non-metallic layer) was measured in the same manner as in Example 2-1. The results are shown in Table 4.

[0213] (Example 2-13) Each material listed in Table 4 was added to 150 mL of ethyl acetate and mixed to prepare a pressure-sensitive adhesive solution. The resulting pressure-sensitive adhesive solution was applied to the release-treated surface of a 50 μm-thick polyethylene terephthalate (PET) film (release PET film) that had been subjected to one-side release treatment, using a doctor knife, so that the thickness after drying was 20 μm. The adhesive layer was then heated and dried at 130 ° C. for 10 minutes to form an adhesive layer. Next, the resulting adhesive layer was thermally laminated onto one side of a 25 μm-thick PEN film (manufactured by Toyobo Co., Ltd., "Teonex Q83", substrate) using a laminator (manufactured by Lamy Corporation, "HOTDOG LEON13DX") at 100 ° C. to form an integrated non-metallic layer. Copper was sputtered using a sputtering device (exhaust capacity: 2600 sccm / Pa) onto the surface of the obtained non-metallic layer that did not have the adhesive layer of the substrate, to form a 200 nm thick copper layer (metal layer), thereby obtaining an adhesive sheet having an adhesive layer, a substrate, and a metal layer in this order. The light transmittance of the adhesive layer, the substrate, and the non-metallic layer was measured in the same manner as in Example 2-1. The respective results are shown in Table 4.

[0214] Example 2-14 An adhesive sheet having a non-metallic layer, substrate, and metal layer in this order was obtained in the same manner as in Example 2-13, except that a 50 μm thick low-oligomer PET film ("Lumirror #50-X10S" manufactured by Toray Industries, Inc.) was used as the substrate instead of the 25 μm thick PEN film, and the thickness of the copper layer (metallic layer) was changed to 500 nm. The light transmittance of the adhesive layer, substrate, and non-metallic layer was measured in the same manner as in Example 2-1. The results are shown in Table 4.

[0215] Example 2-15 An adhesive sheet having a non-metallic layer, substrate, and metal layer in this order was obtained in the same manner as in Example 2-1, except that a 188 μm thick PET film ("Lumirror" manufactured by Toray Industries, Inc.) was used as the substrate instead of the 50 μm thick PET film. The light transmittance of the adhesive layer, substrate, and non-metallic layer was measured in the same manner as in Example 2-1. The results are shown in Table 4.

[0216] (Example 2-16) Each material listed in Table 5 was added to 150 mL of ethyl acetate and mixed to prepare a pressure-sensitive adhesive solution. The resulting pressure-sensitive adhesive solution was applied to the release-treated surface of a 50 μm-thick polyethylene terephthalate (PET) film (release PET film) that had been subjected to one-side release treatment, using a doctor knife, so that the thickness after drying was 20 μm. An adhesive layer was then formed by heating and drying at 130 ° C. for 10 minutes. Next, the resulting adhesive layer was laminated onto one side of a 50 μm-thick low-oligomer PET film (manufactured by Toray Industries, Inc., "Lumirror #50-X10S", substrate) using a laminator (manufactured by Lamy Corporation, "HOTDOG LEON13DX") at 100 ° C. to form a non-metallic layer. Copper was sputtered using a sputtering device (exhaust capacity: 2600 sccm / Pa) onto the surface of the obtained non-metallic layer that did not have the adhesive layer of the substrate, to form a 500 nm thick copper layer (metal layer), thereby obtaining an adhesive sheet having an adhesive layer, a substrate, and a metal layer in this order. The light transmittance of the adhesive layer, the substrate, and the non-metallic layer was measured in the same manner as in Example 2-1. The results are shown in Table 5.

[0217] Example 2-17 An adhesive sheet having a non-metallic layer, substrate, and metal layer in this order was obtained in the same manner as in Example 2-16, except that a 25 μm thick PEN film (Teonex Q83, manufactured by Toyobo Co., Ltd.) was used as the substrate instead of the 50 μm thick low-oligomer PET film. The light transmittance of the adhesive layer, substrate, and non-metallic layer was measured in the same manner as in Example 2-1. The respective results are shown in Table 5.

[0218] (Example 2-18) Each material listed in Table 5 was added to 150 mL of ethyl acetate and mixed to prepare a pressure-sensitive adhesive solution. The resulting pressure-sensitive adhesive solution was applied to the release-treated surface of a 50 μm-thick polyethylene terephthalate (PET) film (release PET film) that had been subjected to one-side release treatment, using a doctor knife, so that the thickness after drying was 20 μm. An adhesive layer was then formed by heating and drying at 130 ° C. for 10 minutes. Next, the resulting adhesive layer was laminated onto one side of a 50 μm-thick low-oligomer PET film (manufactured by Toray Industries, Inc., "Lumirror #50-X10S", substrate) using a laminator (manufactured by Lamy Corporation, "HOTDOG LEON13DX") at 100 ° C., resulting in a non-metallic layer. Copper was sputtered using a sputtering device (exhaust capacity: 2600 sccm / Pa) onto the surface of the obtained non-metallic layer that did not have the adhesive layer of the substrate, to form a 200 nm thick copper layer (metal layer), thereby obtaining an adhesive sheet having an adhesive layer, a substrate, and a metal layer in this order. The light transmittance of the adhesive layer, the substrate, and the non-metallic layer was measured in the same manner as in Example 2-1. The results are shown in Table 5.

[0219] Example 2-19 An adhesive sheet having a non-metallic layer, substrate, and metal layer in this order was obtained in the same manner as in Example 2-18, except that a 25 μm thick PEN film (Teonex Q83, manufactured by Toyobo Co., Ltd.) was used as the substrate instead of the 50 μm thick low-oligomer PET film. The light transmittance of the adhesive layer, substrate, and non-metallic layer was measured in the same manner as in Example 2-1. The respective results are shown in Table 5.

[0220] <Evaluation> The adhesive sheets and adhesives obtained in Examples 1-1 to 1-12, Comparative Examples 1-1 to 1-2, and Examples 2-1 to 2-19 were evaluated by the following methods. The results are shown in Tables 1 to 2 and 6 to 8.

[0221] (1) Preparation of Measurement Samples (Example 1-1) Using a laminator ("HOTDOG LEON 13DX" manufactured by Lamy Corporation), the obtained adhesive sheet was attached to a glass plate having a thickness of 1 mm at room temperature at a lamination speed of 180 mm / min, and then, using a high-pressure mercury lamp, the adhesive sheet was irradiated from the glass plate side with a wavelength of 365 nm and an irradiation intensity of 20 mW / cm. ２ A measurement sample was prepared by irradiating the sample with light of 1000 kJ / cm for 300 seconds.

[0222] (Examples 1-2 to 1-12, Examples 2-1 to 2-19) Using a laminator ("HOTDOG LEON13DX" manufactured by Lamy Corporation), the obtained adhesive sheet was attached to a glass plate having a thickness of 1 mm under conditions of heating at 100°C and a lamination speed of 180 mm / min, to prepare a measurement sample.

[0223] (Comparative Example 1-1) A glass plate was prepared, and the adhesive obtained was laminated onto the glass plate as an adhesive layer having a thickness of 5 μm using a laminator (manufactured by Lamy Corporation, "HOTDOG LEON13DX") at room temperature and a lamination speed of 180 mm / min. The adhesive was then irradiated from the glass plate side with a high-pressure mercury lamp at a wavelength of 365 nm and an irradiation intensity of 20 mW / cm. ２ A measurement sample was prepared by irradiating the sample with light of 1000 kJ / cm for 300 seconds.

[0224] (Comparative Example 1-2) Using a laminator ("HOTDOG LEON13DX" manufactured by Lamy Corporation), the obtained adhesive was laminated onto a glass plate as a 5 μm thick adhesive layer under conditions of heating at 100° C. and a lamination speed of 180 mm / min. Then, using a sputtering device (exhaust capacity 200 sccm / Pa), a 0.2 μm thick layer made of copper was formed on the adhesive layer, and under the same conditions, a 0.2 μm thick layer made of titanium was formed on the copper layer to form a metal seed layer, thereby producing a measurement sample.

[0225] (2) Heat Resistance Evaluation Heat resistance evaluation was carried out to evaluate the practicality of the adhesive sheet against heating for hardening the resist in the process of forming the semiconductor rewiring layer. The heat resistance evaluation was carried out by placing the obtained measurement sample in an oven heated to 200 ° C. and heating for 5 hours, and then air-cooling the heated measurement sample. After that, the measurement sample was visually observed and judged as follows: if there was no peeling or cracking, it was marked as "○", if the peeling or cracking area was within 1% of the total area of ​​the sample, it was marked as "△", and if the peeling or cracking area was greater than 1% of the total area of ​​the sample, it was marked as "×".

[0226] (3) Chemical Resistance Evaluation Chemical resistance evaluation was performed to evaluate the practicality of the adhesive sheet against immersion in a developer for forming a wiring pattern in the process of forming a semiconductor rewiring layer. The chemical resistance evaluation was performed by immersing the obtained measurement sample in cyclopentanone for 1 hour, removing the immersed measurement sample, and visually observing it. If there was no peeling or cracking, it was marked as "○", and if there was peeling or cracking, it was marked as "×".

[0227] (4) Evaluation of Separation of Support Substrate The obtained measurement sample was attached to a dicing tape with a ring frame to prepare a measurement sample with dicing tape. At this time, the side of the sample with the metal layer was attached to the dicing tape. A laser peeling device (Quark Corporation, "QLA-355-2D-2GNNC3") was used, with a wavelength of 355 nm and a pulse energy of 2.1 J / cm. ２The laser light was scanned and irradiated from the glass plate side to the measurement sample with dicing tape. After irradiating the laser light, if the glass plate could be separated from the measurement sample, it was marked "○", and if it could not be separated, it was marked "×", and the separation of the support substrate was evaluated. In Examples 1-1 to 1-2, 2-1 to 2-3, 2-5, 2-8, 2-12, 2-14 to 2-15, and 2-18, laser irradiation caused peeling at the interface between the adhesive layer and the metal layer of the measurement sample with dicing tape, and the glass plate and adhesive layer were separated from the measurement sample with dicing tape. On the other hand, in Examples 1-3 to 1-12, 2-4, 2-6 to 2-7, 2-9 to 2-11, 2-13, 2-16 to 2-17, and 2-19, laser irradiation caused peeling at the interface between the glass plate and the adhesive layer of the measurement sample with dicing tape, and the glass plate was separated from the measurement sample with dicing tape. In addition, for Comparative Examples 1-1 to 1-2, the evaluations of both the above-mentioned "(2) Heat resistance evaluation" and "(3) Chemical resistance evaluation" were "X", so the support substrate was not separated and no evaluation was performed, and the evaluations described below were also not performed.

[0228] (5) Plasma Etching Evaluation (Examples 1-3 to 1-12, 2-4, 2-6 to 2-7, 2-9 to 2-11, 2-13, 2-16 to 2-17, 2-19) For Examples 1-3 to 1-12, 2-4, 2-6 to 2-7, 2-9 to 2-11, 2-13, 2-16 to 2-17, and 2-19, the above-mentioned "(4) Evaluation of Separation of Support Substrate" was performed, and the measurement samples with dicing tape after separation of the glass plate were subjected to O 1 irradiation using a plasma irradiation device (manufactured by SAMCO, "PC-300"). ２ Plasma was irradiated for 30 minutes to remove the adhesive layer by plasma etching. After plasma etching, the measurement sample with the dicing tape after the adhesive layer removal was collected at five equally sized locations to prepare five analysis samples. For each of the five analysis samples, the surface of the metal layer adjacent to the adhesive layer was analyzed by X-ray photoelectron spectroscopy (XPS). In the combined results of the five analysis samples, if the ratio of the carbon atom content to the total element content was less than 10 mass%, it was marked as "○". Furthermore, for measurement samples in which the ratio of the carbon atom content to the total element content was 10 mass% or more, O was marked. ２Plasma etching evaluation was performed again in the same manner as described above, except that the plasma irradiation time was changed to 1 hour. ２ In the plasma etching evaluation in which the plasma irradiation time was set to 1 hour, the results of the five analysis samples were totaled, and the plasma etching evaluation was performed by marking cases in which the ratio of the amount of carbon atoms to the amount of all elements was less than 10 mass% as "△" and cases in which it was 10 mass% or more as "×".

[0229] (6) Etching Evaluation (Examples 1-1 to 1-2, 2-1 to 2-3, 2-5, 2-8, 2-12, 2-14 to 2-15, 2-18) The above-mentioned "(4) Evaluation of Separation of Support Substrate" was performed, and the measurement sample with dicing tape after separation of the glass plate and adhesive layer was immersed in an etching solution (manufactured by Mitsubishi Gas Chemical Company, Inc., "WLC-C2") at room temperature for 5 minutes to etch and remove the metal layer. The dicing tape was removed from the etching solution, dried at 100 ° C. for 10 minutes, and analyzed by energy dispersive X-ray fluorescence spectroscopy (EDX). A 1 mm x 1 mm area from the center of the dicing tape was selected and analyzed, and the area where metal from the metal layer was detected was evaluated as "○" if it was less than 1% of the analyzed area, and as "×" if it was 1% or more of the analyzed area.

[0230] (Examples 1-3 to 1-12, 2-4, 2-6 to 2-7, 2-9 to 2-11, 2-13, 2-16 to 2-17, 2-19) The above-mentioned "(5) Plasma Etching Evaluation" was performed, and the measurement sample with the dicing tape after removing the adhesive layer was immersed in an etching solution ("WLC-C2" manufactured by Mitsubishi Gas Chemical Company, Inc.) at room temperature for 5 minutes to etch and remove the metal layer. The dicing tape was removed from the etching solution, dried at 100 ° C for 10 minutes, and analyzed by energy dispersive X-ray fluorescence spectroscopy (EDX). A 1 mm x 1 mm area from the center of the dicing tape was selected and analyzed, and the etching evaluation was performed with "○" indicating that the area in which metal from the metal layer was detected was less than 1% of the analyzed area, and "×" indicating that the area was 1% or more of the analyzed area.

[0231] (7) Evaluation of Metal Layer Film Quality In Examples 1-1 to 1-12 and Examples 2-1 to 2-19, the surface roughness (Ra) of the metal layer was measured using a laser microscope (Olympus Corporation, "LEXT OLS5100," magnification 40x) to evaluate the film quality of the metal layer. When the measured surface roughness (Ra) was 100 nm or less, it was marked with "◎", when it was more than 100 nm and less than 500 nm, it was marked with "◯", and when it was more than 500 nm, it was marked with "×".

[0232] (8) Photo-Removal Properties For Examples 2-1 to 2-19, the photo-removal properties were evaluated as follows: Using a laminator ("HOTDOG LEON13DX" manufactured by Lamy Corporation), the obtained adhesive sheet was attached to a glass plate having a thickness of 1 mm at room temperature at a lamination speed of 180 mm / min, and then, using a high-pressure mercury lamp, the adhesive sheet was irradiated from the glass plate side with a wavelength of 365 nm and an irradiation intensity of 20 mW / cm. ２ The metal layer of the adhesive sheet was then attached to a dicing tape with a ring frame to prepare a measurement sample. Next, a UV laser irradiation device (Quark Corporation, "QLA-355-2D-2GNNC3") was used to irradiate the sample with a wavelength of 355 nm and a pulse energy density of 0.3 J / cm. ２ The obtained measurement sample was scanned and irradiated with a laser beam of 1.2 J / cm (low pulse energy) from the glass plate side. After irradiation, the photo-peeling property was evaluated by rating "Good" if peeling was possible at the interface between the non-metallic layer and the metallic layer, and rating "Poor" if peeling was not possible. For samples that were rated "Poor," the pulse energy density was increased to 1.2 J / cm. ２ The laser was scanned and irradiated in the same manner as above, except that the laser was changed to (high pulse energy) and the photopeeling property was evaluated in the same manner. Furthermore, the measurement samples prepared in the same manner were scanned and irradiated with a green laser irradiator (manufactured by ESI, "Lode Stone") at a wavelength of 515 nm and a pulse energy density of 1.3 J / cm. ２The obtained measurement sample was scanned and irradiated with a laser beam of 3.0 J / cm (low pulse energy) from the glass plate side. After irradiation, the photo-peeling property was evaluated by rating the sample as "○" if peeling was possible at the interface between the non-metallic layer and the metallic layer, and rating it as "×" if peeling was not possible. For samples that were rated as "×", the pulse energy density was increased to 3.0 J / cm. ２ The laser was scanned and irradiated in the same manner, except that the laser was changed to (high pulse energy), and photodetachment evaluation was performed. Note that even if all the evaluation results were "x," based on the above-mentioned evaluation results, it can be used without any practical problems. Furthermore, even if the evaluation result was "○" at low pulse energy, high pulse energy may damage the metal layer. Even if the evaluation result was "×" at low pulse energy, if the evaluation result was "○" at high pulse energy, it can be used without any practical problems and has excellent photodetachment properties. Furthermore, even if the evaluation result was "×" at both pulse energies at a wavelength of 355 nm, if the evaluation result was "○" at either pulse energy at a wavelength of 515 nm, it can be used without any practical problems and has excellent photodetachment properties.

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[0241] According to the present invention, it is possible to provide a method for manufacturing a semiconductor device that can suppress a decrease in yield during a rewiring process, etc., and improve the yield in the manufacture of semiconductor devices, etc. Also, according to the present invention, it is possible to provide an adhesive sheet for manufacturing a semiconductor device that can suppress a decrease in yield during a rewiring process, etc. Furthermore, according to the present invention, it is possible to provide a wound body in which the adhesive sheet for manufacturing a semiconductor device is wound.

Claims

1. A method for manufacturing a semiconductor device, comprising the following first, second, and third steps: First step: a step of laminating an adhesive sheet having a resin-containing adhesive layer and a metal layer on a support substrate; Second step: a step of forming a semiconductor rewiring layer on the metal layer; and Third step: a step of removing the support substrate and the adhesive layer.

2. A method for manufacturing a semiconductor device according to claim 1, wherein in said third step, at least the supporting substrate is irradiated with light.

3. The method for manufacturing a semiconductor device according to claim 2, wherein said light is laser light.

4. A method for manufacturing a semiconductor device according to claim 1, 2 or 3, wherein the metal layer comprises a layer made of copper.

5. A method for manufacturing a semiconductor device according to claim 1, 2, 3 or 4, wherein the metal layer does not have a layer made of titanium or has a layer made of titanium, and when the metal layer has a layer made of titanium, the thickness of the layer made of titanium is 1.0 μm or less.

6. The method for manufacturing a semiconductor device according to claim 1, 2, 3, 4 or 5, wherein the adhesive sheet has the metal layer on the outermost surface.

7. A method for manufacturing a semiconductor device according to claim 1, 2, 3, 4, 5 or 6, wherein the metal layer includes at least one layer selected from the group consisting of a vapor deposition layer, a sputtering layer and an ion plating layer.

8. An adhesive sheet for use in the production of semiconductor devices, comprising an adhesive layer containing a resin and a metal layer.

9. The adhesive sheet for producing semiconductor device according to claim 8, wherein the resin comprises at least one selected from the group consisting of (meth)acrylic copolymers and resins having an imide skeleton as a repeating unit in the main chain.

10. An adhesive sheet for use in the production of semiconductor devices according to claim 8 or 9, wherein the adhesive layer has an ultraviolet transmittance of 5% or less at a wavelength of 355 nm.

11. The adhesive sheet for producing semiconductor devices according to claim 8 or 9, wherein the adhesive layer has an ultraviolet transmittance of 50% or more at a wavelength of 355 nm.

12. The adhesive sheet for producing semiconductor device according to claim 8, 9, 10 or 11, wherein the metal layer is used as a metal seed layer.

13. An adhesive sheet for use in the production of semiconductor device according to claim 8, 9, 10, 11 or 12, wherein the metal layer comprises a layer made of copper.

14. The adhesive sheet for use in the production of semiconductor device according to claim 13, wherein the thickness of said layer made of copper is 1.0 μm or less.

15. An adhesive sheet for semiconductor device production according to claim 8, 9, 10, 11, 12, 13 or 14, wherein the metal layer does not have a layer made of titanium or has a layer made of titanium, and when the metal layer has a layer made of titanium, the thickness of the layer made of titanium is 1.0 μm or less.

16. The adhesive sheet for producing semiconductor device according to claim 8, 9, 10, 11, 12, 13, 14 or 15, which has the metal layer on the outermost surface.

17. An adhesive sheet for use in the production of semiconductor device according to claim 8, 9, 10, 11, 12, 13, 14, 15 or 16, wherein the metal layer comprises at least one layer selected from the group consisting of a vapor deposition layer, a sputtering layer and an ion plating layer.

18. The adhesive sheet for producing semiconductor devices according to claim 8, 9, 10, 11, 12, 13, 14, 15, 16 or 17, wherein the adhesive layer and the metal layer are directly laminated together.

19. The adhesive sheet for producing semiconductor device according to claim 8, 9, 10, 11, 12, 13, 14, 15, 16 or 17, which comprises the adhesive layer, the substrate and the metal layer in this order.

20. The adhesive sheet for use in the production of semiconductor device according to claim 19, wherein the substrate comprises at least one film selected from the group consisting of a PET film, a PEN film, and a PEEK film.

21. An adhesive sheet for use in the production of semiconductor devices according to claim 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, comprising a non-metallic layer and the metal layer, the metal layer being laminated on one side of the non-metallic layer, the non-metallic layer including the adhesive layer, and the non-metallic layer having a light transmittance of 5% or more at a wavelength of 500 nm.

22. An adhesive sheet for use in the production of semiconductor device according to claim 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 or 21, comprising a non-metallic layer and the metal layer, the metal layer being laminated on one side of the non-metallic layer, the non-metallic layer comprising the adhesive layer, the adhesive layer comprising a base polymer, the base polymer comprising at least one selected from the group consisting of (meth)acrylic copolymers and resins having an imide skeleton in the main chain repeating unit, and the adhesive layer does not contain a black pigment or contains a black pigment in an amount of more than 0 mass % and not more than 1 mass %.

23. The adhesive sheet for use in the production of semiconductor device according to claim 21 or 22, wherein the non-metallic layer has a light transmittance of 5% or more for a wavelength of 355 nm.

24. The adhesive sheet for use in the production of semiconductor device according to claim 21, 22 or 23, wherein the non-metallic layer has a thickness of 1 μm or more and 200 μm or less.

25. The adhesive sheet for semiconductor device production according to claim 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23 or 24, which is used as a photo-peeling adhesive sheet.

26. The adhesive sheet for semiconductor device production according to claim 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25, which is used as a laser peelable adhesive sheet.

27. The adhesive sheet for semiconductor device production according to claim 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25 or 26, which is used to form a semiconductor rewiring layer.

28. A rolled body formed by rolling up the adhesive sheet for semiconductor device production according to claim 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26 or 27.

29. A method for manufacturing a semiconductor device, comprising: a step (i) of attaching an adhesive sheet to a support substrate; and a step (ii) of irradiating the support substrate with the attached adhesive sheet with light of a wavelength of λ nm to peel off the adhesive sheet, wherein the adhesive sheet has a non-metallic layer and a metallic layer, and the metallic layer is laminated on one side of the non-metallic layer, wherein in step (i), the non-metallic layer is attached so as to be in contact with the support substrate, and in step (ii), the light of the wavelength λ nm satisfies a light transmittance of 5% or more for the non-metallic layer.

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