laminate

Abstract

Provided is a laminate in which a support and a device layer are bonded to each other through an adhesive layer, in which the amount of warpage is small, deformation due to an external force is suppressed, and cleaning removability of the adhesive layer is good.SOLUTION: A laminate 100 in which a support 12, a first adhesive layer 3A, a second adhesive layer 3B, and a device layer 45 are laminated in this order, in which the first adhesive layer 3A is a layer formed of a first material having a modulus of elasticity of 0. 1MPa or less under a temperature condition when the support 12 and the device layer 45 are bonded to each other, and the second adhesive layer 3B is a layer formed of a second material having a modulus of elasticity of 20MPa or more at 260 °C.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a laminate in which a support, a first adhesive layer, a second adhesive layer, and a device layer are laminated in this order. [Background technology]

[0002] Semiconductor packaging technology not only protects IC chips from external shocks, but also allows for versatile semiconductor products to be created by using different chip placement methods and various wiring processing methods. One example of semiconductor packaging technology is fan-out technology, which is being developed as a method to achieve higher integration, thinner, and smaller semiconductor packages, for example, through its application to fan-out panel level packages (PLPs), which package semiconductor elements arranged on a panel.

[0003] In order to miniaturize semiconductor packages, it is important to reduce the thickness of the substrate in which the device is incorporated. However, reducing the thickness of the substrate reduces its strength, making the substrate more susceptible to damage during semiconductor package manufacturing. To address this issue, a known technique involves temporarily bonding the substrate to a support using an adhesive to create a laminate, processing the substrate, and then separating the substrate from the support. When bonding a substrate and a support, adhesive compositions containing a polymer having a cycloolefin structure have conventionally been widely used as temporary bonding agents because of their excellent light transmittance. Patent Document 1 discloses an adhesive composition containing a polymer having a cycloolefin structure to which an alkoxysilyl group is bonded. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 2021-070766 Summary of the Invention [Problem to be solved by the invention]

[0005] In semiconductor package manufacturing, for example, a thermal process called TCB (Thermal Compression Bonding) is used to bond a substrate (device layer) and a support via an adhesive. In this thermal process, the device layer is aligned and mounted on the support, and high heat and pressure are simultaneously applied to melt the solder and press it against the terminals of the support, thereby bonding the device layer and the support via the adhesive layer. However, when using conventional laminates, there is a problem that the device layer warps after the thermal process. Furthermore, after the support is separated from the device layer, the adhesive layer remaining on the device layer may not be sufficiently removable by washing.

[0006] The present invention has been made in view of the above circumstances, and has an object to provide a laminate in which a support and a device layer are bonded together via an adhesive layer, which has a small amount of warping, is suppressed in deformation due to external forces, and has an adhesive layer that is easily removable by washing. [Means for solving the problem]

[0007] In order to solve the above problems, the present invention employs the following configuration. That is, one aspect of the present invention is a laminate comprising a support, a first adhesive layer, a second adhesive layer, and a device layer stacked in this order, wherein the first adhesive layer is a layer formed from a first material having an elastic modulus of 0.1 MPa or less under the temperature conditions when the support and the device layer are bonded together, and the second adhesive layer is a layer formed from a second material containing a thermoplastic resin and having an elastic modulus of 20 MPa or more at 260°C. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a laminate in which a support and a device layer are bonded together via an adhesive layer, which has a small amount of warping, is suppressed in deformation due to external forces, and has an adhesive layer that is easily removable by washing. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is a cross-sectional view showing one embodiment of a laminate. [Figure 2A] FIG. 1 is a schematic diagram illustrating a state when a conventional laminate is used in a TCB process. [Figure 2B] 1A and 1B are schematic diagrams illustrating the state when the laminate of this embodiment is used in a TCB process. [Figure 3] FIG. 10 is a cross-sectional view showing another embodiment of the laminate. [Figure 4A] FIG. 2 is a schematic diagram showing a state in which light is irradiated onto the laminate from the support side. [Figure 4B] FIG. 2 is a schematic diagram showing a state in which the support base is separated from the laminate. [Figure 4C] FIG. 2 is a schematic diagram showing a state in which the first adhesive layer, the second adhesive layer, and the separation layer have been washed away from the device layer. DETAILED DESCRIPTION OF THE INVENTION

[0010] In this specification and claims, the term "aliphatic" is defined as a relative concept to aromatic, and refers to groups, compounds, etc. that do not have aromaticity. Unless otherwise specified, the term "alkyl group" includes linear, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to alkyl groups in alkoxy groups. Unless otherwise specified, the term "alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups. A "halogenated alkyl group" is an alkyl group in which some or all of the hydrogen atoms have been substituted with halogen atoms, and examples of such halogen atoms include fluorine, chlorine, bromine, and iodine atoms. The term "fluorinated alkyl group" or "fluorinated alkylene group" refers to an alkyl group or alkylene group in which some or all of the hydrogen atoms have been substituted with fluorine atoms. The term "structural unit" refers to a monomer unit that constitutes a polymeric compound (resin, polymer, copolymer). The phrases "may have a substituent" or "may have a substituent" include both cases where a hydrogen atom (-H) is replaced with a monovalent group and cases where a methylene group (-CH-) is replaced with a divalent group. The term "exposure" is a general concept that includes irradiation with radiation.

[0011] The term "structural unit derived from styrene" refers to a structural unit formed by cleavage of the ethylenic double bond of styrene. The term "structural unit derived from a styrene derivative" refers to a structural unit formed by cleavage of the ethylenic double bond of a styrene derivative. The term "styrene derivative" refers to a styrene in which the hydrogen atom at the α-position is substituted with another substituent such as an alkyl group or a halogenated alkyl group, as well as derivatives thereof. Examples of such derivatives include styrene in which the hydrogen atom at the α-position may be substituted with a substituent, but the hydrogen atom of the hydroxyl group is substituted with an organic group; and styrene in which the hydrogen atom at the α-position may be substituted with a substituent, but a substituent other than a hydroxyl group is bonded to the benzene ring. Unless otherwise specified, the α-position (the carbon atom at the α-position) refers to the carbon atom to which the benzene ring is bonded. Examples of the substituent that substitutes the hydrogen atom at the α-position of styrene include the same as those exemplified as the substituent at the α-position in the above-mentioned α-substituted acrylic ester.

[0012] The alkyl group as the substituent at the α-position is preferably a linear or branched alkyl group, and specific examples thereof include alkyl groups having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc.). Specific examples of the halogenated alkyl group as a substituent at the α-position include groups in which some or all of the hydrogen atoms of the above-mentioned "alkyl group as a substituent at the α-position" have been substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being particularly preferred. Specific examples of the hydroxyalkyl group as the substituent at the α-position include groups in which some or all of the hydrogen atoms of the above-mentioned "alkyl group as the substituent at the α-position" have been substituted with hydroxyl groups. The number of hydroxyl groups in the hydroxyalkyl group is preferably 1 to 5, and most preferably 1.

[0013] The molecular weight of the resin component is determined by polystyrene-equivalent weight average molecular weight (Mw) determined by GPC (gel permeation chromatography). The glass transition point (Tg) of the resin component is a value measured by a dynamic mechanical analysis (DMA) device.

[0014] (Laminate) A laminate according to one embodiment of the present invention is a laminate in which a support and a device layer are bonded together via an adhesive layer, and in which the support, a first adhesive layer, a second adhesive layer, and the device layer are laminated in this order. The first adhesive layer is a layer formed from a first material that exhibits an elastic modulus of 0.1 MPa or less under the temperature conditions when the support and the device layer are bonded together. The second adhesive layer is a layer formed from a second material that contains a thermoplastic resin and has an elastic modulus at 260°C of 20 MPa or more.

[0015] FIG. 1 shows one embodiment of the laminate. The laminate 100 shown in FIG. 1 includes a support 12, a first adhesive layer 3A, a second adhesive layer 3B, and a device layer 45 laminated in this order. The support 12 includes a support base 1 and a separation layer 2. The separation layer 2 and the first adhesive layer 3A are provided adjacent to each other. The device layer 45 includes a substrate 4 and an encapsulant layer 5. The substrate 4 is provided on the second adhesive layer 3B and is encapsulated between the second adhesive layer 3B and the encapsulant layer 5.

[0016] <Support> In the laminate 100 shown in FIG. 1, the support 12 includes a support base 1 and a separation layer 2 provided on the support base 1.

[0017] ≪Supporting base≫ The supporting base has the property of transmitting light. The supporting base is a member that supports the substrate, and is bonded to the substrate via a first adhesive layer and a second adhesive layer. Therefore, the supporting base preferably has the strength required to prevent damage or deformation of the substrate during thinning of the encapsulant, transportation of the substrate, mounting on the substrate, etc. Furthermore, the supporting base preferably transmits light of a wavelength that can alter the separation layer. The material of the support base may be, for example, glass, silicon, acrylic resin, etc. The shape of the support base may be, for example, rectangular, circular, etc., but is not limited to these. Furthermore, for the purpose of achieving higher density integration and improving production efficiency, the support base may be a circular support base with an enlarged size, or a large panel with a rectangular shape in plan view.

[0018] ≪Separation layer≫ The separation layer is adjacent to the first adhesive layer and is altered by irradiation with light, thereby enabling the support base to be separated from the substrate bonded to the support. This separation layer can be formed using the "separation layer-forming composition" described below, for example, by firing the components contained in the separation layer-forming composition or by chemical vapor deposition (CVD). This separation layer is suitably altered by absorbing light irradiated through the support substrate. It is preferable that the separation layer is formed only from a material that absorbs light, but it may also be a layer that contains a material that does not have a structure that absorbs light, as long as the essential property of being altered by irradiation with light is not impaired.

[0019] The term "alteration" of a separation layer refers to a phenomenon in which the separation layer is in a state where it can be destroyed by external force or where the adhesive strength between the separation layer and a layer in contact with it is reduced. The separation layer becomes brittle by absorbing light and loses the strength or adhesiveness it had before being irradiated with light. Such alteration of the separation layer occurs due to decomposition, changes in configuration, dissociation of functional groups, etc. caused by the energy of the absorbed light.

[0020] The thickness of the separation layer is preferably, for example, in the range of 0.05 μm or more and 50 μm or less, and more preferably in the range of 0.3 μm or more and 1 μm or less. If the thickness of the separation layer is within the range of 0.05 μm or more and 50 μm or less, the desired alteration can be caused in the separation layer by short-term light irradiation and low-energy light irradiation. Furthermore, from the viewpoint of productivity, it is particularly preferable that the thickness of the separation layer is within the range of 1 μm or less.

[0021] It is preferable that the surface of the separation layer that comes into contact with the first adhesive layer is flat (no irregularities are formed), which makes it easy to form the first adhesive layer and to uniformly attach the support base and substrate.

[0022] <First adhesive layer> The first adhesive layer is an adhesive layer adjacent to the support, and is a layer formed from a first material exhibiting the following properties. In the laminate 100, the first adhesive layer 3A is provided adjacent to the separation layer 2 constituting the support 12. The first adhesive layer 3A is preferably removable with a cleaning solution containing an organic solvent.

[0023] The thickness of the first adhesive layer is preferably, for example, in the range of 0.1 μm to 100 μm, more preferably in the range of 1 μm to 50 μm, and even more preferably in the range of 10 μm to 40 μm. When the thickness of the first adhesive layer is within the above-mentioned preferred range, the support and the device layer can be bonded together more satisfactorily.

[0024] <Ingredient 1> The first material is a material that exhibits an elastic modulus of 0.1 MPa or less under the temperature conditions when the support and the device layer are attached to each other (hereinafter also referred to as "attachment temperature"). The first material may be an adhesive composition containing a resin component and other components (hereinafter also referred to as "adhesive composition (1)"). The bonding temperature is set appropriately depending on, for example, the resin component contained in the adhesive composition (1).

[0025] The first material has an elastic modulus of 0.1 MPa or less at the application temperature, preferably 0.075 MPa or less, and more preferably 0.05 MPa or less. If the modulus of elasticity at the attachment temperature is equal to or less than the upper limit of the range, the adhesive layer formed from the first material will be less susceptible to deformation due to external forces. The lower limit of the elastic modulus at the application temperature is substantially 0.001 MPa or more, and may be 0.002 MPa or more.

[0026] Method for measuring modulus of elasticity at application temperature: The elastic modulus of the first material at the application temperature is measured as follows. An adhesive layer with a thickness of 50 μm is formed on a silicon wafer. A test piece (film thickness 50 μm, width 5 mm, length 40 mm) of the adhesive layer is cut out, and the tensile modulus is measured using a dynamic viscoelasticity measuring device at a frequency of 1 Hz in the range of 50 to 300° C. The tensile modulus under the temperature conditions when the support and the device layer are bonded together is defined as the modulus at the bonding temperature.

[0027] The adhesive composition (1) exemplified as the first material may be an adhesive composition containing a thermoplastic resin, or may be an adhesive composition containing a thermosetting resin. As the adhesive composition (1), various adhesive compositions known in the art, such as acrylic, novolac, naphthoquinone, hydrocarbon, polyimide, elastomer, polysulfone, and urethane adhesive compositions, can be used.

[0028] The adhesive composition (1) may contain, for example, a thermoplastic resin, a diluent, and other components such as additives. Preferred examples of the thermoplastic resin include hydrocarbon resins, acrylic-styrene resins, maleimide resins, elastomers, polysulfone resins, and combinations thereof.

[0029] The adhesive composition (1) may contain, for example, a thermosetting resin, a crosslinking agent component, a polymerization initiator, and other components such as additives. For example, a urethane resin or the like can be preferably used as the thermosetting resin.

[0030] An adhesive composition containing a thermoplastic resin (hereinafter also referred to as “adhesive composition (11)”): Hydrocarbon resin The hydrocarbon resin has a hydrocarbon skeleton and is obtained by polymerizing a monomer composition. Examples of the hydrocarbon resin include, but are not limited to, a cycloolefin polymer (hereinafter sometimes referred to as "resin (A)") and at least one resin selected from the group consisting of a terpene resin, a rosin resin, and a petroleum resin (hereinafter sometimes referred to as "resin (B)").

[0031] Acrylic-styrene resin Examples of acrylic-styrene resins include resins obtained by polymerizing styrene or a styrene derivative and a (meth)acrylic acid ester as monomers.

[0032] Examples of (meth)acrylic acid esters include (meth)acrylic acid alkyl esters having a chain structure, (meth)acrylic acid esters having an aliphatic ring, and (meth)acrylic acid esters having an aromatic ring. Examples of (meth)acrylic acid alkyl esters having a chain structure include acrylic long-chain alkyl esters having an alkyl group with 15 to 20 carbon atoms and acrylic alkyl esters having an alkyl group with 1 to 14 carbon atoms. Examples of acrylic long-chain alkyl esters include alkyl esters of acrylic acid or methacrylic acid in which the alkyl group is an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, an n-eicosyl group, or the like. The alkyl group may be branched.

[0033] Examples of acrylic alkyl esters having an alkyl group of 1 to 14 carbon atoms include known acrylic alkyl esters used in existing acrylic adhesives, such as alkyl esters of acrylic acid or methacrylic acid in which the alkyl group is a methyl group, ethyl group, propyl group, butyl group, 2-ethylhexyl group, isooctyl group, isononyl group, isodecyl group, dodecyl group, lauryl group, tridecyl group, or the like.

[0034] Examples of the (meth)acrylic acid ester having an aliphatic ring include cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, 1-adamantyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, tetracyclododecanyl (meth)acrylate, and dicyclopentanyl (meth)acrylate, with isobornyl methacrylate and dicyclopentanyl (meth)acrylate being more preferred.

[0035] The (meth)acrylic acid ester having an aromatic ring is not particularly limited, but examples of the aromatic ring include a phenyl group, a benzyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a phenoxymethyl group, and a phenoxyethyl group. The aromatic ring may have a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, phenoxyethyl acrylate is preferred.

[0036] Maleimide resin Examples of maleimide resins include those containing, as a monomer, an alkyl group such as N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, N-isobutylmaleimide, N-sec-butylmaleimide, N-tert-butylmaleimide, Nn-pentylmaleimide, Nn-hexylmaleimide, Nn-heptylmaleimide, Nn-octylmaleimide, N-laurylmaleimide, and N-stearylmaleimide. Examples of the resins include those obtained by polymerizing maleimides having an aliphatic hydrocarbon group such as N-cyclopropylmaleimide, N-cyclobutylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide, and N-cyclooctylmaleimide; and aromatic maleimides having an aryl group such as N-phenylmaleimide, Nm-methylphenylmaleimide, No-methylphenylmaleimide, and Np-methylphenylmaleimide.

[0037] Elastomer The elastomer preferably contains a styrene unit as a structural unit of the main chain, and the "styrene unit" may have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxyalkyl group having 1 to 5 carbon atoms, an acetoxy group, and a carboxyl group. It is more preferable that the content of the styrene unit is in the range of 14% by mass or more and 50% by mass or less. Furthermore, it is preferable that the elastomer has a weight average molecular weight in the range of 10,000 to 200,000.

[0038] When the styrene unit content is within the range of 14% by mass or more and 50% by mass or less and the weight-average molecular weight of the elastomer is within the range of 10,000 to 200,000, the adhesive layer is easily dissolved in the hydrocarbon solvent described below, allowing for easier and faster removal of the adhesive layer. Furthermore, when the styrene unit content and weight-average molecular weight are within the above ranges, the adhesive layer exhibits excellent resistance to resist solvents (e.g., PGMEA, PGME, etc.), acids (hydrofluoric acid, etc.), and alkalis (TMAH, etc.) used in resist lithography.

[0039] The elastomer may further contain the above-mentioned (meth)acrylic acid ester. The content of styrene units is more preferably 17% by mass or more, and more preferably 45% by mass or less. The weight average molecular weight of the elastomer is preferably in the range of 10,000 to 200,000, more preferably in the range of 20,000 to 150,000, and even more preferably in the range of 20,000 to 100,000.

[0040] As the elastomer, various elastomers can be used as long as the content of styrene units is in the range of 14% by mass or more and 50% by mass or less and the weight average molecular weight of the elastomer is in the range of 10,000 to 200,000. For example, polystyrene-poly(ethylene / propylene) block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene-butylene-styrene block copolymer (SBBS), and hydrogenated products thereof, styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (styrene-isoprene-styrene block copolymer) (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), and styrene block copolymers containing styrene blocks are available. Examples include reactive crosslinked styrene-ethylene-ethylene-propylene-styrene block copolymers (Septon V9461 (manufactured by Kuraray Co., Ltd.), Septon V9475 (manufactured by Kuraray Co., Ltd.)), reactive crosslinked styrene-ethylene-butylene-styrene block copolymers in which the styrene block is crosslinked (Septon V9827 (manufactured by Kuraray Co., Ltd.) having a reactive polystyrene-based hard block), and polystyrene-poly(ethylene-ethylene / propylene) block-polystyrene block copolymers (SEEPS-OH: terminal hydroxyl group modified), and those in which the styrene unit content and weight average molecular weight of the elastomer are within the above-mentioned ranges can be used.

[0041] Among elastomers, hydrogenated elastomers are more preferred. Hydrogenated elastomers have improved thermal stability and are less susceptible to deterioration such as decomposition and polymerization. They are also more preferred from the viewpoints of solubility in hydrocarbon solvents and resistance to resist solvents.

[0042] Among elastomers, those which are block polymers with styrene at both ends are more preferred, because by blocking styrene, which has high thermal stability, at both ends, higher heat resistance is exhibited.

[0043] More specifically, the elastomer is preferably a hydrogenated block copolymer of styrene and a conjugated diene. This elastomer has improved thermal stability and is less susceptible to degradation such as decomposition and polymerization. Furthermore, blocking both ends with highly thermally stable styrene provides higher heat resistance. Furthermore, this is more preferable from the viewpoints of solubility in hydrocarbon solvents and resistance to resist solvents.

[0044] Examples of commercially available adhesive compositions that can be used as adhesive compositions containing an elastomer include "TZNR (trade name)" manufactured by Tokyo Ohka Kogyo Co., Ltd. Furthermore, a plurality of types of elastomers may be mixed, that is, the adhesive composition may contain a plurality of types of elastomers.

[0045] Polysulfone resin The adhesive composition (11) may contain a polysulfone resin. By forming the first adhesive layer from a polysulfone resin, even if a high-temperature treatment is performed in the sealing body formation step, the first adhesive layer can be dissolved in a subsequent step, and the support base can be separated from the sealing body. If the first adhesive layer contains a polysulfone resin, a high-temperature process in which treatment is performed at a high temperature of, for example, 300°C or higher can be used in the sealing body formation step. The weight-average molecular weight (Mw) of the polysulfone resin is preferably in the range of 30,000 or more and 70,000 or less, and more preferably in the range of 30,000 or more and 50,000 or less. If the weight-average molecular weight (Mw) of the polysulfone resin is in the range of 30,000 or more, an adhesive composition that can be used at high temperatures, for example, 300°C or more, can be obtained. Furthermore, if the weight-average molecular weight (Mw) of the polysulfone resin is in the range of 70,000 or less, it can be suitably dissolved in a solvent. In other words, an adhesive composition that can be suitably removed by a solvent can be obtained.

[0046] The thermoplastic resins may be used alone or in combination of two or more. The content of the thermoplastic resin in the adhesive composition (11) is not particularly limited as long as it is a concentration that allows application to a support or the like, and is preferably 10 to 50 mass %, more preferably 15 to 40 mass %, and even more preferably 15 to 30 mass %, relative to the total amount (100 mass %) of the adhesive composition (11).

[0047] Furthermore, the content of the thermoplastic resin in the solid content (total amount of blended components excluding the solvent component) in the adhesive composition (11) is preferably 50% by mass or more, and may be 50 to 100% by mass, or 60 to 100% by mass, relative to the total amount of the solid content (100% by mass).

[0048] Dilution solvent Examples of dilution solvents include linear hydrocarbons such as hexane, heptane, octane, nonane, isononane, methyloctane, decane, undecane, dodecane, and tridecane; branched hydrocarbons having 4 to 15 carbon atoms; cyclic hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene, and tetrahydronaphthalene; p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpine, 1,8-terpine, bornane, norbornane, pinane, thujane, carane, longifolene, and geraniol. Terpene solvents such as ethanol, nerol, linalool, citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, terpinen-4-ol, dihydroterpinyl acetate, 1,4-cineole, 1,8-cineole, borneol, carvone, ionone, thujone, camphor, d-limonene, l-limonene, and dipentene; lactones such as γ-butyrolactone; acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n ketones such as 2-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate; derivatives of polyhydric alcohols such as compounds having an ether bond such as monoalkyl ethers, monomethyl ethers, monoethyl ethers, monopropyl ethers, and monobutyl ethers of the above polyhydric alcohols or compounds having an ester bond, or monophenyl ethers (among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred); cyclic ethers such as dioxane; and esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate;Examples of aromatic organic solvents include anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, and butyl phenyl ether;

[0049] Other ingredients The adhesive composition (11) may further contain other compatible substances to the extent that the essential properties are not impaired. For example, various commonly used additives such as additional resins for improving the performance of the adhesive, curable monomers, polymerization inhibitors, polymerization initiators, plasticizers, adhesion aids, stabilizers, colorants, and surfactants can be further used.

[0050] An adhesive composition containing a thermosetting resin (hereinafter also referred to as “adhesive composition (12)”): Urethane resin Suitable examples of the urethane resin include urethane resins containing polymerizable carbon-carbon double bonds (hereinafter also referred to as "component (P1)"). The component (P1) can polymerize and harden via the polymerizable carbon-carbon double bond to form a second adhesive layer. This allows for temporary bonding between a semiconductor substrate or an electronic device and a support. Furthermore, the urethane bond in the component (P1) is decomposable by acid or alkali. Therefore, the second adhesive layer can be easily removed with a treatment liquid containing acid or alkali. Components that fall under the crosslinker component (component (M)) described below are excluded from the component (P1).

[0051] The polymerizable carbon-carbon double bond contained in the component (P1) is not particularly limited, but is preferably radically polymerizable. Examples of the polymerizable carbon-carbon double bond include a methacryloyl group and an acryloyl group. The polymerizable carbon-carbon double bond contained in the component (P1) may be one type or two or more types. The equivalent weight of the polymerizable carbon-carbon double bond contained in component (P1) is preferably 200 to 2000 g / eq. or more, more preferably 300 to 1500 g / eq. or more, even more preferably 400 to 1200 g / eq. or more, and particularly preferably 500 to 1000 g / eq. When the equivalent weight of the polymerizable carbon-carbon double bond is at least the lower limit of the above-mentioned preferred range, the elastic modulus, heat resistance, etc. of the second adhesive layer are further improved. When the equivalent weight of the polymerizable carbon-carbon double bond is at most the upper limit of the above-mentioned preferred range, the second adhesive layer does not become too hard and has good washability. The above-mentioned equivalent weight is the molecular weight of the urethane resin per equivalent of the polymerizable carbon-carbon double bond.

[0052] The weight average molecular weight (Mw) of the component (P1) is preferably from 5,000 to 100,000, more preferably from 1,000 to 50,000, even more preferably from 12,000 to 30,000, and particularly preferably from 13,000 to 25,000.

[0053] The component (P1) can be synthesized by a polymerization addition reaction between a polyisocyanate compound (hereinafter also referred to as "component (I)") and a polyol (hereinafter also referred to as "component (O)"). At least one of the components (I) and (O) preferably contains a polymerizable carbon-carbon double bond.

[0054] Polyisocyanate compound: component (I) In this specification, the term "polyisocyanate compound" refers to a compound having two or more isocyanate groups (-N=C=O) (polyisocyanate) or a compound having two or more blocked isocyanate groups (blocked polyisocyanate). The polyisocyanate is not particularly limited, and any polyisocyanate generally used in the production of urethane resins can be used without any particular limitation. A blocked polyisocyanate is a compound in which the isocyanate groups of a polyisocyanate are blocked and inactivated by reaction with a blocking agent. The blocked polyisocyanate used as component (I) is preferably one in which the isocyanate groups are blocked with a thermally dissociable blocking agent. Examples of the thermally dissociable blocking agent include oximes, diketones, phenols, and caprolactams. In a blocked polyisocyanate with a thermally dissociable blocking agent, the isocyanate groups are inactive at room temperature, and upon heating, the thermally dissociable blocking agent dissociates, regenerating the isocyanate groups.

[0055] Specific examples of polyisocyanates include aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate; alicyclic diisocyanates such as dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, and dicyclohexylmethane-4,4'-diisocyanate; and aromatic diisocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, and naphthylene diisocyanate; as well as their biuret derivatives, isocyanurate derivatives, and trimethylolpropane adducts. One type of polyisocyanate may be used alone, or two or more types may be used in combination.

[0056] Commercially available polyisocyanates may be used. Examples of commercially available polyisocyanates include Duranate (registered trademark) 24A-100, Duranate 22A-75P, Duranate TPA-100, Duranate TKA-100, Duranate P301-75E, Duranate 21S-75E, Duranate MFA-75B, Duranate MHG-80B, Duranate TUL-100, and Duranate 21S-75E. Duranate TLA-100, Duranate TSA-100, Duranate TSS-100, Duranate TSE100, Duranate E402-80B, Duranate E405-70B, Duranate AS700-100, Duranate D101, Duranate D201, and Duranate A201H (all trade names, manufactured by Asahi Kasei Chemicals Corporation). These products may be used alone or in combination of two or more.

[0057] Examples of blocked isocyanates include compounds in which the isocyanate groups of the above-mentioned polyisocyanates are protected by reaction with a blocking agent. The blocking agent is not particularly limited as long as it is a thermally dissociable blocking agent, i.e., a compound that adds to an isocyanate group, is stable at room temperature, but is liberated to generate an isocyanate group when heated to a temperature equal to or higher than the dissociation temperature, and known blocking agents can be used without particular limitation. Specific examples of blocking agents include lactam compounds such as γ-butyrolactam, ε-caprolactam, γ-valerolactam, and propiolactam; oxime compounds such as methyl ethyl ketoxime, methyl isoamyl ketoxime, methyl isobutyl ketoxime, formamide oxime, acetamide oxime, acetoxime, diacetyl monooxime, benzophenone oxime, and cyclohexanone oxime; monocyclic phenol compounds such as phenol, cresol, catechol, and nitrophenol; polycyclic phenol compounds such as 1-naphthol; alcohol compounds such as methyl alcohol, ethyl alcohol, isopropyl alcohol, tert-butyl alcohol, trimethylolpropane, and 2-ethylhexyl alcohol; ether compounds such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether; and active methylene compounds such as malonic acid alkyl esters, malonic acid dialkyl esters, acetoacetic acid alkyl esters, and acetylacetone. The blocking agents may be used alone or in combination.

[0058] Blocked polyisocyanates can be produced by reacting a polyisocyanate with a blocking agent. The reaction between the polyisocyanate and the blocking agent is carried out, for example, in a solvent that does not contain active hydrogen (1,4-dioxane, cellosolve acetate, etc.) under heating at about 50 to 100°C, and if necessary, in the presence of a blocking catalyst. The proportion of polyisocyanate to blocking agent used is not particularly limited, but the equivalent ratio of isocyanate groups in the polyisocyanate to the blocking agent is preferably 0.95:1.0 to 1.1:1.0, and more preferably 1:1.05 to 1.15. Known blocking catalysts can be used, and examples thereof include metal alcoholates such as sodium methylate, sodium ethylate, sodium phenolate, and potassium methylate; hydroxides of tetraalkylammonium such as tetramethylammonium, tetraethylammonium, and tetrabutylammonium; organic weak acid salts thereof such as acetates, octylates, myristates, and benzoates; and alkali metal salts of alkylcarboxylic acids such as acetic acid, caproic acid, octylate, and myristic acid. The blocking catalyst may be used alone or in combination of two or more kinds.

[0059] Commercially available blocked polyisocyanates may be used, such as Duranate MF-K60B, Duranate SBB-70P, Duranate SBN-70D, Duranate MF-B60B, Duranate 17B-60P, Duranate TPA-B80E, and Duranate E402-B80B (all trade names, manufactured by Asahi Kasei Corporation).

[0060] Component (I) is preferably a blocked polyisocyanate in which the isocyanate groups are blocked with a thermally dissociable blocking agent. The component (I) may be used alone or in combination of two or more. For example, the component (I) may be a mixture of an aliphatic diisocyanate and an aromatic diisocyanate. The aliphatic diisocyanate is preferably hydrogenated xylene diisocyanate. The aromatic diisocyanate is preferably 4,4-diphenylmethane diisocyanate.

[0061] Polyol: Component (O) The polyol (component (O)) is a compound having two or more hydroxy groups (-OH). There are no particular limitations on the polyol, and any polyol commonly used in the production of urethane resins can be used without particular limitations. Examples of the component (O) include a polyol containing a polymerizable carbon-carbon double bond (hereinafter also referred to as "component (O1)") and other polyols (hereinafter also referred to as "component (O2)").

[0062] Polyol containing a polymerizable carbon-carbon double bond (component (O1)) The component (O1) may be a polyol containing at least one selected from the group consisting of a methacryloyl group and an acryloyl group. The component (O1) may have one polymerizable carbon-carbon double bond or two or more polymerizable carbon-carbon double bonds.

[0063] Examples of the (O1) component include esters of trivalent or higher polyols with methacrylic acid, acrylic acid, or derivatives thereof. The trivalent or higher polyols are preferably trivalent or higher low-molecular-weight polyols. Examples of the trivalent or higher low-molecular-weight polyols include trivalent alcohols such as glycerin and trimethylolpropane; tetravalent alcohols such as tetramethylolmethane (pentaerythritol) and diglycerin; pentavalent alcohols such as xylitol; hexavalent alcohols such as sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, and dipentaerythritol; heptavalent alcohols such as perseitol; and octavalent alcohols such as sucrose.

[0064] Specific examples of the component (O1) include glycerin mono(meth)acrylate, diglycerin tri(meth)acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, diglycerin di(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, sorbitol mono(meth)acrylate, sorbitol di(meth)acrylate, sorbitol tri(meth)acrylate, and sorbitol tetra(meth)acrylate. The term "(meth)acrylate" is a concept that encompasses methacrylate and acrylate, and means either methacrylate or acrylate.

[0065] The component (O1) may be used alone or in combination of two or more types. Of these, the component (O1) is preferably a diol containing a methacryloyl group or an acryloyl group, and more preferably glycerin mono(meth)acrylate or pentaerythritol di(meth)acrylate.

[0066] Other polyols (O2 components) Component (O2) is a polyol other than the above-mentioned component (O1). Component (O2) is not particularly limited and may be an aliphatic polyol or an aromatic polyol. Component (O2) may be a low-molecular-weight polyol (e.g., molecular weight less than 500) or a high-molecular-weight polyol (e.g., molecular weight 500 or more).

[0067] Examples of low molecular weight polyols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, alkanediols having 7 to 22 carbon atoms, diethylene glycol, triethylene glycol, dipropylene glycol, 3-methyl-1,5-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, alkane-1,2-diols having 17 to 20 carbon atoms, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol. dihydric alcohols such as 1,4-cyclohexanediol, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, and bisphenol A; trihydric alcohols such as glycerin and trimethylolpropane; tetrahydric alcohols such as tetramethylolmethane (pentaerythritol) and diglycerin; pentahydric alcohols such as xylitol; hexahydric alcohols such as sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, and dipentaerythritol; heptahydric alcohols such as perseitol; and octahydric alcohols such as sucrose. Among these, the low molecular weight polyol is preferably a dihydric alcohol (diol).

[0068] Examples of polymer polyols include phenolic resins, resins containing a hydroxystyrene skeleton, polycarbonate polyols, polyester polyols, polyether polyols, polyether ester polyols, polyester amide polyols, acrylic polyols, polyhydroxy alkanes, polyurethane polyols, and vegetable oil-based polyols. The number average molecular weight of the high molecular weight polyol is preferably 500 to 100,000.

[0069] When a low molecular weight polyol is used as the component (O2), the ratio of the low molecular weight polyol to the component (O1) (low molecular weight polyol / component (O1) (mass ratio)) is preferably 0.01 to 0.1, more preferably 0.03 to 0.08.

[0070] [Phenol resin] The phenolic resin may be a novolac-type phenolic resin or a resol-type phenolic resin. The novolac-type phenolic resin can be obtained by addition-condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter referred to as "phenols") with an aldehyde in the presence of an acid catalyst. The resol-type phenolic resin can be obtained by addition-condensation of a phenol with an aldehyde in the presence of an alkali catalyst.

[0071] Examples of the phenols include phenol; cresols such as m-cresol, p-cresol, and o-cresol; xylenols such as 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, and 3,4-xylenol; alkylphenols such as m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-4-methylphenol, and 2-tert-butyl-5-methylphenol; p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, and m-ethoxyphenol. Examples of suitable alkoxyphenols include phenol, p-propoxyphenol, and m-propoxyphenol; isopropenylphenols such as o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, and 2-ethyl-4-isopropenylphenol; arylphenols such as phenylphenol; and polyhydroxyphenols such as 4,4'-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, pyrogallol, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, and 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane.

[0072] Examples of the aldehydes include formaldehyde, paraformaldehyde, trioxane, furfural, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, cinnamaldehyde, 4-isopropylbenzaldehyde, 4-isobutylbenzaldehyde, and 4-phenylbenzaldehyde.

[0073] The acid catalyst used in the addition condensation reaction is not particularly limited, and examples thereof include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, and acetic acid. The alkali catalyst used in the addition condensation reaction is not particularly limited, and examples thereof include sodium hydroxide, lithium hydroxide, potassium hydroxide, aqueous ammonia, triethylamine, sodium carbonate, and hexamethylenetetramine.

[0074] [Resin containing a hydroxystyrene skeleton] The resin containing a hydroxystyrene skeleton is not particularly limited as long as it has a structural unit derived from hydroxystyrene or a hydroxystyrene derivative. Specific examples of structural units derived from hydroxystyrene or a hydroxystyrene derivative include structural units represented by the following general formula (a10-1):

[0075] [ka] [In the formula, R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.] x1 is a single bond or a divalent linking group. x1 is (n ax1 +1)valent aromatic hydrocarbon group. ax1 is an integer between 1 and 3.

[0076] In the formula (a10-1), R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. The alkyl group of 1 to 5 carbon atoms for R is preferably a linear or branched alkyl group of 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The halogenated alkyl group of 1 to 5 carbon atoms for R is a group in which some or all of the hydrogen atoms of the alkyl group of 1 to 5 carbon atoms have been substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being particularly preferred. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and is most preferably a hydrogen atom or a methyl group from the viewpoint of industrial availability.

[0077] In the formula (a10-1), Ya x1 is a single bond or a divalent linking group. Ya x1 Preferred examples of the divalent linking group in the formula include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.

[0078] Optionally substituted divalent hydrocarbon group: Ya x1 When is a divalent hydrocarbon group which may have a substituent, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0079] Ya x1 Aliphatic hydrocarbon groups in The aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, and an aliphatic hydrocarbon group containing a ring in its structure.

[0080] Linear or branched aliphatic hydrocarbon groups The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred, and specific examples include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], and a pentamethylene group [-(CH2)5-]. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include alkyl alkylene groups such as alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0081] The linear or branched aliphatic hydrocarbon group may or may not have a substituent, such as a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, or a carbonyl group.

[0082] Aliphatic hydrocarbon groups containing rings in the structure Examples of the aliphatic hydrocarbon group containing a ring in its structure include a cyclic aliphatic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) which may contain a substituent containing a heteroatom in the ring structure, a group in which the cyclic aliphatic hydrocarbon group is bonded to the end of a straight-chain or branched-chain aliphatic hydrocarbon group, and a group in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group. Examples of the straight-chain or branched-chain aliphatic hydrocarbon group include the same as those described above. The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms. The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane, and specific examples thereof include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0083] The cyclic aliphatic hydrocarbon group may or may not have a substituent, such as an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, or a carbonyl group. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group. Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. Examples of the halogenated alkyl group as the substituent include groups in which some or all of the hydrogen atoms of the alkyl group have been substituted with the halogen atoms. In the cyclic aliphatic hydrocarbon group, some of the carbon atoms constituting the ring structure may be substituted with a substituent containing a heteroatom, and the heteroatom-containing substituent is preferably -O-, -C(=O)-O-, -S-, -S(=O)2-, or -S(=O)2-O-.

[0084] Ya x1 Aromatic hydrocarbon groups in The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, even more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. However, this number of carbon atoms does not include the number of carbon atoms in the substituents. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings. Specific examples of the aromatic hydrocarbon group include groups (arylene groups or heteroarylene groups) in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring or aromatic heterocycle; groups in which two hydrogen atoms have been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups in which one hydrogen atom of a group (aryl group or heteroaryl group) in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle has been substituted with an alkylene group (e.g., groups in which one hydrogen atom has been further removed from the aryl group in an arylalkyl group such as a benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, or 2-naphthylethyl group). The alkylene group bonded to the aryl group or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

[0085] The aromatic hydrocarbon group may have a hydrogen atom substituted with a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. Examples of the alkoxy group, halogen atom and halogenated alkyl group as the substituent include those exemplified as the substituent substituting the hydrogen atom of the cyclic aliphatic hydrocarbon group.

[0086] Divalent linking groups containing heteroatoms: Ya x1is a divalent linking group containing a hetero atom, preferred examples of the linking group include -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H may be substituted with a substituent such as an alkyl group or an acyl group), -S-, -S(=O)2-, -S(=O)2-O-, and groups represented by the general formula -Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -, -[Y 21 -C(=O)-O] m” -Y 22 -, -Y 21 -OC(=O)-Y 22 -or- Y 21 -S(=O)2-OY 22 -, wherein Y 21 and Y 22 are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m″ is an integer of 1 to 3. When the divalent linking group containing a hetero atom is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, or -NH-C(=NH)-, the H may be substituted with a substituent such as an alkyl group, an acyl group, etc. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 5 carbon atoms. General formula-Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -, -[Y 21 -C(=O)-O] m” -Y 22 -, -Y 21 -OC(=O)-Y 22 -or- Y 21 -S(=O)2-OY 22 -Medium, Y 21 and Y 22are each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same groups as those (divalent hydrocarbon groups which may have a substituent) listed above in the description of the divalent linking group. Y 21 As the alkyl group, a straight-chain aliphatic hydrocarbon group is preferred, a straight-chain alkylene group is more preferred, a straight-chain alkylene group having 1 to 5 carbon atoms is even more preferred, and a methylene group or ethylene group is particularly preferred. Y 22 is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. Formula − [Y 21 -C(=O)-O] m” -Y 22 In the group represented by -, m" is an integer of 1 to 3, preferably 1 or 2, and more preferably 1. That is, the group represented by the formula -[Y 21 -C(=O)-O] m” -Y 22 The group represented by - is a group represented by the formula -Y 21 -C(=O)-OY 22 Particularly preferred is a group represented by the formula -(CH2) a’ -C(=O)-O-(CH2) b’ In the formula, a' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, even more preferably 1 or 2, and most preferably 1. b' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, even more preferably 1 or 2, and most preferably 1.

[0087] Ya x1 is preferably a single bond, an ester bond [—C(═O)—O—], an ether bond (—O—), —C(═O)—NH—, a linear or branched alkylene group, or a combination thereof, and among these, a single bond is particularly more preferred.

[0088] In the formula (a10-1), Wa x1 is (n ax1 +1)valent aromatic hydrocarbon group. Wa x1 The aromatic hydrocarbon group in ax1 Examples of the aromatic ring include a group in which 4n+1) hydrogen atoms have been removed. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, even more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in the aromatic heterocycle include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of the aromatic heterocycle include pyridine rings and thiophene rings.

[0089] In the formula (a10-1), n ax1 is an integer of 1 to 3, preferably 1 or 2, and more preferably 1.

[0090] Specific examples of the structural unit represented by general formula (a10-1) are shown below. In the following formula, R α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0091] [ka]

[0092] The resin containing a hydroxystyrene skeleton is preferably a polymer of hydroxystyrene or a hydroxystyrene derivative, and more preferably a polymer of hydroxystyrene (polyhydroxystyrene).

[0093] [Polycarbonate polyol] Examples of polycarbonate polyols include polycarbonate polyols obtained by reacting one or more glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, or hydrogenated bisphenol A with dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene, or the like.

[0094] Among them, the polycarbonate polyol is preferably a polycarbonate diol represented by the following general formula (PC-1).

[0095] [ka] [In the formula, Rp 1 and Rp 2 are each independently a divalent hydrocarbon group, and np is an integer of 2 or greater.

[0096] In the general formula (PC-1), Rp 1 and Rp 2 are each independently a divalent hydrocarbon group. The divalent hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. Examples of the divalent hydrocarbon group include Ya in the general formula (a10-1). x1 The same as those listed in Rp 1 and Rp 2 The divalent hydrocarbon group in Rp is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkylene group. The divalent hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 4 to 6 carbon atoms. 1 and Rp 2 Specific examples include -(CH2)6- and -(CH2)5-.

[0097] The weight average molecular weight (Mw) of the polycarbonate polyol is preferably 500 to 5,000, more preferably 500 to 3,000, further preferably 500 to 2,000, and particularly preferably 500 to 1,000.

[0098] When a polycarbonate polyol is used as the component (O2), the ratio of the polycarbonate polyol to the component (O1) (polycarbonate polyol / component (O1) (mass ratio)) is preferably 0.1 to 5, more preferably 0.3 to 3, and even more preferably 0.4 to 3.

[0099] [Other polyols] Examples of polyester polyols include polyester polyols obtained by reacting a dibasic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, or sebacic acid, or a dialkyl ester thereof, or a mixture thereof, with a glycol such as ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, or polytetramethylene ether glycol, or a mixture thereof; and polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, polyvalerolactone, or poly(β-methyl-γ-valerolactone).

[0100] Examples of polyether polyols include polyether polyols obtained by polymerizing an oxirane compound such as ethylene oxide, propylene oxide, butylene oxide, or tetrahydrofuran using a low-molecular-weight polyol such as water, ethylene glycol, propylene glycol, trimethylolpropane, or glycerin as an initiator.

[0101] Examples of polyether ester polyols include polyether ester polyols obtained by reacting a dibasic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, or sebacic acid, or a dialkyl ester thereof, or a mixture thereof, with the above-mentioned polyether polyol.

[0102] Examples of polyesteramide polyols include polyesteramide polyols obtained by using an aliphatic diamine having an amino group, such as ethylenediamine, propylenediamine, or hexamethylenediamine, as a raw material in the above esterification reaction.

[0103] Examples of acrylic polyols include polyesteramide polyols obtained by copolymerizing hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, etc., which contain one or more hydroxyl groups per molecule, or their corresponding methacrylic acid derivatives, with, for example, acrylic acid, methacrylic acid, or an ester thereof.

[0104] Examples of polyhydroxyalkanes include liquid rubbers obtained by copolymerizing butadiene or butadiene with acrylamide or the like. The polyurethane polyol is a polyol having one or more urethane bonds in one molecule, and examples thereof include polyurethane polyols obtained by reacting a polyether polyol, polyester polyol, polyether ester polyol, or the like having a number average molecular weight of 200 to 20,000 with a polyisocyanate, preferably at an NCO / OH ratio of less than 1, more preferably 0.9 or less.

[0105] Examples of the vegetable oil-based polyol include castor oil, castor oil-modified polyol, dimer acid-modified polyol, soybean oil-modified polyol, etc. Among these, as the vegetable oil-based polyol, castor oil-modified polyol is preferred, and castor oil-modified diol is more preferred. When a vegetable oil-based polyol is used as the component (O2), the ratio of the vegetable oil-based polyol to the component (O1) (vegetable oil-based polyol / component (O1) (mass ratio)) is preferably 0.1 to 5, more preferably 0.3 to 3, and even more preferably 0.4 to 2.5.

[0106] The component (O2) may be used alone or in combination of two or more. Among the above, polycarbonate polyols and low-molecular-weight polyols are preferred as component (O2) from the viewpoint of adjusting the viscosity of the adhesive composition and the hardness of the adhesive layer. Furthermore, castor oil-modified polyols may also be used as component (O2) from the viewpoint of improving the heat resistance of the adhesive layer.

[0107] From the viewpoint of adjusting the viscosity of the adhesive composition and the heat resistance of the adhesive layer, the component (O) is preferably a combination of the components (O1) and (O2). The component (O2) is preferably a low-molecular-weight polyol, a polycarbonate polyol, a castor oil-modified polyol, or a combination thereof. Specific examples of the component (O2) to be combined with the component (O1) include a combination of a polycarbonate polyol, a castor oil-modified polyol, and a low-molecular-weight polyol; a combination of a polycarbonate polyol and a castor oil-modified polyol; and a polycarbonate polyol. The mass ratio of the (O1) component to the (O2) component is preferably (O1):(O2)=1:5 to 5:1, more preferably 1:4 to 2:1, even more preferably 1:4 to 1:1, and particularly preferably 1:4 to 1:2. By setting the mass ratio of the (O1) component to the (O2) component within the above range, the elastic modulus, heat resistance, etc. of the second adhesive layer can be improved.

[0108] The component (P1) can be synthesized by mixing the components (I) and (O) and copolymerizing them according to a known method for synthesizing urethane resins. The copolymerization of components (I) and (O) is preferably carried out in the presence of a known urethane catalyst such as a bismuth catalyst. A polymerization inhibitor may also be added to the reaction system to prevent polymerization of the polymerizable carbon-carbon double bond in component (O1).

[0109] The ratio (mass ratio) of component (I) to component (O) used in the synthesis of component (P1) is, for example, preferably (I):(O)=10:90 to 60:40, more preferably 20:80 to 50:50, and even more preferably 25:75 to 45:55. The molar ratio (NCO / OH) of the isocyanate groups (-NCO) in component (I) to the hydroxyl groups (-OH) in component (O) is preferably 60:40 to 40:60, and more preferably 55:45 to 45:55.

[0110] The component (P1) may be used alone or in combination of two or more types. The content of the component (P1) in the adhesive composition (12) is not particularly limited as long as it is a concentration that allows application to a support, etc. The content of the component (P1) in the adhesive composition (12) is preferably 20 to 75 mass %, more preferably 25 to 70 mass %, even more preferably 30 to 65 mass %, and particularly preferably 30 to 60 mass %, relative to the total amount (100 mass %) of the adhesive composition (12).

[0111] Crosslinking agent component The adhesive composition (12) may contain, in addition to the component (P1), a crosslinking agent component (hereinafter also referred to as "component (M)"). The component (M) may be a caprolactone-modified urethane acrylate (hereinafter also referred to as "component (M1)").

[0112] Caprolactone-modified urethane acrylate (component (M1)) The (M1) component is a polycaprolactone group (-[O(CH2)5CO] n The component (M1) is a urethane acrylate containing a group represented by the following general formula (c1):

[0113] [ka] [In the formula, Rc 1 represents a hydrogen atom or a methyl group; Rc 2 represents an alkylene group; and n represents an integer of 1 to 20.

[0114] In the formula (c1), Rc 2 represents an alkylene group. 2 The alkylene group in Rc may be linear, branched, or cyclic, but is preferably linear. 2 The alkylene group in the formula (I) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms, or 1 or 2 carbon atoms. In the formula (c1), n ​​is preferably an integer of 1 to 10, more preferably an integer of 1 to 8, and even more preferably an integer of 1 to 6.

[0115] The group represented by the formula (c1) is preferably a group represented by the following formula (c1-1).

[0116] [ka] [In the formula, Rc 1 represents a hydrogen atom or a methyl group; m represents an integer of 1 to 10; and n represents an integer of 1 to 20.]

[0117] In the formula (c1-1), m is preferably an integer of 1 to 8, more preferably an integer of 1 to 6, still more preferably an integer of 1 to 4, and particularly preferably an integer of 1 to 3. A specific example of m is 2. In the formula (c1-1), n ​​is preferably an integer of 1 to 10, more preferably an integer of 1 to 8, and even more preferably an integer of 1 to 6.

[0118] The main skeleton of the urethane acrylate in the component (M1) is not particularly limited. The urethane acrylate may be a biuret type, an isocyanurate type, or an adduct type with an aliphatic polyol (e.g., trimethylolpropane). Examples of the biuret type (M1) component include those represented by the following general formula (m1-1). Examples of the isocyanurate type (M1) component include those represented by the following general formula (m1-2). Examples of the adduct type (M1) component include those represented by the following general formula (m1-3).

[0119] [ka] [In the formula, Rx 1 ~Rx 3 Rm each independently represents a group represented by the formula (c1). 1 , Rm 2 , and Rm 3 Rm each independently represents a hydrocarbon group which may have a substituent. 4 ~Rm 6 Rm each independently represents a linear or branched alkylene group. 7 represents a linear or branched alkyl group.

[0120] In the formulae (m1-1) to (m1-3), Rm 1 , Rm 2 , and Rm 3 Each of the groups independently represents a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group which may have a substituent include Ya in the above formula (a10-1). x1 Examples of the divalent hydrocarbon group which may have a substituent include the same as those exemplified as the divalent hydrocarbon group which may have a substituent in the above formula. Rm 1 , Rm 2 , and Rm 3 Rm may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. 1 , Rm 2 , and Rm 3The aliphatic hydrocarbon group in the formula (I) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 6 carbon atoms. The aliphatic hydrocarbon group may be linear, branched, or cyclic. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and even more preferably 2 to 6 carbon atoms. The cyclic aliphatic hydrocarbon group preferably has 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 3 to 6 carbon atoms. Rm 1 , Rm 2 , and Rm 3 The aromatic hydrocarbon group in the formula (I) preferably has 4 to 12 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 10 carbon atoms. The aromatic ring contained in the aromatic hydrocarbon group may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring.

[0121] Rm 1 , Rm 2 , and Rm 3 The hydrocarbon group in Rm may or may not have a substituent. 1 , Rm 2 , and Rm 3 The hydrocarbon group in the formula (a10-1) may have a substituent such as Ya x1 Examples of the substituents include the same as those listed for the optionally substituted divalent hydrocarbon group in the above.

[0122] Rm 1 , Rm 2 , and Rm 3 is preferably a linear or branched alkylene group, more preferably a linear alkylene group, still more preferably a linear alkylene group having 1 to 10 carbon atoms, and particularly preferably a linear alkylene group having 1 to 6 carbon atoms.

[0123] In the formula (m1-3), Rm 4 ~Rm 6 Rm each independently represents a linear or branched alkylene group. 4 ~Rm 6The linear alkylene group in Rm preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms. 4 ~Rm 6 The branched alkylene group in the formula (I) preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, still more preferably 2 to 6 carbon atoms, and particularly preferably 2 or 3 carbon atoms. In the formula (m1-3), Rm 7 represents a linear or branched alkyl group. 7 The linear alkyl group in Rm preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms. 7 The branched alkyl group in preferably has 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, still more preferably 3 to 6 carbon atoms, and particularly preferably 3 or 4 carbon atoms.

[0124] Specific examples of the component (M1) include, but are not limited to, the following:

[0125] [ka] [In the formula, Rx 11 ~Rx 13 represents a group represented by the following formula (c1-1-1):

[0126] [ka] [In the formula, n represents an integer of 1 to 20.]

[0127] The component (M1) can be obtained by a known method, for example, by reacting a polyisocyanate compound with a caprolactone-modified (meth)acrylate.

[0128] Examples of the polyisocyanate compound include the same compounds as those listed above as component (I). Examples of the polyisocyanate compound include biuret compounds of diisocyanates, isocyanurate compounds of diisocyanates, and adduct compounds of diisocyanates and aliphatic polyols (e.g., trimethylolpropane). Examples of biuret compounds of diisocyanates include compounds represented by the following general formula (I-1). Examples of isocyanurate compounds of diisocyanates include compounds represented by the following general formula (I-2). Examples of adduct compounds of diisocyanates include compounds represented by the following general formula (I-3).

[0129] [ka] [In the formula, Rm 1 ~Rm 7 represents Rm in the formulas (m-1) to (m-3). 1 ~Rm 7 are equivalent to

[0130] Examples of diisocyanates for forming the compounds of the formulae (I-1) to (I-3) include, but are not limited to, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, methylcyclohexane diisocyanate, and m-tetramethylxylylene diisocyanate. Among these, tolylene diisocyanate, hexamethylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, and isophorone diisocyanate are preferred as diisocyanates.

[0131] Caprolactone-modified (meth)acrylates are compounds obtained by addition polymerization of ε-caprolactone with (meth)acrylates or hydroxyl group-containing (meth)acrylates. Hydroxyl group-containing (meth)acrylates are compounds having a (meth)acryloyl group and a hydroxyl group. The term "(meth)acryloyl group" encompasses both methacryloyl and acryloyl groups, and refers to either a methacryloyl group or an acryloyl group. Examples of the hydroxy group-containing (meth)acrylate include hydroxyalkyl (meth)acrylate. Specific examples of the hydroxyalkyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate.

[0132] Commercially available caprolactone-modified (meth)acrylate products include, for example, Plaxel FA1, Plaxel FA2D, and Plaxel FA5 (all trade names, manufactured by Daicel Chemical Industries, Ltd.).

[0133] The component (M1) may be used alone or in combination of two or more types. The proportion of the (M1) component in the (M) component is, for example, preferably 40 to 100 mass%, more preferably 50 to 95 mass%, even more preferably 70 to 90 mass%, and particularly preferably 75 to 85 mass%, based on the total amount (100 mass%) of the (M) component. Alternatively, the proportion of the (M1) component in the (M) component is, for example, preferably 40 to 100 mol%, more preferably 50 to 95 mol%, even more preferably 70 to 90 mol%, and particularly preferably 75 to 85 mol%, based on the total amount (100 mol%) of the (M) component. By keeping the proportion of the (M1) component in the (M) component within the above-mentioned preferred range, it is possible to maintain washability while suppressing delamination in high-temperature processes.

[0134] Other crosslinker components (component (M2)) In addition to the component (M1), the component (M) may contain another crosslinking agent component (hereinafter also referred to as "component (M2)"). The component (M2) may be a compound having two or more (meth)acryloyl groups (excluding the component (M1)). Examples of the component (M2) include polyfunctional urethane (meth)acrylates, polyfunctional (meth)acrylates, polyfunctional caprolactone-modified (meth)acrylates, etc. When the adhesive composition of the present embodiment contains the component (M2), the above-mentioned component (P1) does not include components that fall under the category of the component (M2).

[0135] A polyfunctional urethane (meth)acrylate is a compound containing a urethane bond (-NCO-) and two or more (meth)acryloyl groups. Examples of the polyfunctional urethane (meth)acrylate include compounds obtained by reacting the polyisocyanate compound with a (meth)acrylate or a hydroxyl group-containing (meth)acrylate. Specific examples of the polyfunctional urethane (meth)acrylate include compounds represented by any of the following general formulas (m2-1) to (m2-3).

[0136] [ka] [In the formula, Ry 1 ~Ry 3 are each independently -O-(CH2) k Rm represents a group represented by -OCOCH=CH2 (k is an integer of 1 to 10). 1 ~Rm 7 represents Rm in the formulas (m-1) to (m-3). 1 ~Rm 7 are equivalent to

[0137] Preferred specific examples of the polyfunctional urethane (meth)acrylate are shown below, but the invention is not limited to these.

[0138] [ka] [In the formula, Ry 11 ~Ry 13 represents a group represented by -O-(CH2)2-OCOCH=CH2.

[0139] The (meth)acrylate compound is a compound containing a (meth)acryloyl group. Examples of the (meth)acrylate compound as the component (M2) include the same compounds as those listed above for the component (O1).

[0140] Examples of polyfunctional (meth)acrylates include bifunctional (meth)acrylates such as 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, and ethoxylated bisphenol A diacrylate; and trifunctional (meth)acrylates such as trimethylolpropane triacrylate, ethoxylated trimethylolpropane tri(meth)acrylate, ethoxylated glycerin tri(meth)acrylate, and pentaerythritol tri(meth)acrylate.

[0141] Examples of polyfunctional caprolactone-modified (meth)acrylates include caprolactone-modified ((meth)acrylate alkyl) isocyanurates such as caprolactone-modified tris-(2-(meth)acryloxyethyl) isocyanurate.

[0142] The component (M2) may be used alone or in combination of two or more types. The proportion of the (M2) component in the (M) component is, for example, preferably 0 to 60 mass%, more preferably 5 to 50 mass%, even more preferably 10 to 40 mass%, and particularly preferably 10 to 30 mass%, relative to the total amount (100 mass%) of the (M) component. Alternatively, the proportion of the (M2) component in the (M) component is preferably 0 to 60 mol%, more preferably 5 to 50 mol%, even more preferably 10 to 40 mol%, and particularly preferably 10 to 30 mol%, relative to the total amount (100 mass%) of the (M) component. When the (M) component contains the (M2) component, the molar ratio of the (M1) component to the (M2) component ((M1) component:(M2) component) is, for example, 99:1 to 20:80. The molar ratio of the (M1) component to the (M2) component is preferably 95:5 to 30:70, more preferably 90:10 to 40:60, even more preferably 90:10 to 50:50, and particularly preferably 90:10 to 60:40.

[0143] The proportion of the (M) component in the adhesive composition (12) is, for example, preferably 10 to 60 mass %, more preferably 10 to 50 mass %, even more preferably 20 to 40 mass %, and particularly preferably 25 to 35 mass %, relative to the total mass (100 mass %) of the adhesive composition (12). The mass ratio of the above component (P1) to component (M) (component (P1):component (M)) is preferably 95:5 to 50:50, more preferably 90:10 to 60:40, and even more preferably 80:20 to 60:40.

[0144] Polymerization initiator (component (A)) The polymerization initiator (hereinafter also referred to as "component (A)") is a component that has the function of accelerating a polymerization reaction. Examples of component (A) include a thermal polymerization initiator and a photopolymerization initiator.

[0145] Examples of the thermal polymerization initiator include peroxides and azo-based polymerization initiators.

[0146] Examples of the peroxide in the thermal polymerization initiator include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, and peroxyester. Specific examples of such peroxides include acetyl peroxide, dicumyl peroxide, tert-butyl peroxide, t-butylcumyl peroxide, propionyl peroxide, benzoyl peroxide (BPO), 2-chlorobenzoyl peroxide, 3-chlorobenzoyl peroxide, 4-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 4-bromomethylbenzoyl peroxide, lauroyl peroxide, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, tert-butyl triphenylperacetate, tert-butyl hydroperoxide, tert-butyl performate, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl 4-methoxyacetate, and tert-butyl N-(3-toluyl)carbamate.

[0147] As the peroxide, for example, commercially available products such as those manufactured by NOF Corporation under the trade names "Percumyl (registered trademark)", "Perbutyl (registered trademark)", "Peroyl (registered trademark)" and "Perocta (registered trademark)" can be used.

[0148] Examples of the azo-based polymerization initiator in the thermal polymerization initiator include 2,2'-azobispropane, 2,2'-dichloro-2,2'-azobispropane, 1,1'-azo(methylethyl)diacetate, 2,2'-azobis(2-amidinopropane) hydrochloride, 2,2'-azobis(2-aminopropane) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutylamide, 2,2'-azobisisobutyronitrile, and 2,2'-azobis-2-methylpropionic acid methyl ester. Chill, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobisisobutyric acid dimethyl, 1,1'-azobis(1-methylbutyronitrile-3-sodium sulfonate, 2-(4-methylphenylazo)-2-methylmalonodinitrile, 4,4'-azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-allylmalonodinitrile, 2,2'-azobis-2-methylvaleronitrile, 4 ,4'-Azobis-4-cyanodimethylvalerate, 2,2'-Azobis-2,4-dimethylvaleronitrile, 1,1'-Azobiscyclohexanenitrile, 2,2'-Azobis-2-propylbutyronitrile, 1,1'-Azobiscyclohexanenitrile, 2,2'-Azobis-2-propylbutyronitrile, 1,1'-Azobis-1-chlorophenylethane, 1,1'-Azobis-1-cyclohexanecarbonitrile, 1,1'-Azobis-1-cycloheptanenitrile Examples of suitable azobis-1,2-diphenylethane include bisphenol A, 1,1'-azobis-1-phenylethane, 1,1'-azobiscumene, ethyl 4-nitrophenylazobenzylcyanoacetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrophenylazotriphenylmethane, 1,1'-azobis-1,2-diphenylethane, poly(bisphenol A-4,4'-azobis-4-cyanopentanoate), and poly(tetraethylene glycol-2,2'-azobisisobutyrate).

[0149] Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(4-dimethylaminophenyl)ketone, and the like. thion, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(o-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, 4-dimethylamino Ethyl benzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzil dimethyl ketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthone anthraquinone, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-Di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (i.e., Michler's ketone), 4,4'-bisdiethylaminobenzophenone (i.e., ethyl Michler's ketone), 4,4' -Dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzil, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin-t-butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, pt-butylacetophenone, p-dimethylaminoacetophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytriazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl- 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,Examples of such amines include 6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, and 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine.

[0150] As the photopolymerization initiator, for example, commercially available products such as "IRGACURE OXE02", "IRGACURE OXE01", "IRGACURE 369", "IRGACURE 651", and "IRGACURE 907" (all trade names, manufactured by BASF) and "NCI-831" (trade name, manufactured by ADEKA Corporation) can be used.

[0151] The component (A) may be used alone or in combination of two or more. As the component (A), a thermal polymerization initiator is preferred, and a peroxide is more preferred. The amount of component (A) used can be adjusted depending on the amount of component (P1) used. The content of the polymerization initiator in the adhesive composition (12) is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the component (P1).

[0152] Other ingredients In addition to the components (P1), (M), and (A), the adhesive composition (12) may further contain optional components that are compatible with the components (P1), (M), and (A) to the extent that the essential properties are not impaired. The optional components include, but are not limited to, polymerization inhibitors, silane coupling agents, surfactants, solvents, plasticizers, adhesive aids, stabilizers, colorants, etc.

[0153] Polymerization inhibitors A polymerization inhibitor is a component that has the function of preventing radical polymerization reactions caused by heat or light, and is highly reactive to radicals.

[0154] The polymerization inhibitor preferably has a phenol skeleton. For example, a hindered phenol-based antioxidant can be used as the polymerization inhibitor, and examples thereof include pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, amyloxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4,4'-(1-methylethylidene)bis(2-methylphenol), 4,4'-(1-methylethylidene)bis(2,6- dimethylphenol), 4,4'-[1-[4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl]ethylidene]bisphenol, 4,4',4"-ethylidenetris(2-methylphenol), 4,4',4"-ethylidenetrisphenol, 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 2,6-di-tert-butyl-4-methylphenol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol) 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 3,9-bis[2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)-propionyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro(5,5)undecane, triethylene glycol-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyl n-octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythryl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name IRGANOX 1010, manufactured by BASF), tris(3,5-di-tert-butylhydroxybenzyl)isocyanurate, thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and the like.

[0155] The polymerization inhibitor may be used alone or in combination of two or more. The content of the polymerization inhibitor may be determined appropriately depending on the type of resin component, the application of the adhesive composition, and the environment in which it is used.

[0156] Silane coupling agents Examples of the silane coupling agent include silane coupling agents having a reactive substituent such as a carboxy group, a methacryloyl group, an isocyanate group, an epoxy group, etc. Specific examples include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. The silane coupling agents may be used alone or in combination of two or more. When a silane coupling agent is included, its content is preferably 0.1 to 10 parts by mass per 100 parts by mass of component (P1). When the content of the silane coupling agent is within the above-mentioned preferred range, the strength of the cured film is further increased, and the adhesion between the cured film and the substrate is further strengthened.

[0157] Surfactants Examples of surfactants include fluorine-based surfactants and silicone-based surfactants.

[0158] Examples of fluorine-based surfactants include commercially available fluorine-based surfactants such as BM-1000 and BM-1100 (all manufactured by BM Chemie), Megafac F142D, Megafac F172, Megafac F173, and Megafac F183 (all manufactured by DIC Corporation), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, and Fluorad FC-431 (all manufactured by Sumitomo 3M Limited), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, and Surflon S-145 (all manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, and SF-8428 (all manufactured by Toray Silicones Co., Ltd.).

[0159] Examples of silicone surfactants include unmodified silicone surfactants, polyether-modified silicone surfactants, polyester-modified silicone surfactants, alkyl-modified silicone surfactants, aralkyl-modified silicone surfactants, and reactive silicone surfactants. Commercially available silicone surfactants can be used. Specific examples of commercially available silicone surfactants include Paintad M (manufactured by Dow Corning Toray Co., Ltd.), Topika K1000, Topika K2000, and Topika K5000 (all manufactured by Takachiho Sangyo Co., Ltd.), XL-121 (a polyether-modified silicone surfactant manufactured by Clariant), and BYK-310 (a polyester-modified silicone surfactant manufactured by BYK-Chemie).

[0160] The surfactant may be used alone or in combination of two or more. As the surfactant, a silicone surfactant is preferred, and a polyester-modified silicone surfactant is more preferred. When a surfactant is used, the content of the surfactant in the adhesive composition (12) is preferably 0.01 to 1 part by mass, and more preferably 0.05 to 0.5 parts by mass, per 100 parts by mass of the component (P1).

[0161] Solvent components The adhesive composition (12) can be prepared by dissolving the components (P1), (M), and (A), and optionally any other components, in a solvent component and mixing them together. Any solvent component capable of dissolving the above components can be used.

[0162] Examples of solvent components include hydrocarbon solvents, petroleum-based solvents, and other solvents. Hereinafter, hydrocarbon solvents and petroleum-based solvents are collectively referred to as "component (S1)." Solvent components other than component (S1) are also referred to as "component (S2)."

[0163] Hydrocarbon solvents include straight chain, branched chain, or cyclic hydrocarbons. Examples of hydrocarbon solvents include linear hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, and tridecane; branched hydrocarbons such as isooctane, isononane, and isododecane; alicyclic hydrocarbons such as p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpine, 1,8-terpine, bornane, norbornane, pinane, thujane, carane, longifolene, α-terpinene, β-terpinene, γ-terpinene, α-pinene, β-pinene, α-thujone, β-thujone, cyclohexane, cycloheptane, and cyclooctane; and aromatic hydrocarbons such as toluene, xylene, indene, pentalene, indane, tetrahydroindene, naphthalene, tetrahydronaphthalene (tetralin), and decahydronaphthalene (decalin).

[0164] Petroleum-based solvents are solvents refined from heavy oil, and examples thereof include kerosene, paraffin-based solvents, and isoparaffin-based solvents.

[0165] Examples of the component (S2) include terpene solvents having an oxygen atom, a carbonyl group, or an acetoxy group as a polar group, such as geraniol, nerol, linalool, citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, terpinen-4-ol, dihydroterpinyl acetate, 1,4-cineole, 1,8-cineole, borneol, carvone, ionone, thujone, and camphor.

[0166] Examples of the component (S2) include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate; and monomethyl ethers, monoethyl ethers, monopropyl ethers, and monobutyl ethers of the above polyhydric alcohols or compounds having an ester bond. derivatives of polyhydric alcohols such as compounds having an ether bond, for example, monoalkyl ethers or monophenyl ethers such as those listed above (among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred); cyclic ethers such as dioxane; esters such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; and aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, and butyl phenyl ether.

[0167] The solvent component may be used alone or in combination of two or more. The solvent component is preferably inactive to the component (P1). Preferred examples of the solvent component include ester-based solvents, ketone-based solvents, aromatic hydrocarbon-based solvents, PGMEA, PGME, and mixed solvents thereof.

[0168] The content of the solvent component in the adhesive composition (12) may be adjusted appropriately depending on the thickness of the adhesive layer. The content of the solvent component is preferably, for example, within the range of 30 to 90 mass % relative to the total amount (100 mass %) of the adhesive composition (12). That is, the adhesive composition (12) preferably has a solids concentration (total amount of blended components excluding the solvent component) within the range of 10 to 70 mass %. When the content of the solvent component is within the above-mentioned preferred range, viscosity adjustment becomes easy.

[0169] <Second adhesive layer> The second adhesive layer is an adhesive layer provided between the first adhesive layer and the device layer and adjacent to the device layer, and is a layer formed of a second material exhibiting the following properties: In the laminate 100, a substrate 4 is provided on the second adhesive layer 3B, and the substrate 4 is sealed between the second adhesive layer 3B and the sealant layer 5. The second adhesive layer 3B can be removed with a cleaning solution containing an organic solvent.

[0170] The thickness of the second adhesive layer is preferably, for example, in the range of 0.1 μm to 100 μm, more preferably in the range of 1 μm to 75 μm, and even more preferably in the range of 10 μm to 60 μm. When the thickness of the second adhesive layer is within the above-mentioned preferred range, a protective layer that can protect the device during processing is easily formed.

[0171] <Second ingredient> The second material contains a thermoplastic resin and has an elastic modulus at 260°C of 20 MPa or more. The second material may be an adhesive composition containing a resin component and other components (hereinafter also referred to as "adhesive composition (2)").

[0172] The second material has an elastic modulus at 260° C. of 20 MPa or more, preferably 25 MPa or more, more preferably 30 MPa or more, and even more preferably 35 MPa or more. If the modulus of elasticity of the second material at 260° C. is equal to or greater than the lower limit of the above range, the adhesive layer formed from the second material will be less susceptible to deformation due to external forces.

[0173] Method for measuring elastic modulus at 260°C: For the second material, the modulus of elasticity at 260° C. is measured as follows. An adhesive layer with a thickness of 50 μm is formed on a silicon wafer. A test piece (film thickness 50 μm, width 5 mm, length 40 mm) of the adhesive layer is cut out, and the tensile modulus is measured using a dynamic viscoelasticity measuring device at a frequency of 1 Hz in the range of 50 to 300° C. The measured value at 260° C. is the modulus at 260° C.

[0174] The second material preferably exhibits a film stress of 15 MPa or less, more preferably 10 MPa or less, and even more preferably 5 MPa or less. If the film stress of the second material is equal to or less than the upper limit of the above-mentioned preferable range, the adhesive layer formed from the second material becomes less susceptible to deformation due to an external force. The lower limit of the film stress of the second material is substantially 1 MPa or more, and may be 2 MPa or more.

[0175] Examples of the adhesive composition (2) exemplified as the second material include a cycloolefin-based adhesive composition and an elastomer-based adhesive composition.

[0176] Examples of such adhesive composition (2) include a cycloolefin-based adhesive composition that contains a thermoplastic resin containing a cyclic olefin block copolymer, a diluent solvent, and other components such as additives, and that exhibits an elastic modulus of 20 MPa or more at 260°C. Furthermore, examples of such adhesive composition (2) include elastomer-based adhesive compositions that contain a thermoplastic resin containing a hydrogenated styrene-based thermoplastic elastomer, a diluent solvent, and other components such as additives, and that exhibit an elastic modulus of 20 MPa or more at 260°C.

[0177] Cycloolefin-based adhesive composition (hereinafter also referred to as “adhesive composition (21)”): Cyclic olefin block copolymer A cyclic olefin block copolymer is a polymer in which multiple types of blocks (partial constituent components in which the same type of constituent units are repeatedly bonded) are bonded together. The number of types of blocks constituting the block copolymer may be two or more. One embodiment of the cyclic olefin block copolymer (hereinafter also referred to as "(BCP) component") is a block copolymer (BCP12) having a first block and a second block. Another embodiment of the cyclic olefin block copolymer is a block copolymer (BCP123) having a first block, a second block, and a third block.

[0178] The weight average molecular weight (Mw) of the (BCP) component is, for example, 10,000 or more and 700,000 or less. The content of the (BCP) component in the adhesive composition (21) is preferably 5% by mass or more, and may be 5 to 50% by mass, or may be 10 to 25% by mass, relative to the total amount (100% by mass) of the adhesive composition (21).

[0179] Block 1 The first block is composed of a polymer consisting of a repeating structure of a structural unit (u1) derived from a cycloolefin monomer. Examples of the cycloolefin monomer include monomers such as bicyclic compounds such as norbornene and norbornadiene, tricyclic compounds such as dicyclopentadiene and hydroxydicyclopentadiene, tetracyclic compounds such as tetracyclododecene, pentacyclic compounds such as cyclopentadiene trimer, heptacyclic compounds such as tetracyclopentadiene, and alkyl (methyl, ethyl, propyl, butyl, etc.) substituted compounds, alkenyl (vinyl, etc.) substituted compounds, alkylidene (ethylidene, etc.) substituted compounds, or aryl (phenyl, tolyl, naphthyl, etc.) substituted compounds of these polycyclic compounds.

[0180] Among the above, the cycloolefin monomer is preferably a monomer having a norbornene structure selected from the group consisting of norbornene, tetracyclododecene, and substituted derivatives thereof, and more preferably norbornene which may have a substituent. That is, the first block is preferably a block composed of a polymer consisting of a repeating structure of structural unit (u1) derived from norbornene which may have a substituent. Examples of the substituent that norbornene may have include alkyl groups having 1 to 16 carbon atoms, preferably alkyl groups having 1 to 12 carbon atoms, and more preferably alkyl groups having 6 to 12 carbon atoms. Among these, the cycloolefin monomer is particularly preferably unsubstituted norbornene.

[0181] Specific examples of the structural unit (u1) are shown below.

[0182] [ka]

[0183] The glass transition point (Tg) of the polymer constituting the first block is, for example, 200 to 300°C, and preferably 220 to 270°C.

[0184] Block 2 The second block is composed of a polymer that exhibits an elastic modulus of 20 MPa or more at 260°C when an adhesive composition (21) containing the block copolymer (BCP12) bonded to the first block forms an adhesive layer with a thickness of 50 μm. For example, the second block may be a block composed of a polymer consisting of a repeating structure of a structural unit (u2) derived from norbornene which may have a substituent and which has a different structure from the structural unit (u1). Examples of the structural unit in the second block that is derived from norbornene and that may have a substituent include the same structural units as those described above for the structural unit (u1).

[0185] The glass transition point (Tg) of the polymer constituting the second block is, for example, 100 to 180°C, and preferably 120 to 170°C.

[0186] The block copolymer (BCP12) having a first block and a second block is preferably a block copolymer in which the first block is a block composed of a polymer consisting of a repeating structure of a structural unit derived from unsubstituted norbornene as the structural unit (u1), and the second block is a block composed of a polymer consisting of a repeating structure of a structural unit derived from norbornene having, as the structural unit (u2), an alkyl group having 1 to 16 carbon atoms (preferably 1 to 12 carbon atoms) as a substituent.

[0187] Specific examples of combinations of the first block and the second block are shown below: R is an alkyl group having 1 to 12 carbon atoms.

[0188] [ka]

[0189] In the block copolymer (BCP12), the molar ratio of the first block to the second block (first block / second block) is preferably 40 / 60 to 75 / 25, more preferably 45 / 55 to 70 / 30, and even more preferably 50 / 50 to 60 / 40. The weight average molecular weight of the block copolymer (BCP12) is, for example, from 10,000 to 700,000, and preferably from 50,000 to 600,000. The difference between the glass transition point of the polymer constituting the first block and the glass transition point of the polymer constituting the second block is preferably 50°C or more, more preferably 80 to 120°C.

[0190] Block 3 The third block is composed of a polymer that exhibits an elastic modulus of 20 MPa or more at 260°C when an adhesive composition (21) containing a block copolymer (BCP123) bonded to the first block and the second block forms an adhesive layer with a thickness of 50 μm. For example, the third block may be a block composed of a polymer consisting of a repeating structure of a structural unit (u3) derived from norbornene which may have a substituent. Examples of the structural unit in the third block derived from norbornene which may have a substituent include the same structural units as the structural unit (u1).Of these, the structural unit (u3) is preferably a structural unit derived from unsubstituted norbornene. The structural unit (u3) may have the same structure as the structural unit (u1), or may have a different structure.

[0191] The glass transition point (Tg) of the polymer constituting the third block is, for example, 200 to 300°C, and preferably 220 to 270°C.

[0192] The block copolymer (BCP123) having a first block, a second block, and a third block is preferably a block copolymer in which the first block is a block composed of a polymer consisting of a repeating structure of a structural unit derived from unsubstituted norbornene as the structural unit (u1), the second block is a block composed of a polymer consisting of a repeating structure of a structural unit derived from norbornene having, as the structural unit (u2), an alkyl group having 1 to 16 carbon atoms (preferably 1 to 12 carbon atoms) as a substituent, and the third block is a block composed of a polymer consisting of a repeating structure of a structural unit derived from unsubstituted norbornene as the structural unit (u3).

[0193] Specific examples of combinations of the first block, second block, and third block are shown below: R is an alkyl group having 1 to 12 carbon atoms.

[0194] [ka]

[0195] In the block copolymer (BCP123), the molar ratio of the first block to the second block to the third block (first block / second block) is preferably 40 / 60 to 75 / 25, more preferably 45 / 55 to 70 / 30, and even more preferably 50 / 50 to 60 / 40. In the block copolymer (BCP123), the molar ratio of the first block to the third block (first block / third block) is preferably 30 / 70 to 70 / 30, more preferably 40 / 60 to 60 / 40, and even more preferably 45 / 55 to 55 / 45.

[0196] The weight average molecular weight of the block copolymer (BCP123) is, for example, from 10,000 to 700,000, and preferably from 50,000 to 600,000. The difference between the glass transition point of the polymer constituting the first block and the glass transition point of the polymer constituting the second block is preferably 50°C or more, more preferably 80 to 120°C. The difference between the glass transition point of the polymer constituting the third block and the glass transition point of the polymer constituting the second block is preferably 50°C or more, more preferably 80 to 120°C.

[0197] The (BCP) component can be produced by a method of synthesizing the polymers constituting each block and then polymerizing them, or by a method of continuously polymerizing monomers to elongate the polymer, and can be produced by appropriately using a block copolymer synthesis method (radical polymerization, ionic polymerization, etc.).

[0198] Dilution solvent Examples of dilution solvents include linear hydrocarbons such as hexane, heptane, octane, nonane, isononane, methyloctane, decane, undecane, dodecane, and tridecane; branched hydrocarbons having 4 to 15 carbon atoms; cyclic hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene, and tetrahydronaphthalene; p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpine, 1,8-terpine, bornane, norbornane, pinane, thujane, carane, longifolene, and geraniol. Terpene solvents such as ethanol, nerol, linalool, citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, terpinen-4-ol, dihydroterpinyl acetate, 1,4-cineole, 1,8-cineole, borneol, carvone, ionone, thujone, camphor, d-limonene, l-limonene, and dipentene; lactones such as γ-butyrolactone; acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n ketones such as 2-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate; derivatives of polyhydric alcohols such as compounds having an ether bond such as monoalkyl ethers, monomethyl ethers, monoethyl ethers, monopropyl ethers, and monobutyl ethers of the above polyhydric alcohols or compounds having an ester bond, or monophenyl ethers (among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred); cyclic ethers such as dioxane; and esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate;Examples of aromatic organic solvents include anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, and butyl phenyl ether;

[0199] Other ingredients The adhesive composition (21) may further contain other compatible substances to the extent that the essential properties are not impaired. For example, various commonly used additives such as additional resins (e.g., cycloolefin polymers other than the above-mentioned cyclic olefin block copolymers, acrylic resins, elastomers, etc.) to improve the performance of the adhesive, curable monomers, polymerization inhibitors, polymerization initiators, plasticizers, adhesion aids, stabilizers, colorants, surfactants, and antioxidants can be further used.

[0200] Cycloolefin polymers other than the above cyclic olefin block copolymers Suitable examples of the cycloolefin polymer include a ring-opening polymer of a monomer component containing a cycloolefin monomer, and an addition polymer obtained by addition polymerization of a monomer component containing a cycloolefin monomer.

[0201] Examples of cycloolefin monomers include bicyclic compounds such as norbornene and norbornadiene, tricyclic compounds such as dicyclopentadiene and hydroxydicyclopentadiene, tetracyclic compounds such as tetracyclododecene, pentacyclic compounds such as cyclopentadiene trimer, heptacyclic compounds such as tetracyclopentadiene, and alkyl (methyl, ethyl, propyl, butyl, etc.) substituted compounds, alkenyl (vinyl, etc.) substituted compounds, alkylidene (ethylidene, etc.) substituted compounds, or aryl (phenyl, tolyl, naphthyl, etc.) substituted compounds of these polycyclic compounds.

[0202] Among the above, polymers having structural units derived from a monomer having a norbornene structure selected from the group consisting of norbornene, tetracyclododecene, and alkyl-substituted derivatives thereof are particularly preferred. By using such a cycloolefin polymer having a norbornene structure, it becomes easier to obtain an adhesive composition that can form an adhesive layer that has high chemical resistance to resist solvents and is easily dissolved and removed in a hydrocarbon solvent.

[0203] The cycloolefin polymer may have, as a monomer unit, a monomer copolymerizable with the cycloolefin monomer. Suitable examples of such copolymerizable monomers include alkene monomers. These alkene monomers may be linear or branched, and include alkene monomers having 2 to 10 carbon atoms, such as α-olefins such as ethylene, propylene, 1-butene, isobutene, and 1-hexene. Among these, ethylene is more preferred as the monomer unit. Suitable examples of such copolymerizable monomers include monomers containing a maleimide skeleton.

[0204] Acrylic resin Examples of acrylic resins include resins (homopolymers and copolymers) polymerized using (meth)acrylic acid esters as monomers. "(Meth)acrylic" refers to at least one of acrylic and methacrylic. By including an acrylic resin, the adhesion between the support and the device layer can be further improved.

[0205] Examples of the (meth)acrylic acid ester include a (meth)acrylic acid alkyl ester having a chain structure, a (meth)acrylic acid ester having an aliphatic ring, and a (meth)acrylic acid ester having an aromatic ring. Among these, it is preferable to use a (meth)acrylic acid ester having an aliphatic ring.

[0206] Examples of alkyl (meth)acrylate esters having a chain structure include acrylic alkyl esters having an alkyl group with 1 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms herein may be linear or branched, and examples thereof include methyl, ethyl, propyl, butyl, 2-ethylhexyl, isooctyl, isononyl, isodecyl, dodecyl, lauryl, tridecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl (stearyl), n-nonadecyl, and n-eicosyl groups, with acrylic alkyl esters having an alkyl group having 15 to 20 carbon atoms being preferred.

[0207] Examples of (meth)acrylic acid esters having an aliphatic ring include cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, 1-adamantyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, tetracyclododecanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, etc. Among these, 1-adamantyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate are preferred.

[0208] In the (meth)acrylic acid ester having an aromatic ring, examples of the aromatic ring include a phenyl group, a benzyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a phenoxymethyl group, a phenoxyethyl group, etc. The aromatic ring may have a substituent, and may have a linear or branched alkyl group having 1 to 5 carbon atoms.

[0209] In the acrylic resin, the above-mentioned (meth)acrylic acid esters may be used alone or in combination of two or more.

[0210] The acrylic resin is preferably a resin obtained by polymerizing one or more selected from the group consisting of alkyl (meth)acrylate esters having a chain structure, (meth)acrylate esters having an aliphatic ring, and (meth)acrylate esters having an aromatic ring. Among these, a resin obtained by polymerizing a (meth)acrylic acid alkyl ester and a (meth)acrylic acid ester having an aliphatic ring is more preferable.

[0211] The acrylic resin may be a resin obtained by polymerizing a (meth)acrylic acid ester monomer with another monomer polymerizable therewith. Examples of such polymerizable monomers include styrene, styrene derivatives, and monomers containing a maleimide group. The styrene derivatives herein are the same as those described above for the "styrene derivatives." The monomers containing a maleimide group herein include the same monomers as those from which the structural unit (u21) is derived.

[0212] Among acrylic resins, resins obtained by polymerizing a (meth)acrylic acid ester monomer and styrene are preferred. The presence of styrene units in acrylic resins improves the heat resistance of the acrylic resins. In addition, the compatibility with other resins and the solubility in hydrocarbon solvents are improved. Among these, the acrylic resin is particularly preferably a resin obtained by polymerizing a (meth)acrylic acid alkyl ester having a chain structure, a (meth)acrylic acid ester having an aliphatic ring, and styrene.

[0213] ··Elastomer Suitable examples of elastomers include those having, as a structural unit of the main chain, a structural unit derived from styrene or a structural unit derived from a styrene derivative (collectively referred to as a "styrene unit"). The elastomer is preferably a styrene-based thermoplastic elastomer, and more preferably a hydrogenated styrene-based thermoplastic elastomer. Hydrogenated elastomers have further improved thermal stability and are less susceptible to deterioration such as decomposition and polymerization. In addition, they are more preferred from the viewpoints of solubility in hydrocarbon solvents and resistance to resist solvents. Among elastomers, block polymers in which both ends are styrene are more preferred. By blocking both ends with styrene, which has high thermal stability, higher heat resistance is likely to be obtained. More specifically, the elastomer is preferably a hydrogenated block copolymer of styrene and a conjugated diene. This further improves thermal stability and makes it less susceptible to degradation such as decomposition or polymerization. Furthermore, since both ends are blocked with highly thermally stable styrene, it exhibits higher heat resistance. Furthermore, this is more preferable from the viewpoints of solubility in hydrocarbon solvents and resistance to resist solvents.

[0214] Examples of commercially available elastomers that can be used as the resin component include "Septon (product name)" manufactured by Kuraray Co., Ltd., "Hybler (product name)" manufactured by Kuraray Co., Ltd., "Tuftec (product name)" manufactured by Asahi Kasei Corporation, and "Dynalon (product name)" manufactured by JSR Corporation.

[0215] Examples of the antioxidant include tocopherol-based compounds, phenol-based antioxidants, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, benzotriazole-based antioxidants, benzophenone-based antioxidants, hydroxylamine-based antioxidants, salicylic acid ester-based antioxidants, and triazine-based antioxidants.

[0216] Elastomer adhesive composition (hereinafter also referred to as “adhesive composition (22)”): Hydrogenated styrene-based thermoplastic elastomer The hydrogenated styrene-based thermoplastic elastomer preferably contains a styrene unit as a structural unit of the main chain, and the "styrene unit" may have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxyalkyl group having 1 to 5 carbon atoms, an acetoxy group, and a carboxyl group. It is more preferable that the content of the styrene unit is in the range of 14% by mass or more and 50% by mass or less. Furthermore, it is preferable that the hydrogenated styrene-based thermoplastic elastomer has a weight average molecular weight in the range of 100,000 or more and 200,000 or less.

[0217] When the styrene unit content is within the range of 14% by mass or more and 50% by mass or less, and the weight-average molecular weight of the hydrogenated styrene-based thermoplastic elastomer is within the range of 100,000 or more and 200,000 or less, the desired elastic modulus is achieved and deformation due to external forces is suppressed. In addition, because the elastomer is thermoplastic, it is easily dissolved in hydrocarbon solvents described below, allowing for easier and faster removal of the adhesive layer. Furthermore, when the styrene unit content and weight-average molecular weight are within the above ranges, the elastomer exhibits excellent resistance to resist solvents (e.g., PGMEA, PGME, etc.), acids (e.g., hydrofluoric acid), and alkalis (e.g., TMAH) used in resist lithography. The hydrogenated styrene-based thermoplastic elastomer may further contain the above-mentioned (meth)acrylic acid ester. The content of styrene units is more preferably 17% by mass or more, and more preferably 45% by mass or less. The hydrogenated styrene-based thermoplastic elastomer preferably has a weight average molecular weight in the range of 100,000 to 200,000, and more preferably in the range of 100,000 to 150,000.

[0218] Various elastomers can be used as the hydrogenated styrene-based thermoplastic elastomer, as long as the content of styrene units is within the range of 14% by mass or more and 50% by mass or less, and the weight average molecular weight of the elastomer is within the range of 100,000 or more and 200,000 or less. Examples of hydrogenated styrene-based thermoplastic elastomers include hydrogenated polystyrene-poly(ethylene / propylene) block copolymers (SEP), hydrogenated styrene-isoprene-styrene block copolymers (SIS), hydrogenated styrene-butadiene-styrene block copolymers (SBS), hydrogenated styrene-butadiene-butylene-styrene block copolymers (SBBS), hydrogenated styrene-ethylene-butylene-styrene block copolymers (SEBS), hydrogenated styrene-ethylene-propylene-styrene block copolymers (styrene-isoprene-styrene block copolymers) (SEPS), hydrogenated styrene-ethylene-ethylene-propylene-styrene block copolymers (SEEPS), and hydrogenated polystyrene-poly(ethylene-ethylene / propylene) block-polystyrene block copolymers (SEEPS-OH: terminally hydroxyl group-modified), and those having a styrene unit content and weight average molecular weight within the above-mentioned ranges can be used.

[0219] Being a hydrogenated product improves thermal stability, makes it less susceptible to deterioration such as decomposition or polymerization, and also tends to improve solubility in hydrocarbon solvents and resistance to resist solvents.

[0220] Among the hydrogenated styrene-based thermoplastic elastomers, those which are block polymers with styrene at both ends are more preferred, because by blocking styrene, which has high thermal stability, at both ends, higher heat resistance is exhibited.

[0221] More specifically, the hydrogenated styrene-based thermoplastic elastomer is preferably a hydrogenated block copolymer of styrene and a conjugated diene. This elastomer has improved thermal stability and is less susceptible to degradation, such as decomposition or polymerization. Furthermore, blocking both ends with highly thermally stable styrene provides higher heat resistance. Furthermore, this elastomer is more preferable from the viewpoints of solubility in hydrocarbon solvents and resistance to resist solvents.

[0222] Examples of commercially available products that can be used as adhesive compositions containing hydrogenated styrene-based thermoplastic elastomers include "Septon (product name)" manufactured by Kuraray Co., Ltd., "Hybler (product name)" manufactured by Kuraray Co., Ltd., "Tuftec (product name)" manufactured by Asahi Kasei Corporation, and "Dynalon (product name)" manufactured by JSR Corporation.

[0223] The content of the (BCP) component in the adhesive composition (22) is preferably 5% by mass or more, and may be 10 to 50% by mass, or 15 to 25% by mass, relative to the total amount (100% by mass) of the adhesive composition (22). By keeping the thickness within these ranges, deformation due to external forces can be suppressed while maintaining heat resistance, and the substrate can be suitably fixed to the support.

[0224] Furthermore, a plurality of types of hydrogenated styrene-based thermoplastic elastomers may be mixed together, that is, the adhesive composition (22) may contain a plurality of types of hydrogenated styrene-based thermoplastic elastomers.

[0225] Dilution solvent Examples of the dilution solvent include the same dilution solvents as those exemplified in the description of the adhesive composition (21) above.

[0226] Other ingredients The adhesive composition (22) may further contain other compatible substances to the extent that the essential properties are not impaired. For example, various commonly used additives such as additional resins (e.g., acrylic resins) for improving the performance of the adhesive, curable monomers, polymerization inhibitors, polymerization initiators, plasticizers, adhesion aids, stabilizers, colorants, surfactants, and antioxidants can be further used.

[0227] Regarding the combination of the first adhesive layer and the second adhesive layer: In the laminate of this embodiment, preferred combinations of the first adhesive layer and the second adhesive layer are listed below.

[0228] Combination (1): The first adhesive layer is a layer formed from a first material, which is an adhesive composition (11) containing a thermoplastic resin, and the second adhesive layer is a layer formed from a second material, which is a cycloolefin-based adhesive composition (21).

[0229] Combination (2): The first adhesive layer is a layer formed from a first material, which is an adhesive composition (11) containing a thermoplastic resin, and the second adhesive layer is a layer formed from a second material, which is an elastomeric adhesive composition (22).

[0230] Combination (3): The first adhesive layer is a layer formed from a first material, which is an adhesive composition (12) containing a thermosetting resin, and the second adhesive layer is a layer formed from a second material, which is a cycloolefin-based adhesive composition (21).

[0231] Combination (4): The first adhesive layer is a layer formed from a first material, which is an adhesive composition containing an elastomer, and the second adhesive layer is a layer formed from a second material, which is a cycloolefin-based adhesive composition containing a thermoplastic resin including a cyclic olefin block copolymer.

[0232] Combination (5): The first adhesive layer is a layer formed from a first material, which is an adhesive composition containing an elastomer, and the second adhesive layer is a layer formed from a second material, which is an elastomeric adhesive composition containing a thermoplastic resin including a hydrogenated styrene-based thermoplastic elastomer.

[0233] Combination (6): The first adhesive layer is a layer formed from a first material, which is an adhesive composition containing a urethane resin, and the second adhesive layer is a layer formed from a second material, which is a cycloolefin-based adhesive composition containing a thermoplastic resin including a cyclic olefin block copolymer.

[0234] Combination (7): The first adhesive layer is a layer formed from a first material, which is an adhesive composition containing an elastomer, and the weight average molecular weight of the elastomer is in the range of 10,000 or more and 200,000 or less. The second adhesive layer is a layer formed from a second material, which is a cycloolefin-based adhesive composition containing a thermoplastic resin including a cyclic olefin block copolymer. The cyclic olefin block copolymer is a block copolymer having a first block and a second block. The first block is a block composed of a polymer consisting of a repeating structure of a structural unit (u1) derived from norbornene which may have a substituent. The second block is a block composed of a polymer consisting of a repeating structure of a structural unit (u2) derived from norbornene which may have a substituent and which has a structure different from that of the structural unit (u1).

[0235] Combinations (8): The first adhesive layer is a layer formed from a first material, which is an adhesive composition containing an elastomer, and the weight-average molecular weight of the elastomer is within the range of 10,000 or more and 200,000 or less. The second adhesive layer is a layer formed from a second material, which is an elastomer-based adhesive composition containing a thermoplastic resin including a hydrogenated styrene-based thermoplastic elastomer, and the weight-average molecular weight of the hydrogenated styrene-based thermoplastic elastomer is within the range of 100,000 or more and 200,000 or less.

[0236] Combinations (9): The first adhesive layer is a layer formed from a first material, which is an adhesive composition containing a urethane resin, and the urethane resin is a urethane resin containing a polymerizable carbon-carbon double bond. The second adhesive layer is a layer formed from a second material, which is a cycloolefin-based adhesive composition containing a thermoplastic resin including a cyclic olefin block copolymer. The cyclic olefin block copolymer is a block copolymer having a first block and a second block, and the first block is a block composed of a polymer consisting of a repeating structure of a structural unit (u1) derived from norbornene which may have a substituent, and the second block is a block composed of a polymer consisting of a repeating structure of a structural unit (u2) derived from norbornene which may have a substituent and which has a structure different from that of the structural unit (u1).

[0237] Combinations (10): The first adhesive layer is a layer formed from a first material, which is an adhesive composition (12) containing a thermosetting resin, and the second adhesive layer is a layer formed from a second material, which is an elastomeric adhesive composition (22).

[0238] In the laminate of this embodiment, the thickness ratio between the first adhesive layer and the second adhesive layer is preferably first adhesive layer / second adhesive layer = 1 / 9 to 9 / 1. When the thickness ratio is within the above-mentioned preferred range, deformation due to external force is easily suppressed while maintaining adhesion between the support and the device layer. The thickness ratio is more preferably first adhesive layer / second adhesive layer = 3 / 7 to 7 / 3.

[0239] <Device Layer> The device layer is a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member. Specifically, the device layer includes at least one of an encapsulant layer and a rewiring layer, and may further include a substrate. In the laminate 100 shown in FIG. 1, the device layer 45 is composed of a substrate 4 and an encapsulant layer 5.

[0240] <Substrate> The substrate (bare chip) is supported by a support and is subjected to processes such as thinning, mounting, etc. Structures such as integrated circuits and metal bumps are mounted on the substrate. The substrate is typically a silicon wafer substrate, but is not limited to this, and may be a ceramic substrate, a thin film substrate, a flexible substrate, or the like.

[0241] The substrate may be a semiconductor element or other element, and may have a single-layer or multi-layer structure. When the substrate is a semiconductor element, the electronic component obtained by dicing the device layer becomes a semiconductor device. Preferably, the substrate is a semiconductor element.

[0242] ≪Encapsulation material layer≫ The encapsulant layer is provided to encapsulate the substrate and is formed using an encapsulant that can insulate or encapsulate a member made of metal or semiconductor. As the sealing material, for example, a resin composition containing a resin is used. The resin used for the sealing material is not particularly limited as long as it can seal and / or insulate metals or semiconductors, and examples thereof include epoxy resins. The sealing material may contain other components such as a filler in addition to the resin. Examples of the filler include spherical silica particles.

[0243] <Laminate manufacturing method (1)> The laminate 100 shown in FIG. 1 can be produced, for example, by a production method including a separation layer forming step, an adhesive layer forming step, a device layer forming step, and a device layer fixing step.

[0244] [Separation layer formation process] The separation layer forming step is a step of forming a separation layer on one surface of a support substrate using the [separation layer forming composition] described below, thereby producing a support 12 composed of a support substrate 1 and a separation layer 2.

[0245] The method for forming the separation layer 2 on the support base 1 is not particularly limited, but examples thereof include spin coating, dipping, roller blade coating, spray coating, slit coating, and chemical vapor deposition (CVD). For example, in the separation layer formation process, the support 12 can be obtained by removing the solvent component from the coating layer of the separation layer forming composition applied to the support substrate 1 in a heated environment or a reduced pressure environment to form a film, or by forming a film on the support substrate 1 by a vapor deposition method.

[0246] [Adhesive layer formation process] The adhesive layer forming step includes an adhesive layer forming operation (1) for forming a first adhesive layer and an adhesive layer forming operation (2) for forming a second adhesive layer.

[0247] Adhesive layer forming operation (1): In the adhesive layer forming operation (1), a first adhesive layer 3A is formed on the separation layer 2 of the support 12 using an adhesive composition, which is a first material.

[0248] The method for forming the first adhesive layer 3A on the support 12 is not particularly limited, and examples thereof include spin coating, dipping, roller blade coating, spray coating, slit coating, etc. Then, the first material is applied to the support 12 and heated, or the solvent component contained in the first material is removed under a reduced pressure environment.

[0249] Thereafter, when the first adhesive layer 3A contains a curable monomer and a thermal polymerization initiator, the curable monomer may be polymerized by heating. The conditions for heating the first adhesive layer 3A may be appropriately set based on the one-minute half-life temperature and one-hour half-life temperature of the thermal polymerization initiator. Heating is preferably performed at a temperature in the range of, for example, 50 to 300°C under vacuum or in an inert gas atmosphere such as nitrogen gas, and more preferably in an inert gas atmosphere.

[0250] Furthermore, when the first adhesive layer 3A contains a curable monomer and a photopolymerization initiator, the curable monomer may be polymerized by exposure to light in an inert gas atmosphere such as nitrogen gas. The exposure conditions may be appropriately set depending on the type of photopolymerization initiator, etc.

[0251] Adhesive layer forming operation (2): In the adhesive layer forming operation (2), a second adhesive layer 3B is formed on the device layer 45 or on the first adhesive layer 3A using an adhesive composition, which is a second material. When forming the second adhesive layer 3B, the second adhesive layer 3B may be formed on the device layer 45 (sealant) using the second material, or the second adhesive layer 3B may be formed on the first adhesive layer 3A using the second material.

[0252] The method for forming the second adhesive layer 3B on the device layer 45 or the first adhesive layer 3A is not particularly limited, but examples include spin coating, dipping, roller blade, spray coating, slit coating, chemical vapor deposition (CVD), etc. For example, in the adhesive layer formation operation (2), the second adhesive layer 3B can be formed on the device layer 45 or the first adhesive layer 3A by removing the solvent component from the coating layer of the second material applied to the device layer 45 or the first adhesive layer 3A under a heated or reduced pressure environment and forming a film.

[0253] [Device layer formation process] The device layer forming step is a step of forming a device layer which is a composite of a member made of a metal or semiconductor and a resin that seals or insulates the member. The device layer formation step may include a sealing operation of sealing the substrate with an encapsulant.

[0254] Sealing operation: In the sealing operation, the substrates are sealed with a sealing material to produce a sealed body. The sealed body is used as device layer 45 in the method for producing a laminate according to this embodiment. The number of substrates to be sealed with the sealing material is not particularly limited, and may be the number necessary to form the desired device layer.

[0255] In the sealing operation, for example, a substrate is placed on a holding plate, and a sealing material heated to 130 to 170°C is supplied onto the holding plate so as to cover the substrate while maintaining a high viscosity, and then compression-molded to produce a sealed body. At this time, the temperature condition is, for example, 130 to 170°C. The pressure applied to the substrate is, for example, 50 to 500 N / cm 2 is.

[0256] [Device layer fixing process] The device layer fixing step is a step of fixing the device layer (encapsulated body) onto the support via an adhesive layer, thereby obtaining a laminate. In manufacturing the laminate 100, the device layer 45 is fixed onto the support 12 via the first adhesive layer 3A and the second adhesive layer 3B, thereby obtaining the laminate 100.

[0257] The method for fixing the device layer 45 on the support 12 is not particularly limited, and any known method used for bonding substrates or the like may be used. For example, the first adhesive layer 3A and the second adhesive layer 3B are placed opposite each other, and the device layer 45 is placed at a predetermined position on the support 12. Next, the support 12 and the substrate 4 are pressure-bonded together using a die bonder or the like while being heated under vacuum (for example, at about 100°C) (a so-called TCB process), thereby fixing the device layer 45 on the support 12. The temperature and pressure conditions in the TCB process are, for example, 200 to 350°C and 0.5 to 3.0 N / mm 2 The pressing time is 0.5 to 20 seconds.

[0258] As described above, in the laminate of this embodiment, the support and the device layer are bonded together via an adhesive layer, which is composed of a first adhesive layer adjacent to the support and a second adhesive layer adjacent to the device layer. The first adhesive layer and the second adhesive layer are each made of a specific material. By adopting this configuration, the laminate has a small amount of warping and is less resistant to deformation due to external forces (effect (i)), and the adhesive layer has good washability (effect (ii)).

[0259] Regarding effect (i): Figure 2A is a schematic diagram showing a state where a conventional laminate is used in a TCB process, and Figure 2B is a schematic diagram showing a state where laminate 100 is used in a TCB process.

[0260] In manufacturing the laminate, for example, die bonding may be performed on a device layer 45 (also called a bump substrate) that includes a substrate on which metal bumps are mounted.

[0261] FIG. 2A shows a case where a support 12 and a bump substrate are bonded together using a conventional laminate in a TCB process, and die bonding is performed on the bump substrate. The adhesive layer 3' in the laminate is, for example, a single layer formed from the first material described above. In this case, during die bonding, the adhesive layer 3' may be thermally deformed, sinking, causing the bumps to come into contact with the support 12, resulting in warping of the substrate and damage to the bumps.

[0262] FIG. 2B shows a case where the support 12 and the bump substrate are bonded together using the laminate 100 in the TCB process, and die bonding is performed on the bump substrate. In the laminate 100, the first adhesive layer 3A is a layer formed of a first material exhibiting an elastic modulus of 0.1 MPa or less under the temperature conditions when the support 12 and the device layer 45 (bump substrate) are bonded together. The second adhesive layer 3B is a layer formed of a second material containing a thermoplastic resin and exhibiting an elastic modulus of 20 MPa or more at 260°C. In this case, the increased elastic modulus of the second adhesive layer 3B makes the second adhesive layer 3B less susceptible to thermal deformation and sinking during die bonding (i.e., deformation due to external force is suppressed). This prevents contact between the bumps and the support 12. In addition, the second adhesive layer 3B has increased adhesion to the device layer 45 (bump substrate), making it less likely to peel off from the bump substrate. Furthermore, the laminate 100 also suppresses gas generation from the sealing body during heat treatment.

[0263] (Another embodiment of the laminate) FIG. 3 shows another embodiment of the laminate. The laminate 200 shown in FIG. 3 has the same configuration as the laminate 100 , except that the device layer is a device layer 456 made up of a substrate 4 , a sealing material layer 5 , and a rewiring layer 6 .

[0264] <Device Layer in Other Embodiments of the Laminate> In the stacked body 200 shown in FIG. 3, the device layer 456 is composed of a substrate 4, a sealing material layer 5, and a rewiring layer 6. The substrate 4 and the sealing material layer 5 are the same as those described above for the <<substrate>> and <<sealing material layer>>.

[0265] ≪Rewiring layer≫ The redistribution layer (RDL) is a thin-film wiring body that forms wiring connected to a substrate and may have a single-layer or multi-layer structure. The redistribution layer may be, but is not limited to, wiring formed by a conductor (for example, metals such as aluminum, copper, titanium, nickel, gold, and silver, and alloys such as silver-tin alloy) between patterned resin materials (such as photosensitive polyimide and photosensitive acrylic resin).

[0266] <Laminate manufacturing method (2)> The laminate 200 shown in FIG. 3 can be manufactured by a manufacturing method including, as an example, a separation layer forming step, an adhesive layer forming step, a device layer forming step, a device layer fixing step, a grinding step, and a rewiring layer forming step.

[0267] The separation layer forming step, adhesive layer forming step, device layer forming step, and device layer fixing step are the same as those described for the separation layer forming step, adhesive layer forming step, device layer forming step, and device layer fixing step in the above-mentioned <Laminate manufacturing method (1)>.

[0268] [Grinding process] The grinding step is a step in which, after the above-mentioned sealing operation, the sealant portion of the sealant (sealant layer 5) is ground so that part of the substrate 4 is exposed. Grinding of the sealing material portion is carried out by grinding the sealing material layer 5 until it has a thickness substantially equal to that of the substrate 4, for example, as shown in FIG.

[0269] [Rewiring layer formation process] The rewiring formation step is a step of forming a rewiring layer 6 on the exposed substrate 4 after the grinding step. The redistribution layer (RDL) is a thin-film wiring body that forms wiring connected to elements and can have a single-layer or multi-layer structure. For example, the redistribution layer can be made of a dielectric (silicon oxide (SiO x), photosensitive resin such as photosensitive epoxy, etc.) on which wiring is formed using a conductor (metal such as aluminum, copper, titanium, nickel, gold, silver, etc., and alloy such as silver-tin alloy, etc.), but is not limited to this.

[0270] The rewiring layer 6 is formed by first depositing silicon oxide (SiO x ), a dielectric layer of a photosensitive resin or the like is formed. The dielectric layer of silicon oxide can be formed by, for example, a sputtering method, a vacuum deposition method, or the like. The dielectric layer of a photosensitive resin can be formed by applying the photosensitive resin onto the encapsulant layer 5 by, for example, a method such as spin coating, dipping, roller blade, spray coating, or slit coating.

[0271] Subsequently, wiring is formed on the dielectric layer using a conductor such as a metal. The wiring can be formed by known semiconductor process techniques such as lithography processes such as photolithography (resist lithography), etching processes, etc. Examples of such lithography processes include lithography processes using a positive resist material and lithography processes using a negative resist material. Thus, when performing photolithography processing, etching processing, etc., the laminate is exposed to an acid such as hydrofluoric acid, an alkali such as tetramethylammonium hydroxide (TMAH), or a resist solvent for dissolving the resist material, and is also treated at high temperatures.

[0272] The method (2) for manufacturing a laminate explained above may further include a step of forming a bump on the rewiring layer 6 or mounting an element thereon, in addition to the above-mentioned embodiment. The elements can be mounted on the rewiring layer 6 using, for example, a chip mounter.

[0273] Regarding the laminate manufacturing method (2), in the above-described embodiment, the grinding step and the rewiring layer forming step are performed after the device layer forming step, but the grinding operation of the sealing material portion and the rewiring layer forming operation may also be performed during the device layer forming step.

[0274] (Electronic component manufacturing method) According to another aspect of the present invention, a method for manufacturing an electronic component is a manufacturing method including a separation step and a removal step after obtaining a laminate by the above-mentioned <Laminate manufacturing method (2)>.

[0275] 4A to 4C are schematic process diagrams illustrating one embodiment of a method for manufacturing a semiconductor package (electronic component). Fig. 4A shows a state in which light is irradiated onto the laminate from the support side. Fig. 4B shows a state in which the support base has been separated from the laminate. Fig. 4C shows a state in which the first adhesive layer, the second adhesive layer, and the separation layer have been removed by washing from the device layer.

[0276] [Separation process] The separation step is a step in which light (arrow) is irradiated onto separation layer 2 through support base 1 to alter separation layer 2, thereby separating device layer 456 from support base 1. In FIG. 4A, separation layer 2 is irradiated with light (arrow) through support base 1, thereby altering separation layer 2.

[0277] The wavelength capable of altering the separation layer 2 is, for example, in the range of 600 nm or less. The type and wavelength of the light to be irradiated may be appropriately selected depending on the transparency of the support base 1 and the material of the separation layer 2, and may include, for example, laser light or non-laser light, such as a solid-state laser such as a YAG laser, ruby ​​laser, glass laser, YVO4 laser, LD laser, or fiber laser, a liquid laser such as a dye laser, a gas laser such as a CO2 laser, excimer laser, Ar laser, or He-Ne laser, a semiconductor laser, or a free electron laser. This alters the separation layer 2, making it possible to easily separate the support base 1 and the device layer 456.

[0278] When irradiating with laser light, the following conditions can be given as an example of the laser light irradiation conditions. The average output power of the laser beam is preferably 1.0 W or more and 7.0 W or less, and more preferably 3.0 W or more and 7.0 W or less. The repetition frequency of the laser beam is preferably 20 kHz or more and 60 kHz or less, and more preferably 30 kHz or more and 50 kHz or less. The scanning speed of the laser beam is preferably 100 mm / s or more and 10,000 mm / s or less.

[0279] Separation layer 2 is irradiated with light (arrow) to alter the properties of separation layer 2, and then supporting base 1 is separated from device layer 456 as shown in FIG. 4B. For example, the support base 1 and the device layer 456 are separated by applying a force in a direction that moves them apart. Specifically, the support base 1 and the device layer 456 can be separated by fixing one of the support base 1 and the device layer 456 to a stage and lifting the other while suction-holding it with a separation plate equipped with an adsorption pad such as a bellows pad. The force applied to the laminate 200 can be adjusted appropriately depending on the size of the laminate 200, etc., and is not limited to any particular value. For example, for a laminate with a diameter of approximately 300 mm, the support base 1 and the device layer 456 can be suitably separated by applying a force of approximately 0.1 to 5 kgf (0.98 to 49 N).

[0280] [Removal process] The removal step is a step of removing the separation layer, the first adhesive layer, and the second adhesive layer attached to the device layer after the separation step. FIG. 4B shows a state in which the separation layer 2, the first adhesive layer 3A, and the second adhesive layer 3B remain attached to the device layer 456 after the separation step.

[0281] A method for removing the first adhesive layer 3A and the second adhesive layer 3B attached to the device layer 456 includes, for example, a method of removing the separation layer 2, the first adhesive layer 3A and the second adhesive layer 3B using a cleaning solution. The cleaning liquid preferably contains an organic solvent.

[0282] Regarding effect (ii): In FIG. 4C, in the removal step, the separation layer 2, the first adhesive layer 3A, and the second adhesive layer 3B attached to the device layer 456 are removed, thereby obtaining the electronic component 50. In the laminate 200, the second adhesive layer 3B adjacent to the device layer 456 is a layer formed from a second material that contains a thermoplastic resin and has an elastic modulus of 20 MPa or more at 260°C. Because the second adhesive layer 3B contains a thermoplastic resin, it is easily dissolved in the cleaning solution. This allows the adhesive layer to be easily removed from the device layer 456 by cleaning.

[0283] That is, according to the laminate to which the present invention is applied, it is possible to provide a laminate in which the amount of warping is small, deformation due to an external force is suppressed, and the adhesive layer is easily removable by washing.

[0284] Other embodiments: In the laminate 100 shown in FIG. 1 and the laminate 200 shown in FIG. 3, the support 12 is composed of a support base 1 and a separation layer 2, but is not limited to this, and the support may be composed of only a support base by using a first adhesive layer or a second adhesive layer that also functions as a separation layer.

[0285] In the laminate 100 and the laminate 200, the support base 1 and the separation layer 2 are adjacent to each other, but this is not limiting, and other layers may be provided between the support base 1 and the separation layer 2. In this embodiment, the other layers only need to be made of a material that transmits light. This allows layers that impart desirable properties to the laminate to be added as appropriate without preventing light from entering the separation layer 2. The wavelengths of light that can be used vary depending on the type of material that constitutes the separation layer 2. Therefore, the material that constitutes the other layers does not need to transmit light of all wavelengths, and can be appropriately selected from materials that transmit light of wavelengths that can alter the material that constitutes the separation layer 2.

[0286] In the method for manufacturing an electronic component according to the embodiment described above, after the removal step, the electronic component 50 may be further subjected to processes such as solder ball formation, dicing, and oxide film formation.

[0287] [Composition for forming separation layer] The separation layer-forming composition, which is a material for forming the separation layer, may contain, for example, a fluorocarbon, a polymer having a repeating unit including a structure having light absorption properties, an inorganic substance, a compound having an infrared absorbing structure, an infrared absorbing substance, a reactive polysilsesquioxane, or a resin component having a phenol skeleton. The separation layer-forming composition may also contain optional components such as a filler, a plasticizer, a thermal acid generator component, a photoacid generator component, an organic solvent component, a surfactant, a sensitizer, or a component that can improve the separability of the supporting substrate.

[0288] Fluorocarbon The separation layer may contain a fluorocarbon. A separation layer made of a fluorocarbon is altered by absorbing light, and as a result, loses the strength or adhesiveness it had before being irradiated with light. Therefore, by applying a slight external force (for example, by lifting the support), the separation layer is destroyed, making it easier to separate the support and the device layer. The fluorocarbon that constitutes the separation layer can be suitably formed into a film by a plasma CVD method. Fluorocarbons absorb light within a specific wavelength range depending on the type of fluorocarbon. By irradiating the separation layer with light within the range of wavelengths absorbed by the fluorocarbon used in the separation layer, the fluorocarbon can be suitably altered. The light absorption rate of the separation layer is preferably 80% or more.

[0289] The light to be irradiated onto the separation layer may be laser light, such as a solid-state laser (e.g., YAG laser, ruby ​​laser, glass laser, YVO4 laser, LD laser, fiber laser), a liquid laser (e.g., dye laser), a gas laser (e.g., CO2 laser, excimer laser, Ar laser, He-Ne laser), a semiconductor laser, a free electron laser, or a non-laser light, depending on the wavelength that can be absorbed by the fluorocarbon. Wavelengths that can alter the fluorocarbon include, for example, wavelengths in the range of 600 nm or less.

[0290] Polymers having repeating units containing light-absorbing structures The separation layer may contain a polymer having a repeating unit containing a structure having light absorption properties, and the polymer is altered when irradiated with light. Examples of the light-absorbing structure include an atomic group containing a conjugated π-electron system consisting of a substituted or unsubstituted benzene ring, a fused ring, or a heterocyclic ring. More specific examples of the light-absorbing structure include a cardo structure, or a benzophenone structure, a diphenylsulfoxide structure, a diphenylsulfone structure (bisphenylsulfone structure), a diphenyl structure, or a diphenylamine structure present in the side chain of the polymer. The light-absorbing structure can absorb light having a wavelength in a desired range depending on the type of the structure. For example, the wavelength of light that can be absorbed by the light-absorbing structure is preferably in the range of 100 to 2000 nm, and more preferably in the range of 100 to 500 nm.

[0291] Examples of light that can be absorbed by the light-absorbing structure include light emitted from a high-pressure mercury lamp (wavelength of 254 nm or more and 436 nm or less), a KrF excimer laser (wavelength of 248 nm), an ArF excimer laser (wavelength of 193 nm), an F2 excimer laser (wavelength of 157 nm), a XeCl laser (wavelength of 308 nm), a XeF laser (wavelength of 351 nm), or a solid-state UV laser (wavelength of 355 nm), or g-line (wavelength of 436 nm), h-line (wavelength of 405 nm), or i-line (wavelength of 365 nm).

[0292] ·Inorganic matter The separation layer may be made of an inorganic material. The inorganic material may be any material that changes its properties by absorbing light, and suitable examples include one or more materials selected from the group consisting of metals, metal compounds, and carbon. Metal compounds are compounds containing metal atoms, and examples include metal oxides and metal nitrides. Such inorganic materials include one or more selected from the group consisting of gold, silver, copper, iron, nickel, aluminum, titanium, chromium, SiO2, SiN, Si3N4, TiN, and carbon. The term "carbon" is a concept that may include allotropes of carbon, such as diamond, fullerene, diamond-like carbon, and carbon nanotubes. The inorganic substances absorb light having wavelengths in a specific range depending on the type of inorganic substance.

[0293] The light to be irradiated onto the separation layer made of an inorganic material may be laser light such as a solid laser such as a YAG laser, ruby ​​laser, glass laser, YVO4 laser, LD laser, or fiber laser, a liquid laser such as a dye laser, a gas laser such as a CO2 laser, excimer laser, Ar laser, or He-Ne laser, a semiconductor laser, or a free electron laser, or non-laser light, depending on the wavelength that can be absorbed by the inorganic material. The inorganic separation layer can be formed on the support substrate by known techniques such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, and spin coating.

[0294] Compounds with infrared absorbing structures The separation layer may contain a compound having an infrared absorbing structure, which is altered by absorbing infrared rays. Examples of structures having infrared absorption properties or compounds having such structures include alkanes, alkenes (vinyl, trans, cis, vinylidene, trisubstituted, tetrasubstituted, conjugated, cumulenic, cyclic), alkynes (monosubstituted, disubstituted), monocyclic aromatics (benzene, monosubstituted, disubstituted, trisubstituted), alcohols or phenols (free OH, intramolecular hydrogen bond, intermolecular hydrogen bond, saturated secondary, saturated tertiary, unsaturated secondary, unsaturated tertiary), acetals, ketals, aliphatic ethers, aromatic ethers, vinyl ethers, oxirane ring ethers, peroxide ethers, ketones, dialkyl carbonyls, aromatic carbonyls, enols of 1,3-diketones, o-hydroxyaryl ketones, dialkyl aldehydes, aromatic aldehydes, carboxylic acids (dimers, carboxylic acid anions), formates, acetates, conjugated esters, non-conjugated esters, aromatic esters, lactones (β-, γ-, δ-), aliphatic acid chlorides, and aromatic acid salts. compounds, acid anhydrides (conjugated, non-conjugated, cyclic, acyclic), primary amides, secondary amides, lactams, primary amines (aliphatic, aromatic), secondary amines (aliphatic, aromatic), tertiary amines (aliphatic, aromatic), primary amine salts, secondary amine salts, tertiary amine salts, ammonium ions, aliphatic nitriles, aromatic nitriles, carbodiimides, aliphatic isonitriles, aromatic isonitriles, isocyanates, thiocyanates, aliphatic isothiocyanates, aromatic isothiocyanates, aliphatic nitro compounds, aromatic nitro compounds, nitroamines, nitrosamines, nitrates, nitrites, nitroso bonds (aliphatic, aromatic, monomers, dimers), sulfur compounds such as mercaptans, thiophenols, or thiolic acids, thiocarbonyl groups, sulfoxides, sulfones, sulfonyl chlorides, primary sulfonamides, secondary sulfonamides, sulfates, carbon-halogen bonds, Si-A 1 Join(A 1 is H, C, O or halogen), PA 2 Join(A 2 is a H, C or O) or Ti—O bond.

[0295] Examples of the structure containing the carbon-halogen bond include -CH2Cl, -CH2Br, -CH2I, -CF2-, -CF3, -CH=CF2, -CF=CF2, aryl fluoride, and aryl chloride.

[0296] The above Si-A 1 Examples of structures containing bonds include SiH, SiH2, SiH3, Si-CH3, Si-CH2-, Si-C6H5, SiO-aliphatic, Si-OCH3, Si-OCH2CH3, Si-OC6H5, Si-O-Si, Si-OH, SiF, SiF2, and SiF3. Si-A 1 As the structure containing the bond, it is particularly preferable that a siloxane skeleton or a silsesquioxane skeleton is formed.

[0297] The above PA 2 Examples of structures containing bonds include PH, PH2, P-CH3, P-CH2-, P-C6H5, and A 3 3-PO(A 3 is an aliphatic group or an aromatic group), (A 4 O)3-PO(A 4 is an alkyl group), P-OCH3, P-OCH2CH3, P-OC6H5, POP, P-OH, or O=P-OH.

[0298] Examples of the compounds containing the Ti-O bond include: (i) alkoxytitanium compounds such as tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis(2-ethylhexyloxy)titanium, and titanium-i-propoxyoctylene glycolate; (ii) chelate titanium compounds such as di-i-propoxy bis(acetylacetonato)titanium and propanedioxytitanium bis(ethylacetoacetate); and (iii) i-C3H7O-[-Ti(Oi-C3H7)2-O-]. n -i-C3H7 or n-C4H9O-[-Ti(On-C4H9)2-O-] n(iv) titanium acylates such as tri-n-butoxytitanium monostearate, titanium stearate, di-i-propoxytitanium diisostearate, and (2-n-butoxycarbonylbenzoyloxy)tributoxytitanium; and (v) water-soluble titanium compounds such as di-n-butoxybis(triethanolaminato)titanium. Among them, di-n-butoxybis(triethanolaminato)titanium (Ti(OC4H9)2[OC2H4N(C2H4OH)2]2) is preferred as a compound containing a Ti-O bond.

[0299] The infrared absorbing structure can absorb infrared rays having wavelengths in a desired range depending on the type of structure selected. Specifically, the infrared absorbing structure can absorb infrared rays having wavelengths in the range of 1 to 20 μm, for example, and more preferably in the range of 2 to 15 μm. Furthermore, when the structure is an Si—O bond, an Si—C bond, or a Ti—O bond, the thickness is preferably within the range of 9 to 11 μm.

[0300] Those skilled in the art can easily understand the infrared wavelengths that can be absorbed by each of the above structures. For example, the absorption bands of each structure can be found in the non-patent literature, "Spectroscopic Identification of Organic Compounds (5th Edition) - Combined Use of MS, IR, NMR, and UV" (published in 1992), pages 146 to 151, by Silverstein, Bassler, and Morrill.

[0301] The compound having an infrared absorbing structure used to form the separation layer is not particularly limited, as long as it can be dissolved in a solvent for application and solidified to form a solid layer among the compounds having the structure described above. However, in order to effectively alter the compound in the separation layer and facilitate separation of the support substrate and the device layer, it is preferable that the separation layer has high infrared absorption, that is, low infrared transmittance when irradiated with infrared rays. Specifically, the infrared transmittance of the separation layer is preferably less than 90%, and more preferably less than 80%.

[0302] Infrared absorbing materials The separation layer may contain an infrared absorbing material, which may be any material that changes its properties when it absorbs light, and suitable examples of such materials include carbon black, iron particles, and aluminum particles. Each type of infrared absorbing material absorbs light having a specific range of wavelengths. By irradiating the separation layer with light having a wavelength within the range absorbed by the infrared absorbing material used in the separation layer, the infrared absorbing material can be suitably altered.

[0303] Reactive polysilsesquioxane The separation layer can be formed by polymerizing a reactive polysilsesquioxane, and the resulting separation layer has high chemical resistance and high heat resistance.

[0304] The term "reactive polysilsesquioxane" refers to a polysilsesquioxane having a silanol group or a functional group capable of forming a silanol group upon hydrolysis at the end of the polysilsesquioxane skeleton. The silanol groups or the functional groups capable of forming a silanol group can be polymerized with each other by condensing them. Furthermore, as long as the reactive polysilsesquioxane has a silsesquioxane skeleton with a random structure, a cage structure, a ladder structure, or the like, it is possible to use a reactive polysilsesquioxane having a silanol group or a functional group capable of forming a silanol group.

[0305] The siloxane content of the reactive polysilsesquioxane is preferably 70 to 99 mol %, and more preferably 80 to 99 mol %. When the siloxane content of the reactive polysilsesquioxane is within the above-mentioned preferred range, a separation layer can be formed that can be suitably altered by irradiation with infrared rays (preferably far infrared rays, more preferably light with a wavelength of 9 to 11 μm).

[0306] The weight average molecular weight (Mw) of the reactive polysilsesquioxane is preferably 500 to 50,000, and more preferably 1,000 to 10,000. When the weight average molecular weight (Mw) of the reactive polysilsesquioxane is within the above-mentioned preferred range, it can be suitably dissolved in a solvent and can be suitably applied onto a support plate.

[0307] Examples of commercially available reactive polysilsesquioxanes that can be used include SR-13, SR-21, SR-23, and SR-33 (trade names) manufactured by Konishi Chemical Industry Co., Ltd.

[0308] Resin components with a phenolic skeleton The separation layer may contain a resin component having a phenol skeleton, which is easily altered (oxidized, etc.) by heating or the like, thereby increasing photoreactivity. Here, "having a phenol skeleton" means containing a hydroxybenzene structure. The resin component having a phenol skeleton has film-forming ability and preferably has a molecular weight of 1,000 or more. When the molecular weight of the resin component is 1,000 or more, the film-forming ability is improved. The molecular weight of the resin component is more preferably 1,000 to 30,000, further preferably 1,500 to 20,000, and particularly preferably 2,000 to 15,000. When the molecular weight of the resin component is equal to or less than the upper limit of the above-mentioned preferred range, the solubility of the separation layer-forming composition in a solvent is increased.

[0309] Examples of resin components having a phenol skeleton include novolac phenol resins, resol phenol resins, hydroxystyrene resins, hydroxyphenyl silsesquioxane resins, hydroxybenzyl silsesquioxane resins, acrylic resins containing a phenol skeleton, etc. Among these, novolac phenol resins and resol phenol resins are more preferred. [Example]

[0310] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0311] The materials used in this example are listed below.

[0312] Resin component in the first material Q-1: Hydrogenated styrene-based thermoplastic elastomer. Q-2: Hydrogenated styrene-based thermoplastic elastomer. Q-3: Hydrogenated styrene-based thermoplastic elastomer.

[0313] Q-4: Urethane resin obtained in the synthesis example below. A mixture was prepared by adding propylene glycol monomethyl ether acetate (PGMEA), 53 parts by mass of polycarbonate diol (Mw 1000), 18 parts by mass of pentaerythritol diacrylate (PEDA), 1 part by mass of neopentyl diol, and 2.5 parts by mass of hydroxyethyl acrylate (HEA) to a flask equipped with a stirrer, a dropping funnel, a condenser, and a thermometer, and mixing the contents uniformly under a nitrogen stream. Next, 7 parts by mass of diphenylmethane diisocyanate (MDI) and 21 parts by mass of hydrogenated xylylene diisocyanate (H6XDI) were charged into the dropping funnel and added dropwise to the mixed liquid at a constant rate over 30 minutes. After the dropwise addition, the mixture was aged for 30 minutes. Then, a bismuth catalyst was added, and the mixture was heated to 65°C and aged for 4 to 5 hours. Next, methanol was added, and the mixture was aged for 1 hour. The reaction was terminated when the isocyanate group (NCO) disappeared, yielding urethane resin Q-4. The molecular weight (Mw) of the resulting urethane resin Q-4 was 30,000.

[0314] The polycarbonate diol used was a compound represented by the following chemical formula (PC-1-1) (R=-(CH2)6-, -(CH2)5-), where n represents the number of repeats.

[0315] [ka]

[0316] Q-5: Urethane resin obtained in the synthesis example below. A mixture was prepared by adding propylene glycol monomethyl ether acetate (PGMEA), 57 parts by mass of polycarbonate diol (Mw 1000), 14 parts by mass of pentaerythritol diacrylate (PEDA), 1 part by mass of neopentyl diol, and 2.5 parts by mass of hydroxyethyl acrylate (HEA) to a flask equipped with a stirrer, a dropping funnel, a condenser, and a thermometer, and mixing the contents uniformly under a nitrogen stream. Next, 7 parts by mass of diphenylmethane diisocyanate (MDI) and 21 parts by mass of hydrogenated xylylene diisocyanate (H6XDI) were charged into the dropping funnel and added dropwise to the mixed liquid at a constant rate over 30 minutes. After the dropwise addition, the mixture was aged for 30 minutes. After that, a bismuth catalyst was added, and the mixture was heated to 65°C and aged for 4 to 5 hours. Next, methanol was added, and the mixture was aged for 1 hour. The reaction was terminated when the isocyanate group (NCO) disappeared, yielding urethane resin Q-5. The molecular weight (Mw) of the resulting urethane resin Q-5 was 30,000.

[0317] Resin component in the second material P-1: Block copolymer represented by the following chemical formula (BCP-1). Weight average molecular weight (Mw) 320,000; n / m = 1 / 1 (molar ratio), R is a linear alkyl group with 10 carbon atoms. PRZ-X10495 (manufactured by Sumitomo Bakelite Co., Ltd.)

[0318] [ka]

[0319] P-2: Block copolymer represented by the following chemical formula (BCP-2). Weight average molecular weight (Mw) 410,000; n / m / l = 1 / 1 / 1 (molar ratio), R is a linear alkyl group with 10 carbon atoms. PRZ-X10496 (manufactured by Sumitomo Bakelite Co., Ltd.)

[0320] [ka]

[0321] P-3: Hydrogenated styrene-based thermoplastic elastomer represented by the following chemical formula (P-3). Mw 150,000.

[0322] [ka]

[0323] P-4: Homopolymer (poly n-butylnorbornene) represented by the following chemical formula (P-4). Mw 500,000.

[0324] [ka]

[0325] P-5: Thermosetting novolac epoxy resin represented by the following chemical formula (P-5). Mw 1300. Ra 11 is a methyl group, Ra 12 is a methyl group, R EP is a glycidyl group.

[0326] [ka]

[0327] <Preparation of the adhesive composition as the first material (1)> As the adhesive composition, which is the first material, the following elastomer adhesives were used.

[0328] Elastomer adhesive containing Q-1 as a resin component: TZNR-A4017 (product name), manufactured by Tokyo Ohka Kogyo Co., Ltd. Elastomer adhesive containing Q-2 as a resin component: TZNR-A4035 (product name), manufactured by Tokyo Ohka Kogyo Co., Ltd. Elastomer adhesive containing Q-3 as a resin component: TZNR-A4031 (trade name), manufactured by Tokyo Ohka Kogyo Co., Ltd.

[0329] <Preparation of the adhesive composition as the first material (2)> An adhesive composition (solid content concentration 54% by mass) was prepared by mixing and dissolving 70 parts by mass of the above Q-4, 30 parts by mass of the following urethane acrylate, 1 part by mass of the following polymerization initiator, 5 parts by mass of the following silane coupling agent, 0.1 parts by mass of BYK-310 (polyester-modified silicone surfactant, manufactured by BYK-Chemie), and 90 parts by mass of propylene glycol monomethyl ether acetate, thereby obtaining a first material.

[0330] An adhesive composition (solid content concentration 54% by mass) was prepared by mixing and dissolving 70 parts by mass of the above Q-5, 30 parts by mass of the following urethane acrylate, 1 part by mass of the following polymerization initiator, 5 parts by mass of the following silane coupling agent, 0.1 parts by mass of BYK-310 (polyester-modified silicone surfactant, manufactured by BYK-Chemie), and 90 parts by mass of propylene glycol monomethyl ether acetate, thereby obtaining a first material.

[0331] [ka]

[0332] <Preparation of the adhesive composition as the second material> An adhesive composition (solid content concentration 15% by mass) was prepared as the second material by mixing and dissolving 100 parts by mass of the resin component of P-1 described above with 570 parts by mass of decahydronaphthalene as a solvent. An adhesive composition (solid content concentration 15% by mass) was prepared as the second material by mixing and dissolving 100 parts by mass of the resin component of P-2 described above with 570 parts by mass of decahydronaphthalene as a solvent. An adhesive composition (solid content concentration 20% by mass) was prepared as the second material by mixing and dissolving 100 parts by mass of the resin component of P-3 described above with 400 parts by mass of decahydronaphthalene as a solvent. An adhesive composition (solid content concentration 20% by mass) was prepared as the second material by mixing and dissolving 100 parts by mass of the resin component of P-4 described above with 400 parts by mass of decahydronaphthalene as a solvent. An adhesive composition (solid content concentration 60% by mass) was prepared as the second material by mixing and dissolving 100 parts by mass of the resin component of P-5 described above and 70 parts by mass of PGMEA as a solvent.

[0333] <Laminate manufacturing example> Example 1 TZNR-CTRL9 (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was spin-coated onto an 8-inch glass (support) as a composition for forming a separation layer, baked at 90°C for 3 minutes, and then baked in an oven at 320°C for 60 minutes to form a separation layer. Meanwhile, a second material containing P-1 was spin-coated onto an 8-inch silicon wafer (device layer) and baked at temperatures of 90°C, 160°C, and 220°C for 3 minutes each to form a second adhesive layer with a thickness of 30 μm. Next, a first material containing Q-1 was applied onto the second adhesive layer and baked for 3 minutes at temperatures of 90°C, 160°C, and 220°C, respectively, to form a first adhesive layer with a film thickness of 30 μm. Next, the support on which the separation layer was formed was laminated on the first adhesive layer to obtain a laminate in which the support, separation layer, first adhesive layer, second adhesive layer and device layer were laminated in this order.

[0334] Example 2 Except for changing the second material containing P-1 to a second material containing P-2, a laminate was obtained in the same manner as in Example 1, in which a support, a separation layer, a first adhesive layer, a second adhesive layer, and a device layer were stacked in this order.

[0335] Example 3 Except for changing the first material containing Q-1 to the first material containing Q-2, a laminate was obtained in the same manner as in Example 1, in which a support, a separation layer, a first adhesive layer, a second adhesive layer, and a device layer were stacked in this order.

[0336] Example 4 Except for changing the first material containing Q-1 to a first material containing Q-3, a laminate was obtained in the same manner as in Example 1, in which a support, a separation layer, a first adhesive layer, a second adhesive layer, and a device layer were stacked in this order.

[0337] Example 5 Except for changing the second material containing P-1 to a second material containing P-3, a laminate was obtained in the same manner as in Example 1, in which a support, a separation layer, a first adhesive layer, a second adhesive layer, and a device layer were stacked in this order.

[0338] Example 6 The separation layer-forming composition was spin-coated on an 8-inch glass (support), baked at 90°C for 3 minutes, and then baked in an oven at 320°C for 60 minutes to form a separation layer. Meanwhile, a second material containing P-1 was spin-coated onto an 8-inch silicon wafer (device layer) and baked at temperatures of 90°C, 160°C, and 220°C for 3 minutes each to form a second adhesive layer with a thickness of 30 μm. Next, a first material containing Q-4 was applied onto the second adhesive layer and baked at 100° C. for 10 minutes to form a first adhesive layer with a film thickness of 30 μm. Next, the support on which the separation layer was formed was laminated on the first adhesive layer, and heated in an oven under a nitrogen atmosphere at 200°C for 1 hour to harden each adhesive layer, thereby obtaining a laminate in which the support, separation layer, first adhesive layer, second adhesive layer, and device layer were laminated in this order.

[0339] Example 7 Except for changing the first material containing Q-4 to the first material containing Q-5, a laminate was obtained in the same manner as in Example 6, in which a support, a separation layer, a first adhesive layer, a second adhesive layer and a device layer were stacked in this order.

[0340] (Comparative Example 1) The separation layer-forming composition was spin-coated on an 8-inch glass (support), baked at 90°C for 3 minutes, and then baked in an oven at 320°C for 60 minutes to form a separation layer. Meanwhile, a first material containing Q-1 was applied to an 8-inch silicon wafer (device layer) and baked at temperatures of 90°C, 160°C, and 220°C for 3 minutes each to form a first adhesive layer with a film thickness of 30 μm. Next, the support on which the separation layer was formed was laminated on the first adhesive layer to obtain a laminate in which the support, separation layer, first adhesive layer, and device layer were laminated in this order.

[0341] (Comparative Example 2) Except for changing the second material containing P-1 to a second material containing P-4, a laminate was obtained in the same manner as in Example 1, in which a support, a separation layer, a first adhesive layer, a second adhesive layer, and a device layer were stacked in this order.

[0342] (Comparative Example 3) A second material containing P-5 was applied to an 8-inch silicon wafer (device layer) and baked at 100°C for 5 minutes to form a second adhesive layer with a thickness of 30 μm. The wafer was then heated in an oven under a nitrogen atmosphere at 200°C for 1 hour to harden the P-5. Next, a first material containing Q-2 was applied onto the second adhesive layer and baked at temperatures of 90°C, 160°C, and 220°C for 3 minutes each to form a first adhesive layer with a film thickness of 30 μm. Next, the support on which the separation layer was formed was laminated on the first adhesive layer to obtain a laminate in which the support, separation layer, first adhesive layer, second adhesive layer and device layer were laminated in this order.

[0343] <Evaluation> The first adhesive layer was evaluated for its modulus of elasticity at the attachment temperature. The second adhesive layer was evaluated for its modulus of elasticity at 260° C., film stress, amount of warpage, adhesion, and removability by washing.

[0344] [Elastic modulus at application temperature] The first material containing each resin component was spin-coated onto a silicon wafer using a spin coater method, and baked for 4 minutes at temperatures of 90°C, 160°C, and 220°C, respectively, to form an adhesive layer with a thickness of 50 μm. A test piece (film thickness 50 μm, width 5 mm, length 40 mm) of the adhesive layer was cut out, and the tensile modulus was measured at a frequency of 1 Hz in the range of 50 to 300° C. using Rheogel-E4000 (manufactured by UBM). The modulus of elasticity at the attachment temperatures shown in Table 1 (temperature conditions when the support and device layer were attached) is also shown in Table 1.

[0345] [Elastic modulus at 260℃] The second material containing each resin component was spin-coated onto a silicon wafer using a spin coater method, and baked for 4 minutes at temperatures of 90°C, 160°C, and 220°C, respectively, to form an adhesive layer with a thickness of 50 μm. A test piece (film thickness 50 μm, width 5 mm, length 40 mm) of the adhesive layer was cut out, and the tensile modulus was measured at a frequency of 1 Hz in the range of 50 to 300° C. using Rheogel-E4000 (manufactured by UBM). The modulus at 260° C. is shown in Table 1.

[0346] [Membrane stress, warpage] The "warpage amount" of an 8-inch silicon wafer with a thickness of 725 μm±25 μm was measured in advance using a residual stress measuring device (manufactured by Tencor Corporation, model name FLX3300-T). The second material containing each resin component was spin-coated onto the 8-inch silicon wafer and baked at temperatures of 90°C, 160°C, and 220°C for 4 minutes each to form an adhesive layer with a thickness of 50 μm. The amount of warpage [μm] of the 8-inch silicon wafer on which the adhesive layer was formed was measured using the residual stress measurement device, and the film stress [MPa] generated between the 8-inch silicon wafer and the adhesive layer was evaluated. The film stress [MPa] and the amount of warpage [μm] are shown in Table 1.

[0347] [Virtual TCB Test] After producing the stack for each example, the 8-inch silicon wafer (device layer) that constituted the stack was ground to a thickness of 50 μm. After grinding, a Si chip cut to 2 mm x 2 mm was attached to the device layer surface with a force of 3 N / mm using a benchtop die bonder T-3000-FC3 with a stage temperature of 100°C and a bonder terminal temperature of 300°C. 2 The device was pressed down with a force of 1000 for 5 seconds. This Si chip pressing operation was repeated eight times. After that, the depth [μm] of the second adhesive layer pressed by the Si chip was measured. The results are shown in Table 1 as virtual TCB test [μm]. It is considered that there is no problem if the pressing depth is 3 μm or less, and the second adhesive layer is unlikely to deform during the thermal process.

[0348] [Washing removability of adhesive layer (1)] A first material containing Q-1 to Q-3 and a second material containing P-1 to P-4 were spin-coated onto a Si substrate using a spin coater, and baked for 3 minutes at temperatures of 90°C, 160°C, and 220°C, respectively, to form an adhesive layer with a thickness of 20 μm. The Si substrate with the adhesive layer formed was immersed in HC-thinner (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at room temperature. If the substrate dissolved within 30 minutes of immersion, it was rated as "A." If the adhesive layer remained after 30 minutes, it was rated as "B." The evaluation results for the first material and the second material are shown in Table 1 as "cleaning removability of the first adhesive layer" and "cleaning removability of the second adhesive layer," respectively.

[0349] [Washability of adhesive layer (2)] A first material containing Q-4 to Q-5 and a second material containing P-5 were applied to a thickness of 20 μm on a Si substrate using a spin coater method, and the resulting mixture was heated in an oven under a nitrogen atmosphere at 180°C for 1 hour to form an adhesive layer. The Si substrate with the adhesive layer formed thereon was immersed in an alkali-containing cleaning solution (ST-120 (trade name), manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 70°C. If the substrate dissolved within 30 minutes of immersion, it was rated as "A," and if the adhesive layer remained after 30 minutes, it was rated as "B." The evaluation results for the first material and the second material are shown in Table 1 as "cleaning removability of the first adhesive layer" and "cleaning removability of the second adhesive layer," respectively.

[0350] [Adhesion] The second materials containing each resin component were applied onto a silicon substrate (size 6 inches, thickness 675 μm) by spin coating while rotating at 1000 rpm. Next, each of the silicon substrates coated with the second material was preheated at 90° C. for 4 minutes to form an adhesive layer with a thickness of 35 μm. Next, the adhesive layer was linearly cut using a cutter. The cutting line of the adhesive layer thus formed was set to cross the silicon substrate. The distance [mm] from the cutting line to which the adhesive layer peeled was measured, and the adhesion between the silicon substrate and the adhesive layer was evaluated. The results are shown in Table 1. A shorter peel distance indicates better adhesion of the adhesive layer to the silicon substrate.

[0351] [Table 1]

[0352] From the results shown in Table 1, it can be confirmed that the laminates of Examples 1 to 7 had a small amount of warping, were less susceptible to deformation due to external forces, and all of the adhesive layers had good removability by washing. It was also confirmed that the adhesive layer formed from the second material was resistant to deformation during the thermal process and had good adhesion to the silicon substrate. [Explanation of symbols]

[0353] 1 Supporting base 2 separation layer 3' adhesive layer 3A First Adhesive Layer 3B Second adhesive layer 4 boards 5 Encapsulant layer 6 Redistribution layer 12 Support 45 Device Layer 50 Electronic Components 100 laminate 200 laminate 456 Device Layer

Claims

1. A laminate in which a support, a first adhesive layer, a second adhesive layer, and a device layer are laminated in this order, the first adhesive layer is a layer formed of a first material exhibiting an elastic modulus of 0.1 MPa or less under temperature conditions when the support and the device layer are bonded together, A laminate, wherein the second adhesive layer is a layer formed from a second material that contains a thermoplastic resin and exhibits an elastic modulus of 20 MPa or more at 260°C.

2. The laminate according to claim 1 , wherein the second material further exhibits a membrane stress of 15 MPa or less.

3. The laminate according to claim 1 , wherein the thermoplastic resin contained in the second material comprises a cyclic olefin block copolymer.

4. The laminate of claim 1 , wherein the first adhesive layer is removable with a cleaning solution containing an organic solvent.

5. The laminate according to claim 1 , wherein the thermoplastic resin contained in the second material includes a hydrogenated styrene-based thermoplastic elastomer.

6. The laminate of claim 1 , wherein the first material is an adhesive composition containing a thermoplastic resin.

7. The laminate of claim 1 , wherein the first material is an adhesive composition containing a thermosetting resin.

8. the support includes a support base that transmits light, and a separation layer that is formed on the support base and that changes in quality when irradiated with light; The laminate according to any one of claims 1 to 7, wherein the separation layer and the first adhesive layer are provided adjacent to each other.

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