Adhesive composition, laminate, laminate manufacturing method, and electronic component manufacturing method

Abstract

To provide an adhesive composition which dispenses with a separation layer, a laminate manufactured using the adhesive composition, a method for manufacturing the laminate, and a method for manufacturing an electronic component using the adhesive composition.SOLUTION: An adhesive composition is used for forming an adhesive layer for temporarily bonding a semiconductor substrate or an electronic device to a support for transmitting light, and contains a resin (P1), and a polymerization initiator (A), wherein the resin (P1) has a structural unit (u1) having such a structure as to absorb at least a part of light of a wavelength of 300-800 nm, and the storage elastic modulus (G') at 150°C of the adhesive layer formed of the adhesive composition is 1.5×105 Pa or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an adhesive composition, a laminate, a method for producing a laminate, and a method for producing an electronic component. [Background technology]

[0002] Semiconductor packages (electronic components) containing semiconductor elements come in a variety of forms depending on the corresponding size, such as wafer level packages (WLPs) and panel level packages (PLPs). Semiconductor packaging technologies include fan-in technology and fan-out technology. Known semiconductor packages using fan-in technology include fan-in WLP (Fan-in Wafer Level Package), which rearranges terminals at the edge of a bare chip within the chip area. Known semiconductor packages using fan-out technology include fan-out WLP (Fan-out Wafer Level Package), which rearranges the terminals outside the chip area.

[0003] In recent years, fan-out technology in particular has been attracting attention as a method for achieving even higher integration, thinner and smaller semiconductor packages, for example, through its application to fan-out panel level packages (PLPs), in which semiconductor elements are arranged on a panel and packaged.

[0004] In order to miniaturize semiconductor packages, it is important to reduce the thickness of the substrate in which the integrated device is mounted. 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 technique is known in which the substrate is temporarily attached to a support using an adhesive, and then the substrate and support are separated after processing.

[0005] Thermoplastic adhesives are often used as adhesives for temporarily bonding a substrate and a support, because the adhesive layer can be easily removed using a solvent, etc. For example, Patent Document 1 discloses an adhesive composition containing a thermoplastic elastomer, a high-boiling point solvent, and a low-boiling point solvent. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2016 / 052315 Summary of the Invention [Problem to be solved by the invention]

[0007] Conventional adhesives usually require a separation layer to separate the support and the substrate after processing the substrate, which requires the formation of the separation layer and the adhesive layer separately, making the process complicated.

[0008] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an adhesive composition that does not require a separation layer, a laminate produced using the adhesive composition, a method for producing the laminate, and a method for producing an electronic component using the adhesive composition. [Means for solving the problem]

[0009] In order to solve the above problems, the present invention employs the following configuration. That is, a first aspect of the present invention is an adhesive composition used to form an adhesive layer that temporarily bonds a semiconductor substrate or an electronic device to a light-transmitting support, the adhesive composition comprising a resin (P1) and a polymerization initiator (A), the resin (P1) having a structural unit (u1) that includes a structure that absorbs at least a portion of light in a wavelength range of 300 to 800 nm, and an adhesive composition layer formed from the adhesive composition having a storage modulus (G') at 150°C of 1.5 × 10 5 The adhesive composition has a viscosity of 100 Pa or less.

[0010] A second aspect of the present invention is a laminate comprising a light-transmitting support, an adhesive layer, and a semiconductor substrate or an electronic device laminated in this order, wherein the adhesive layer is a cured product of the adhesive composition according to the first aspect.

[0011] A third aspect of the present invention is a method for producing a laminate in which a light-transmitting support, an adhesive layer, and a semiconductor substrate are laminated in this order, the method comprising the steps of applying the adhesive composition according to the first aspect to the support or the semiconductor substrate to form an adhesive composition layer, placing the semiconductor substrate on the support with the adhesive composition layer interposed therebetween, and curing the adhesive composition layer to form the adhesive layer.

[0012] A fourth aspect of the present invention is a method for producing a laminate in which a light-transmitting support, an adhesive layer, and an electronic device are laminated in this order, the method further comprising an electronic device formation step of forming an electronic device, which is a composite of a member made of a metal or semiconductor and a resin that seals or insulates the member, after obtaining a laminate by the method for producing a laminate according to the third aspect.

[0013] A fifth aspect of the present invention is a method for manufacturing an electronic component, comprising the steps of: obtaining a laminate by the method for manufacturing a laminate according to the fourth aspect; separating the electronic device from the support by irradiating the adhesive layer with light through the support to alter the adhesive layer; and removing the adhesive layer attached to the electronic device. [Effects of the Invention]

[0014] According to the present invention, there are provided an adhesive composition that allows easy removal of an adhesive layer that does not require a separation layer, a laminate produced using the adhesive composition, a method for producing the laminate, and a method for producing an electronic component using the adhesive composition. [Brief explanation of the drawings]

[0015] [Figure 1]1 is a schematic diagram showing an embodiment of a laminate to which the present invention is applied. [Figure 2] 1 is a schematic diagram showing an embodiment of a laminate to which the present invention is applied. [Figure 3] 1 is a schematic diagram showing an embodiment of a laminate to which the present invention is applied. [Figure 4] 1 is a schematic diagram showing an embodiment of a laminate to which the present invention is applied. [Figure 5] 5A and 5B are schematic process diagrams illustrating one embodiment of a method for producing a laminate 100' in which a support, an adhesive composition layer, and a semiconductor substrate are laminated in this order. Fig. 5A is a diagram illustrating the adhesive composition layer forming step, and Fig. 5B is a diagram illustrating the semiconductor substrate placing step. [Figure 6] 10A to 10C are diagrams illustrating an adhesive layer forming step. [Figure 7] 7A and 7B are schematic process diagrams illustrating one embodiment of a method for manufacturing a laminate 120. Fig. 7A is a diagram illustrating a sealing process, Fig. 7B is a diagram illustrating a grinding process, and Fig. 7C is a diagram illustrating a wiring layer formation process. [Figure 8] 8A and 8B are schematic process diagrams illustrating one embodiment of a method for manufacturing a semiconductor package (electronic component) from the laminate 120. Fig. 8A is a diagram illustrating the laminate 200, Fig. 8B is a diagram illustrating the separation step, and Fig. 8C is a diagram illustrating the adhesive layer removal step. DETAILED DESCRIPTION OF THE INVENTION

[0016] 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.

[0017] A "structural unit derived from hydroxystyrene" refers to a structural unit formed by cleavage of the ethylenic double bond of hydroxystyrene. A "structural unit derived from a hydroxystyrene derivative" refers to a structural unit formed by cleavage of the ethylenic double bond of a hydroxystyrene derivative. The term "hydroxystyrene derivative" encompasses hydroxystyrenes 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 hydroxystyrenes 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 hydroxystyrenes 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 the hydroxystyrene include the same groups as those exemplified as the substituent at the α-position in the above-mentioned α-substituted acrylic ester.

[0018] 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.

[0019] In this specification and claims, some structures represented by chemical formulas may have asymmetric carbon atoms, and may have enantiomers or diastereomers, but in such cases, a single formula will be used to represent all of these isomers. These isomers may be used alone or as a mixture.

[0020] (Adhesive composition) The adhesive composition according to a first aspect of the present invention is used to form an adhesive layer that temporarily bonds a semiconductor substrate or an electronic device to a light-transmitting support. The adhesive composition according to this aspect contains a resin (P1) and a polymerization initiator (A). The resin (P1) has a structural unit (u1) that includes a structure that absorbs at least a portion of light in a wavelength range of 300 to 800 nm. The storage modulus (G') at 150°C of the adhesive composition layer formed from the adhesive composition is 1.5 x 10 5 Pa or less.

[0021] <Target for temporary adhesion> The adhesive composition according to the present embodiment is used to form an adhesive layer that temporarily bonds a semiconductor substrate or an electronic device to a support. In this specification, "temporary bonding" refers to the temporary bonding of the objects to be bonded (for example, during any work process). More specifically, the semiconductor substrate or electronic device is temporarily bonded to a support and fixed on the support (temporary bonding) for purposes such as thinning the device, transporting the semiconductor substrate, and mounting on the semiconductor substrate, and is then separated from the support after the process is completed.

[0022] <Semiconductor substrate> The semiconductor substrate to which the adhesive composition according to the present embodiment is applied is not particularly limited, and may be a substrate generally used as a semiconductor substrate. The semiconductor substrate (bare chip) is subjected to processes such as thinning and mounting while supported on a support. Structures such as integrated circuits and metal bumps may be mounted on the semiconductor substrate. A typical example of a semiconductor substrate is 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.

[0023] <Electronic Devices> In this specification, the term "electronic device" refers to a member that constitutes at least a part of an electronic component. The electronic device is not particularly limited and may be one in which various mechanical structures or circuits are formed on the surface of a semiconductor substrate. The electronic device may preferably be a composite of a member made of a metal or semiconductor and a resin that seals or insulates the member. The electronic device may be one in which a rewiring layer (described later) and / or a semiconductor element or other element is sealed or insulated with a sealing material or an insulating material, and may have a single-layer or multi-layer structure.

[0024] ≪Support≫ The support is a member that supports a semiconductor substrate or an electronic device. As will be described later, the support is made of a member that has optical transparency and supports a semiconductor substrate.

[0025] <Resin (P1): (P1) component> The adhesive composition according to this embodiment contains a resin (hereinafter also referred to as "component (P1)"). Component (P1) has a structural unit (u1) that includes a structure that absorbs at least a portion of light within a wavelength range of 300 to 800 nm. As a result, when the adhesive layer is irradiated with light within a wavelength range of 300 to 800 nm, the structural unit (u1) absorbs the light and generates heat, thereby altering the adhesive layer.

[0026] Examples of the structure contained in the structural unit (u1) that absorbs at least a portion of light within a wavelength range of 300 to 800 nm (hereinafter also referred to as "structure X") include an aromatic fused ring skeleton, a benzophenone skeleton, a dibenzoylmethane skeleton, a dibenzoylbenzene skeleton, and a benzotriazole skeleton. The aromatic fused ring skeleton contains a fused ring 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 an aromatic hydrocarbon ring or an aromatic heterocycle. The number of aromatic rings in the fused ring is preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 4, and particularly preferably 2 or 3. The fused ring may be composed of only aromatic rings or a fused ring of an aromatic ring and an aliphatic hydrocarbon ring, but a fused ring composed of only aromatic rings is preferred. Specific examples of the fused ring include naphthalene, anthracene, phenanthrene, and pyrene. Among these, anthracene or phenanthrene is preferred. The component (P1) having the structural unit (u1) can be obtained by polymerizing a polymerizable monomer containing a structure X. The component (P1) may contain a structural unit other than the structural unit (u1). In this case, the component (P1) can be obtained by polymerizing a polymerizable monomer containing a structure X with a polymerizable monomer that derives the other structural unit.

[0027] The component (P1) is an adhesive composition layer formed from the adhesive composition having a storage modulus (G') at 150°C of 1.5 x 10 5The resin is one that has a storage modulus of not more than the upper limit of the above range after curing, thereby providing good adhesive properties.

[0028] The storage modulus (G') of the adhesive composition at 150°C can be measured as follows. The adhesive composition is applied to a PET film with a release agent and heated in an atmospheric oven at 50°C and 100°C for 60 minutes each to form an adhesive composition layer with a thickness of 0.5 mm. The adhesive composition layer is then peeled from the PET film and its storage modulus (G') at 150°C is measured using a dynamic viscoelasticity measuring device. A Rheogel-E4000 (manufactured by UBM Inc.) can be used as the dynamic viscoelasticity measuring device. The measurement conditions are as follows: a sample of the adhesive composition layer has a size of 2.5 mm x 2.5 mm x 0.5 mm, and is heated from room temperature to 215°C at a rate of 5°C / min under shear conditions at a frequency of 1 Hz, and the storage modulus (G') at 150°C is measured.

[0029] The component (P1) is not particularly limited as long as it is a resin that can achieve the above storage modulus. The component (P1) is preferably a thermosetting resin having a curing temperature of 150°C or higher. Examples of thermosetting resins include resins containing polymerizable carbon-carbon unsaturated bonds. Specific examples of the component (P1) include urethane resins, acrylic resins, epoxy resins, and silicone resins containing polymerizable carbon-carbon unsaturated bonds.

[0030] The polymerizable carbon-carbon unsaturated bond contained in the component (P1) is not particularly limited, but is preferably radically polymerizable. The polymerizable carbon-carbon unsaturated bond may be a polymerizable carbon-carbon double bond or a polymerizable carbon-carbon triple bond, but a polymerizable carbon-carbon double bond is preferred. Examples of the polymerizable carbon-carbon unsaturated bond include a methacryloyl group and an acryloyl group. The polymerizable carbon-carbon unsaturated bond contained in the component (P1) may be one type or two or more types. The equivalent weight of the polymerizable carbon-carbon unsaturated bond contained in the (P1) component 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 polymerizable carbon-carbon unsaturated bond equivalent weight is at least the lower limit of the above-mentioned preferred range, the elastic modulus, heat resistance, etc. of the adhesive layer are further improved. When the polymerizable carbon-carbon unsaturated bond equivalent weight is at most the upper limit of the above-mentioned preferred range, the adhesive layer does not become too hard and has good cleanability. The above-mentioned equivalent weight number is the molecular weight of the (P1) component per equivalent of the polymerizable carbon-carbon unsaturated bond.

[0031] 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.

[0032] The (P1) component is preferably a urethane resin containing a polymerizable carbon-carbon unsaturated bond. When the (P1) component is a urethane resin, the (P1) component can be synthesized by a polymerization addition reaction between a polyisocyanate compound (hereinafter also referred to as "component (I)"), a polyol (hereinafter also referred to as "component (O)"), and a compound that derives the structural unit (u1) (hereinafter also referred to as "component (U1)"). At least one of the (I) and (O) components preferably contains a polymerizable carbon-carbon unsaturated bond. When the (U1) component is also the (I) component, the (P1) component may be obtained by a polymerization addition reaction between the (U1) component as the (I) component and the (O) component. When the (U1) component is also the (O) component, the (P1) component may be obtained by a polymerization addition reaction between the (I) component and the (U1) component as the (O) component.

[0033] <Polyisocyanate compound: component (I)> In this specification, the term "polyisocyanate compound" refers to a compound (polyisocyanate) having two or more isocyanate groups (-N=C=O) or a compound (blocked polyisocyanate) having two or more blocked isocyanate groups. The polyisocyanate is not particularly limited, and any polyisocyanate commonly used in the production of urethane resins can be used without 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.

[0034] 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.

[0035] 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. Examples of such products include 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.

[0036] 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.

[0037] Blocked polyisocyanates can be produced by reacting polyisocyanates with blocking agents. The reaction between polyisocyanates and blocking agents is carried out, for example, in a solvent lacking active hydrogen (e.g., 1,4-dioxane, cellosolve acetate, etc.) under heating at approximately 50 to 100°C, and optionally in the presence of a blocking catalyst. The ratio of polyisocyanates to blocking agents is not particularly limited, but is preferably 0.95:1.0 to 1.1:1.0, more preferably 1:1.05 to 1.15, in terms of equivalent ratio of isocyanate groups in the polyisocyanate to blocking agent. Known blocking catalysts can be used, including, for example, 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. One type of blocking catalyst may be used alone, or two or more types may be used in combination.

[0038] 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).

[0039] 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.

[0040] <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 unsaturated bond (hereinafter also referred to as "component (O1)") and other polyols (hereinafter also referred to as "component (O2)").

[0041] Polyol containing polymerizable carbon-carbon unsaturated bonds (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 unsaturated bond or two or more polymerizable carbon-carbon unsaturated bonds.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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).

[0046] 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).

[0047] Examples of polymer polyols include phenol resins, resins containing a hydroxystyrene skeleton, polyester polyols, polyether polyols, polyether ester polyols, polyester amide polyols, acrylic polyols, polycarbonate polyols, polyhydroxy alkanes, polyurethane polyols, and vegetable oil-based polyols. The number average molecular weight of the polymer polyol is preferably 500 to 100,000.

[0048] 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.

[0049] [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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] [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):

[0054] [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.

[0055] 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.

[0056] 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 (I) include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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-.

[0063] 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.

[0064] 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.

[0065] 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 0 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 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, in 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.

[0066] 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.

[0067] 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.

[0068] In the formula (a10-1), n ax1 is an integer of 1 to 3, preferably 1 or 2, and more preferably 1.

[0069] 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.

[0070] [ka]

[0071] The resin containing a hydroxystyrene skeleton is preferably a polymer of hydroxystyrene or a hydroxystyrene derivative, and more preferably a polymer of hydroxystyrene (polyhydroxystyrene).

[0072] [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.

[0073] Among them, the polycarbonate polyol is preferably a polycarbonate diol represented by the following general formula (PC-1).

[0074] [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.

[0075] 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 2Specific examples include -(CH2)6- and -(CH2)5-.

[0076] 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.

[0077] 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.

[0078] [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).

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] Examples of polyhydroxyalkanes include liquid rubbers obtained by copolymerizing butadiene or butadiene with acrylamide or the like.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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 adhesive layer can be improved.

[0088] 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.

[0089] <Compounds that derive structural unit (u1): (U1) component> The component (U1) is a compound containing a structure that absorbs at least a portion of light within a wavelength range of 300 to 800 nm. The component (U1) is preferably a polyisocyanate compound or a polyol. That is, the component (U1) may be contained in the component (I) or the component (O). The component (U1) is preferably a polyol. When the component (U1) is a polyol, the component (U1) may be either the component (O1) or the component (O2).

[0090] The (U1) component contains a structure (hereinafter also referred to as "structure X") that absorbs light having a wavelength within a range of 300 to 800 nm. Therefore, the structural unit (u1) derived from the (U1) component also contains structure X. In the (P1) component, structure X acts as a light-absorbing group that absorbs light having a wavelength within a range of 300 to 800 nm. Structure X can absorb light having a wavelength within a range of 300 to 800 nm and convert it into thermal energy sufficient to alter the adhesive layer. Structure X is preferably capable of absorbing light having a wavelength within a range of 300 to 700 nm, more preferably capable of absorbing light having a wavelength within a range of 300 to 600 nm, even more preferably capable of absorbing light having a wavelength within a range of 300 to 550 nm, and particularly preferably capable of absorbing light having a wavelength within a range of 300 to 400 nm. Structure X preferably has an absorption peak within the above wavelength range. Depending on the wavelength of light used for separating the support from the semiconductor substrate or the like, a structure X capable of absorbing light having the wavelength can be used.

[0091] The structure X is not particularly limited, but examples thereof include an aromatic fused ring skeleton, a benzophenone skeleton, a dibenzoylmethane skeleton, a dibenzoylbenzene skeleton, and a benzotriazole skeleton. The aromatic fused ring skeleton contains a fused ring 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 an aromatic hydrocarbon ring or an aromatic heterocycle. The number of aromatic rings in the fused ring is preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 4, and particularly preferably 2 or 3. The fused ring may be composed of only aromatic rings or a fused ring of an aromatic ring and an aliphatic hydrocarbon ring, but a fused ring composed of only aromatic rings is preferred. Specific examples of the fused ring include naphthalene, anthracene, phenanthrene, and pyrene. Among these, anthracene or phenanthrene is preferred.

[0092] Examples of the component (U1) include compounds represented by the following general formula (u1-1) or (u1-2).

[0093] [ka] [In formula (u1-1), X 1 is an n1-valent group containing a structure that absorbs at least a portion of light within a wavelength range of 300 to 800 nm; Y 1 is a divalent linking group, and n1 is an integer of 2 to 4. 1 may be the same as or different from each other. In formula (u1-2), X 2 is a monovalent group containing a structure that absorbs at least a part of light within a wavelength range of 300 to 800 nm; Y 2 is a trivalent linking group; Y 3 is a linking group having a valence of n2; n2 is an integer of 2 to 4. 2 may be the same as or different from each other. 2 may be the same as or different from each other.]

[0094] In general formula (u1-1), Y 1 is a divalent linking group. 2 is a trivalent linking group. The divalent or trivalent linking group may be a hydrocarbon group which may have a substituent. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be saturated or unsaturated, but is preferably saturated. The aliphatic hydrocarbon group may be linear or branched, or may contain a ring in its structure. The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 or 3 carbon atoms. The aliphatic hydrocarbon group containing a ring structure preferably has 3 to 10 carbon atoms, and preferably 3 to 6 carbon atoms. The aliphatic hydrocarbon group may have a substituent. The substituent may replace a hydrogen atom, or may replace a methylene group (-CH2-) in the carbon chain. Examples of the substituent that replaces a hydrogen atom include a hydroxy group, an amino group, an alkoxy group, a halogen atom, a carboxy group, and a cyano group, with a hydroxy group or an amino group being preferred. Examples of the substituent that replaces a methylene group (-CH2-) in the carbon chain include -O-, -CO-, -NH-, -COO-, and -CONH-.

[0095] The aromatic hydrocarbon group is a hydrocarbon group containing at least one aromatic ring. The aromatic ring contained in the aromatic hydrocarbon group may be monocyclic or polycyclic. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The number of aromatic rings contained in the aromatic hydrocarbon group is not particularly limited, but is preferably 1 to 3, and more preferably 1 or 2. The aromatic hydrocarbon group may be a group in which an aromatic ring and an aliphatic hydrocarbon group are linked together. The aromatic hydrocarbon group may have a substituent. The substituent may substitute a hydrogen atom of the aromatic ring, or may substitute a carbon atom constituting the aromatic ring with a heteroatom. Examples of the substituent substituting the hydrogen atom include a hydroxy group, an amino group, an alkoxy group, a halogen atom, a carboxy group, and a cyano group, with a hydroxy group or an amino group being preferred. Examples of the heteroatom substituting the aromatic ring include a nitrogen atom, an oxygen atom, and a sulfur atom, with a nitrogen atom being preferred.

[0096] In general formula (u1-2), Y 3 is an n2-valent linking group. 3 Examples of the hydrocarbon group include a hydrocarbon group which may have a substituent. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be saturated or unsaturated, but is preferably saturated. The aliphatic hydrocarbon group may be linear or branched, or may contain a ring in its structure. The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 or 3 carbon atoms. The aliphatic hydrocarbon group containing a ring structure preferably has 3 to 10 carbon atoms, and preferably 3 to 6 carbon atoms. The aliphatic hydrocarbon group may or may not have a substituent. The substituent may replace a hydrogen atom, or may replace a methylene group (-CH2-) in the carbon chain. Examples of the substituent that replaces a hydrogen atom include a hydroxy group, an amino group, an alkoxy group, a halogen atom, a carboxy group, and a cyano group, with a hydroxy group or an amino group being preferred. Examples of the substituent that replaces a methylene group (-CH2-) in the carbon chain include -O-, -CO-, -NH-, -COO-, and -CONH-.

[0097] The aromatic hydrocarbon group is a hydrocarbon group containing at least one aromatic ring. The aromatic ring contained in the aromatic hydrocarbon group may be monocyclic or polycyclic. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The number of aromatic rings contained in the aromatic hydrocarbon group is not particularly limited, but is preferably 1 to 3, and more preferably 1 or 2. The aromatic hydrocarbon group may be a group in which an aromatic ring and an aliphatic hydrocarbon group are linked together. The aromatic hydrocarbon group may have a substituent. The substituent may substitute a hydrogen atom of the aromatic ring, or may substitute a carbon atom constituting the aromatic ring with a heteroatom. Examples of the substituent substituting the hydrogen atom include a hydroxy group, an amino group, an alkoxy group, a halogen atom, a carboxy group, and a cyano group, with a hydroxy group or an amino group being preferred. Examples of the heteroatom substituting the aromatic ring include a nitrogen atom, an oxygen atom, and a sulfur atom, with a nitrogen atom being preferred.

[0098] Y 3 is preferably an aliphatic hydrocarbon group which may have a substituent, more preferably a saturated aliphatic hydrocarbon group which may have a substituent, even more preferably a saturated aliphatic hydrocarbon group which has no substituent, and particularly preferably a linear or branched alkyl group. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, still more preferably 1 to 4, and particularly preferably 1 to 3, or 1 or 2.

[0099] In general formula (u1-1), X 1 is an n1-valent group containing a structure (structure X) that absorbs at least a part of light within a wavelength range of 300 to 800 nm. X 1 Examples of the group include an n-valent group containing a group containing an aromatic fused ring skeleton, a benzophenone skeleton, a dibenzoylmethane skeleton, a dibenzoylbenzene skeleton, or a benzotriazole skeleton. In general formula (u1-2), X 2 is a monovalent group containing a structure (structure X) that absorbs at least a part of light within a wavelength range of 300 to 800 nm. X 2Examples of the group include monovalent groups containing a group containing an aromatic fused ring skeleton, a benzophenone skeleton, a dibenzoylmethane skeleton, a dibenzoylbenzene skeleton, or a benzotriazole skeleton.

[0100] In the general formula (u1-1) and the formula (u1-2), n1 and n2 each independently represent an integer of 2 to 4. n1 and n2 are preferably 2 or 3, and more preferably 2.

[0101] As the component (U1), for example, a compound represented by the following general formula (u1-1-1) or (u1-2-1) is preferred.

[0102] [ka] [In formula (u1-1-1), X 1 is an n1-valent group containing a structure that absorbs at least a portion of light within a wavelength range of 300 to 800 nm; Y 11 is a divalent linking group; L 11 is a linear or branched alkyl group; and n1 is an integer of 2 to 4. 11 may be the same or different. 11 may be the same as or different from each other. In formula (u1-2-1), X 2 is a monovalent group containing a structure that absorbs at least a part of light within a wavelength range of 300 to 800 nm; Y 21 is a trivalent linking group; L 21 is a linear or branched alkyl group; Y 3 is a linking group having a valence of n2; n2 is an integer of 2 to 4. 2 may be the same as or different from each other. 21 may be the same or different. 21 may be the same as or different from each other.]

[0103] In the formula (u1-1-1), Y 11In the formula (u1-2-1), Y is a divalent linking group. 21 is a trivalent linking group. The divalent or trivalent linking group includes the above Y 1 and Y 2 Examples of the divalent or trivalent linking group include the same as those exemplified above as the divalent or trivalent linking group in the above formula (I).

[0104] In the formulas (u1-1-1) and (u1-2-1), L 11 and L 21 are each independently a linear or branched alkyl group. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 5 carbon atoms.

[0105] X in general formulae (u1-1-1) and (u1-2-1) 1 , X 2 , n1, n2, and Y 3 represents X in the formulas (u1-1) and (u1-2). 1 , X 2 , n1, n2, and Y 3 are the same as

[0106] X having an aromatic fused ring skeleton 1 or X 2 Examples of X include those represented by the following general formula (Xa-1) or (Xa-2). 1 In this case, n in the general formula (Xa-1) or (Xa-2) is an integer of 2 to 4, preferably 2. 2 In this case, n in the general formula (Xa-1) or (Xa-2) is 1.

[0107] [ka] [In the formula, L a1 and L a2 each independently represents a single bond or a divalent linking group, R a1 and R a2 each independently represents a substituent; n represents an integer of 1 to 4; m represents an integer of 0 to 9, and m+n≦10; when n is 2 or more, a plurality of L a1and L a2 may be the same or different. When m is 2 or more, multiple R a1 and R a2 may be the same or different. * is a bond.]

[0108] In the general formulas (Xa-1) and (Xa-2), L a1 and L a2 each independently represents a single bond or a divalent linking group. Examples of the divalent linking group include hydrocarbon groups which may have a substituent. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be saturated or unsaturated, but is preferably saturated. The aliphatic hydrocarbon group may be linear or branched, or may contain a ring in its structure. The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 or 3 carbon atoms. The aliphatic hydrocarbon group containing a ring structure preferably has 3 to 10 carbon atoms, and preferably 3 to 6 carbon atoms. The aliphatic hydrocarbon group may have a substituent. The substituent may replace a hydrogen atom, or may replace a methylene group (-CH2-) in the carbon chain. Examples of the substituent that replaces a hydrogen atom include a hydroxy group, an amino group, an alkoxy group, a halogen atom, a carboxy group, and a cyano group, with a hydroxy group or an amino group being preferred. Examples of the substituent that replaces a methylene group (-CH2-) in the carbon chain include -O-, -CO-, -NH-, -COO-, and -CONH-.

[0109] The aromatic hydrocarbon group is a hydrocarbon group containing at least one aromatic ring. The aromatic ring contained in the aromatic hydrocarbon group may be monocyclic or polycyclic. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The number of aromatic rings contained in the aromatic hydrocarbon group is not particularly limited, but is preferably 1 to 3, and more preferably 1 or 2. The aromatic hydrocarbon group may be a group in which an aromatic ring and an aliphatic hydrocarbon group are linked together. The aromatic hydrocarbon group may have a substituent. The substituent may substitute a hydrogen atom of the aromatic ring, or may substitute a carbon atom constituting the aromatic ring with a heteroatom. Examples of the substituent substituting the hydrogen atom include a hydroxy group, an amino group, an alkoxy group, a halogen atom, a carboxy group, and a cyano group, with a hydroxy group or an amino group being preferred. Examples of the heteroatom substituting the aromatic ring include a nitrogen atom, an oxygen atom, and a sulfur atom, with a nitrogen atom being preferred.

[0110] In the general formulas (Xa-1) and (Xa-2), R a1 and R a2 R each independently represents a substituent. a1 and R a2 Examples of the alkyl group include an alkyl group, a hydroxy group, an amino group, an alkoxy group, a halogen atom, a carboxy group, a cyano group, a nitrile group, a nitrile alkyl group, and an alicyclic group. The alkyl group, alkoxy group, and nitrile alkyl group preferably have 1 to 5 carbon atoms, and more preferably have 1 to 3 carbon atoms. The alicyclic group preferably has 1 to 6 carbon atoms. An example of a nitrile alkyl group is a malonylnitrile group. The alicyclic group may be an alicyclic hydrocarbon ring or an alicyclic heterocycle. Examples of the alicyclic heterocycle include those containing a sulfur atom, a nitrogen atom, or an oxygen atom. A specific example of an alicyclic heterocycle is dithiolane.

[0111] In the general formulae (Xa-1) and (Xa-2), m represents an integer of 0 to 9. m is preferably an integer of 0 to 6, more preferably an integer of 0 to 5, still more preferably an integer of 0 to 3, and particularly preferably an integer of 0 to 2. The relationship between m and n is m+n≦10.

[0112] X with a benzophenone skeleton 1 or X 2 Examples of the X include those represented by the following general formula (Xb): 1 In this case, p+q in the general formula (Xb) is an integer of 2 to 4, preferably 2. 2 In this case, p+q in general formula (Xb) is 1.

[0113] [ka] [In the formula, L b1 and L b2 each independently represents a single bond or a divalent linking group, R b1 and R b2 each independently represents a substituent; p and q each independently represent an integer of 0 to 4; m1 and m2 each independently represent an integer of 0 to 5, and m1+p≦5, m2+q≦5. When p is 2 or more, a plurality of L b1 may be the same or different. When q is 2 or more, multiple L b2 may be the same or different. When m1 is 2 or more, multiple R b1 may be the same or different. When m2 is 2 or more, multiple R b2 may be the same or different. * is a bond.]

[0114] In general formula (Xb), L b1 and L b2 each independently represents a single bond or a divalent linking group. Examples of the divalent linking group include L in formulas (Xa-1) and (Xa-2). a1 and L a2 The same as those listed in L. b1 and L b2is preferably a single bond or an aliphatic hydrocarbon group which may have a substituent, and is preferably a single bond or an alkyl group which may have a substituent. The alkyl group which may have a substituent preferably has 1 to 5 carbon atoms, and more preferably has 1 to 3 carbon atoms. The alkyl group which may have a substituent is preferably an alkyl group or an alkyl group in which some of the methylene groups (-CH2-) constituting the carbon chain are substituted with -O-, -CO-, -NH-, -COO- or -CONH-.

[0115] In general formula (Xb), R b1 and R b2 R each independently represents a substituent. b1 and R b2 As the group, R in the formulas (Xa-1) and (Xa-2) a1 and R a2 The same as those mentioned above can be mentioned.

[0116] In general formula (Xb), m1 and m2 each independently represent an integer of 0 to 5, and m1+p≦5 and m2+q≦5. m1 and m2 are preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1.

[0117] X having a dibenzoylmethane skeleton 1 or X 2 Examples of the compound represented by the general formula (Xc) include: X 1 In this case, p+q in the general formula (Xc) is an integer of 2 to 4, preferably 2. 2 In this case, p+q in general formula (Xc) is 1.

[0118] [ka] [In the formula, L c1 and L c2 each independently represents a single bond or a divalent linking group, R c1 and R c2each independently represents a substituent; p and q each independently represent an integer of 0 to 4; m1 and m2 each independently represent an integer of 0 to 5, and m1+p≦5, m2+q≦5. When p is 2 or more, a plurality of L c1 may be the same or different. When q is 2 or more, multiple L c2 may be the same or different. When m1 is 2 or more, multiple R c1 may be the same or different. When m2 is 2 or more, multiple R c2 may be the same or different. * is a bond.]

[0119] In general formula (Xc), L c1 and L c2 each independently represents a single bond or a divalent linking group. Examples of the divalent linking group include L in formulas (Xa-1) and (Xa-2). a1 and L a2 The same as those listed in L. c1 and L c2 is preferably a single bond or an aliphatic hydrocarbon group which may have a substituent, and is preferably a single bond or an alkyl group which may have a substituent. The alkyl group which may have a substituent preferably has 1 to 5 carbon atoms, and more preferably has 1 to 3 carbon atoms. The alkyl group which may have a substituent is preferably an alkyl group or an alkyl group in which some of the methylene groups (-CH2-) constituting the carbon chain are substituted with -O-, -CO-, -NH-, -COO- or -CONH-.

[0120] In general formula (Xc), R c1 and R c2 R each independently represents a substituent. c1 and R c2 As the group, R in the formulas (Xa-1) and (Xa-2) a1 and R a2 The same as those mentioned above can be mentioned.

[0121] In formula (Xc), m1 and m2 each independently represent an integer of 0 to 5, and m1+p≦5 and m2+q≦5. m1 and m2 each preferably represent an integer of 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1.

[0122] X having a dibenzoylbenzene skeleton 1 or X 2 Examples of X include those represented by the following general formula (Xd): 1 In this case, p+q+r in the general formula (Xd) is an integer of 2 to 4, preferably 2. 2 In this case, p+q+r in general formula (Xd) is 1.

[0123] [ka] [In the formula, L d1 , L d2 and L d3 each independently represents a single bond or a divalent linking group, R d1 , R d2 and R d3 each independently represents a substituent. p, q, and r each independently represent an integer of 0 to 4. m1 and m2 each independently represent an integer of 0 to 5, and m3 represents an integer of 1 to 4, and m1+p≦5, m2+q≦5, and m3+r=4. When p is 2 or more, a plurality of L d1 may be the same or different. When q is 2 or more, multiple L d2 may be the same or different. When r is 2 or more, multiple L d3 may be the same or different. When m1 is 2 or more, multiple R d1 may be the same or different. When m2 is 2 or more, multiple R d2 may be the same or different. When m3 is 2 or more, multiple R d3 may be the same or different. * is a bond.]

[0124] In general formula (Xd), L d1 , Ld2 and L d3 each independently represents a single bond or a divalent linking group. Examples of the divalent linking group include L in formulas (Xa-1) and (Xa-2). a1 and L a2 The same as those listed in L. d1 , L d2 and L d3 is preferably a single bond or an aliphatic hydrocarbon group which may have a substituent, and is preferably a single bond or an alkyl group which may have a substituent. The alkyl group which may have a substituent preferably has 1 to 5 carbon atoms, and more preferably has 1 to 3 carbon atoms. The alkyl group which may have a substituent is preferably an alkyl group or an alkyl group in which some of the methylene groups (-CH2-) constituting the carbon chain are substituted with -O-, -CO-, -NH-, -COO- or -CONH-.

[0125] In general formula (Xd), R d1 , R d2 and R d3 R each independently represents a substituent. d1 , R d2 and R d3 As the group, R in the formulas (Xa-1) and (Xa-2) a1 and R a2 The same as those mentioned above can be mentioned.

[0126] In general formula (Xd), m1 and m2 each independently represent an integer of 0 to 5, and m3 represents an integer of 1 to 4, provided that m1+p≦5, m2+q≦5, and m3+r=4. m1, m2, and m3 are each preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and still more preferably 0 or 1.

[0127] X having a benzotriazole skeleton 1 or X 2 Examples of X include those represented by the following general formula (Xe): 1 In this case, n in the general formula (Xe) is an integer of 2 to 4, preferably 2. 2 In this case, n in the general formula (Xe) is 1.

[0128] [ka] [In the formula, L e represents a single bond or a divalent linking group, R e represents a substituent; n represents an integer of 0 to 4; m represents an integer of 0 to 4, and m+n≦5; when n is 2 or more, a plurality of L e may be the same or different. When m is 2 or more, multiple R e may be the same or different. * is a bond.]

[0129] In general formula (Xe), L e represents a single bond or a divalent linking group. Examples of the divalent linking group include L in the formulas (Xa-1) and (Xa-2). a1 and L a2 The same as those listed in L. e is preferably a single bond or an optionally substituted hydrocarbon group, more preferably a single bond, an optionally substituted alkyl group, or a group in which one hydrogen atom on a benzene ring has been substituted with an alkyl group. The optionally substituted alkyl group and the alkyl group bonded to a benzene ring preferably have 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms.

[0130] In the general formula (Xe), R e represents a substituent. e As the group, R in the formulas (Xa-1) and (Xa-2) a1 and R a2 The same as those mentioned above can be mentioned.

[0131] In the general formula (Xe), m represents an integer of 0 to 4. m is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and even more preferably 0 or 1. The relationship between m and n is m+n≦5.

[0132] Specific examples of the component (U1) are shown below, but are not limited to these.

[0133] [ka]

[0134] The component (U1) may be used alone or in combination of two or more types. The ratio of the (U1) component to all monomers used in the synthesis of the (P1) component is, for example, 10% by mass or more, 15% by mass or more, or 20% by mass or more, based on the mass of all monomers (100% by mass). When the ratio of the (U1) component is equal to or greater than the preferred lower limit, separation performance is improved. The ratio of the (U1) component to all monomers used in the synthesis of the (P1) component is, for example, 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, or 50% by mass or less, based on the mass of all monomers (100% by mass). When the ratio of the (U1) component is equal to or less than the preferred upper limit, it is easier to achieve a balance with other monomers.

[0135] When component (P1) is a urethane resin, component (P1) can be synthesized by mixing components (I), (O), and (U1) 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 be added to the reaction system to prevent polymerization of the polymerizable carbon-carbon unsaturated bond in component (O1). Component (O) preferably contains components (O1) and (O2). Component (U1) is preferably added as component (O), more preferably as component (O2).

[0136] 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 of this embodiment 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 is preferably 10 to 60 mass %, more preferably 20 to 60 mass %, and even more preferably 30 to 60 mass %, relative to the total amount (100 mass %) of the adhesive composition.

[0137] <Polymerization initiator: component (A)> The adhesive composition of this embodiment contains a polymerization initiator (hereinafter also referred to as component (A)). A polymerization initiator 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.

[0138] Examples of the thermal polymerization initiator include peroxides and azo-based polymerization initiators.

[0139] 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.

[0140] 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.

[0141] 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).

[0142] 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.

[0143] 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.

[0144] The component (A) may be used singly or in combination of two or more. The component (A) is preferably a thermal polymerization initiator, more preferably a peroxide. 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 is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of component (P1).

[0145] <Optional ingredients> In addition to the components described above, the adhesive composition of the present embodiment may contain optional components within a range that does not impair the effects of the present invention. The optional components are not particularly limited, but examples thereof include a polymerization inhibitor, a solvent component, a plasticizer, an adhesive aid, a stabilizer, a colorant, a surfactant, etc.

[0146] <Polymerization inhibitor> 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.

[0147] 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.

[0148] 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.

[0149] <Surfactants> The adhesive composition of this embodiment can be prepared by dissolving the components (P1) and (A), and optionally any other components, in a solvent component and mixing them together. Any solvent capable of dissolving the above components can be used as the solvent component.

[0150] Examples of solvent components include hydrocarbon solvents, petroleum-based solvents, and other solvents. Hereinafter, hydrocarbon solvents and petroleum-based solvents will be collectively referred to as "component (S1)." Solvent components other than component (S1) will be referred to as "component (S2)."

[0151] 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).

[0152] Petroleum-based solvents are solvents refined from heavy oil, and examples thereof include kerosene, paraffin-based solvents, and isoparaffin-based solvents.

[0153] 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.

[0154] 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.

[0155] 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.

[0156] The content of the solvent component in the adhesive composition of this embodiment may be adjusted appropriately depending on the thickness of the adhesive composition layer. The content of the solvent component is preferably, for example, within the range of 40 to 90 mass % relative to the total amount (100 mass %) of the adhesive composition. That is, the adhesive composition of this embodiment preferably has a solids concentration (total amount of blended components excluding the solvent component) within the range of 10 to 80 mass %. When the content of the solvent component is within the above-mentioned preferred range, viscosity adjustment is easy.

[0157] When a polymerization initiator is used, the polymerization initiator can be blended by a known method immediately before use of the adhesive composition. The polymerization initiator or polymerization inhibitor may be blended in the form of a solution in which it is dissolved in the component (S2) above in advance. The amount of component (S2) used can be adjusted appropriately depending on the type of polymerization initiator or polymerization inhibitor, and is, for example, preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass, per 100 parts by mass of component (S1). When the amount of component (S2) used is within the above-mentioned preferred range, the polymerization initiator or polymerization inhibitor can be sufficiently dissolved.

[0158] According to the adhesive composition of this embodiment, the resin (P1) contained in the adhesive layer that temporarily bonds a semiconductor substrate or the like to a support contains a structure X that absorbs at least a portion of light in a wavelength range of 300 to 800 nm. When this adhesive layer is irradiated with light such as laser light, the structure X in the adhesive layer absorbs the light and the adhesive layer is altered. This reduces the adhesive strength of the adhesive layer, allowing the semiconductor substrate or the like to be separated from the support. Therefore, there is no need to provide a separation layer. Furthermore, because the structure X is incorporated into the (P1) component, solubility is not an issue, and the content of the structure X can be increased. This allows for good separability to be obtained. Furthermore, the storage modulus (G') at 150°C of the adhesive composition layer formed from the adhesive composition of this embodiment is 1.5 × 10 5 Pa or less, and therefore the adhesiveness between the semiconductor substrate or the like and the support is good.

[0159] When the resin (P1) is a thermosetting resin, an adhesive composition layer is formed between the semiconductor substrate or the like and the support, and then cured. This forms an adhesive layer that temporarily bonds the semiconductor substrate or the like to the support. Because the adhesive layer is cured by a crosslinked structure, it has high heat resistance and does not lose its elastic modulus even at high temperatures (e.g., 200°C or higher). Therefore, even when high-temperature processing is performed during processing of semiconductor substrates or electronic devices, problems such as misalignment and sinking are unlikely to occur. Furthermore, when the resin (P1) is a urethane resin, the adhesive layer can be decomposed by decomposing the urethane bond with an acid or alkali. Therefore, even if residues of the adhesive layer adhere to the semiconductor substrate or the like separated from the support, the residues of the adhesive layer can be easily removed by washing with an acid or alkali.

[0160] (Laminate) A laminate according to a second aspect of the present invention is a laminate comprising a light-transmitting support, an adhesive layer, and a semiconductor substrate or an electronic device laminated in this order, characterized in that the adhesive layer is a cured product of the adhesive composition according to the first aspect.

[0161] FIG. 1 shows an embodiment of the laminate according to the second aspect. 1 includes a light-transmitting support 1, an adhesive layer 3, and a semiconductor substrate 4. In the stack 100, the support 1, the adhesive layer 3, and the semiconductor substrate 4 are stacked in this order.

[0162] FIG. 2 shows another embodiment of the laminate according to the second aspect. The laminate 200 shown in FIG. 2 has the same configuration as the laminate 100, except that an electronic device 456 consisting of a semiconductor substrate 4, a sealing material layer 5, and a wiring layer 6 is laminated on an adhesive layer 3.

[0163] FIG. 3 shows yet another embodiment of the laminate according to the second aspect. The laminate 300 shown in FIG. 3 has the same configuration as the laminate 100 except that the electronic device is made of a wiring layer 6.

[0164] FIG. 4 shows yet another embodiment of the laminate according to the second aspect. The laminate 400 shown in FIG. 4 has the same configuration as the laminate 100, except that an electronic device 645 made up of a wiring layer 6, a semiconductor substrate 4, and a sealing material layer 5 is laminated on an adhesive layer 3.

[0165] <Support> The support is a member that supports a semiconductor substrate or an electronic device. The support has optical transparency. The support is attached to the semiconductor substrate or the electronic device via an adhesive layer. Therefore, the support preferably has sufficient strength to prevent damage or deformation of the semiconductor substrate during thinning of the device, transportation of the semiconductor substrate, mounting on the semiconductor substrate, etc. Examples of materials that can be used for the support include glass, silicon, and acrylic resin. Examples of shapes of the support include, but are not limited to, rectangular and circular shapes. For the support, a circular support that is enlarged in size or a large panel that is rectangular in plan view can also be used in order to achieve higher density integration and improve production efficiency.

[0166] <Adhesive layer> The adhesive layer is provided to temporarily adhere a semiconductor substrate or an electronic device to a support. The adhesive layer is formed from the adhesive composition according to the first embodiment. When the component (P1) is a thermosetting resin, the adhesive layer is a cured product of the component (P1). When the component (P1) is a thermosetting resin, the adhesive composition can be cured by heating the adhesive composition. The thickness of the adhesive layer is preferably, for example, in the range of 1 μm or more and 200 μm or less, and more preferably in the range of 5 μm or more and 150 μm or less.

[0167] When the adhesive layer is a cured product of a thermosetting resin, the material (cured product) constituting the adhesive layer preferably satisfies the following properties. When the complex modulus of elasticity of the cured material was measured under the following conditions, the complex modulus at 200°C was 1.0 x 10 4 Pa or more, and 5.0 × 10 4 Pa or more is more preferable, and 1.0 × 10 5 It is more preferable that the complex modulus at 200°C is 1.0 × 10 6 Pa or more is more preferable, and 5.0 × 10 6 More preferably, the temperature is 1.0×10 Pa or higher. 7 The upper limit of the complex elastic modulus at 200°C is, for example, 1.0 × 10 10 Pa or less. In addition, when the complex modulus of elasticity of the cured body was measured under the following conditions, the complex modulus at 250°C was 5.0 × 10 6 Pa or more, and 1.0 × 10 7 The upper limit of the complex elastic modulus at 250°C is, for example, 1.0 × 10 10 Pa or less.

[0168] The complex modulus of the cured product can be measured using a dynamic viscoelasticity measuring device, Rheogel-E4000 (manufactured by UBM). Specifically, the adhesive composition is applied to a PET film with a release agent, and heated in an oven under a nitrogen atmosphere at 180°C for 1 hour to form a 50 μm thick test piece. The test piece (size: 5 mm × 40 mm, thickness: 50 μm) is then peeled from the PET film and measured using the measuring device described above. The measurement conditions are a tensile condition with a frequency of 1 Hz, and a temperature increase rate of 5°C / min from a starting temperature of 50°C to 300°C.

[0169] <Semiconductor substrate or electronic device> The semiconductor substrate or electronic device is temporarily attached to the support via an adhesive layer.

[0170] <Semiconductor substrate> The semiconductor substrate is not particularly limited, and examples thereof include those similar to those exemplified above in "(Adhesive composition)." The semiconductor substrate may be a semiconductor element or other element, and may have a single-layer or multi-layer structure.

[0171] <Electronic Devices> The electronic device is not particularly limited, and examples include those similar to those exemplified in "(Adhesive composition)" above. The electronic device is preferably a composite of a member made of metal or semiconductor and a resin that seals or insulates the member. Specifically, the electronic device includes at least one of an encapsulant layer and a wiring layer, and may further include a semiconductor substrate. In the laminate 200 shown in Fig. 2, the electronic device 456 is composed of a semiconductor substrate 4, an encapsulant layer 5, and a wiring layer 6. In the laminate 300 shown in Fig. 3, the electronic device 6 is composed of a wiring layer 6. In the laminate 400 shown in Fig. 4, the electronic device 645 is composed of a wiring layer 6, a semiconductor substrate 4, and a encapsulant layer 5.

[0172] [Encapsulant layer] The encapsulant layer is provided to encapsulate the semiconductor substrate and is formed using an encapsulant that can insulate or encapsulate components made of metal or semiconductor. As the encapsulant, for example, a resin composition can be used. The encapsulant layer 5 is preferably not provided for each individual semiconductor substrate 4, but is provided so as to cover the entire semiconductor substrate 4 on the adhesive layer 3. The resin used for the encapsulant is not particularly limited as long as it can encapsulate and / or insulate metals or semiconductors, and examples thereof include epoxy resins and silicone 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.

[0173] ≪Wiring layer≫ The wiring layer, also called RDL (Redistribution Layer), is a thin-film wiring body that forms wiring connected to a substrate, and can have a single-layer or multi-layer structure. The wiring layer is made of a dielectric (silicon oxide (SiO x ), photosensitive resin such as photosensitive epoxy, etc.) between which wiring is formed by a conductor (for example, metals such as aluminum, copper, titanium, nickel, gold, and silver, and alloys such as silver-tin alloy, etc.), but is not limited to this.

[0174] In the laminates of FIGS. 1 to 4, the support 1 and the adhesive layer 3 are adjacent to each other, but this is not limiting, and another layer may be formed between the support 1 and the adhesive layer 3. In this case, the other layer may be made of a light-transmitting material. This allows layers that impart desirable properties to the laminates 100 to 400 to be added as appropriate without interfering with the incidence of light on the adhesive layer 3. The wavelength of light that can be used varies depending on the type of material that constitutes the adhesive layer 3. Therefore, the material that constitutes the other layer 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 adhesive layer 3.

[0175] (Laminate manufacturing method (1)) The method for manufacturing a laminate according to the third aspect of the present invention is a method for manufacturing a laminate in which a light-transmitting support, an adhesive layer, and a semiconductor substrate are laminated in this order, and is characterized by comprising the steps of applying the adhesive composition according to the first aspect to the support or the semiconductor substrate to form an adhesive composition layer (hereinafter also referred to as the ``adhesive composition layer forming step''), placing the semiconductor substrate on the support with the adhesive composition layer interposed therebetween (hereinafter also referred to as the ``semiconductor substrate placing step''), and curing the adhesive composition layer by a polymerization reaction of the urethane resin to form the adhesive layer (hereinafter also referred to as the ``adhesive layer forming step'').

[0176] 5 and 6 are schematic process diagrams illustrating one embodiment of a method for producing a laminate according to this embodiment. 5(a) and 5(b) are diagrams illustrating the steps of manufacturing a laminate 100' in which a support 1, an adhesive composition layer 3', and a semiconductor substrate 4 are laminated in this order. Fig. 5(a) is a diagram illustrating the adhesive composition layer forming step. Fig. 5(b) is a diagram illustrating the semiconductor substrate placing step. 6 is a diagram illustrating the adhesive layer forming step. The adhesive composition layer 3' in the laminate 100' is thermally cured to form the adhesive layer 3, thereby obtaining the laminate 100.

[0177] [Adhesive composition layer forming step] The method for producing a laminate according to this embodiment includes an adhesive composition layer-forming step of applying an adhesive composition to a support or a semiconductor substrate to form an adhesive composition layer. In FIG. 5(a), an adhesive composition layer 3' is formed on a support 1 using an adhesive composition.

[0178] The method for forming the adhesive composition layer 3' on the support 1 is not particularly limited, but examples thereof include spin coating, dipping, roller blade coating, spray coating, and slit coating. An adhesive composition layer may be formed on the semiconductor substrate 4 in a similar manner.

[0179] After forming the adhesive composition layer, a baking treatment may be carried out. The baking temperature conditions are lower than the heating temperature in the adhesive layer forming step described below. The baking conditions may vary depending on the type of curable component contained in the adhesive composition, but examples include a temperature condition of 70 to 100°C for 1 to 10 minutes.

[0180] [Semiconductor substrate placement process] The method for producing a laminate according to this embodiment includes a semiconductor substrate mounting step. The semiconductor substrate mounting step is a step of mounting a semiconductor substrate on a support via an adhesive composition layer. This allows a laminate 100′ to be obtained. In FIG. 5(c), a semiconductor substrate 4 is placed on the support 1 via an adhesive composition layer 3' formed on the support 1.

[0181] The method for placing the semiconductor substrate 4 on the support 1 via the adhesive composition layer 3' is not particularly limited, and any method commonly used for placing a semiconductor substrate in a predetermined position can be used.

[0182] [Adhesive layer formation process] When the component (P1) is a thermosetting resin, the method for producing a laminate according to this embodiment may include an adhesive layer-forming step. The adhesive layer-forming step is a step in which the adhesive composition layer is cured by a curing reaction of the component (P1) in the adhesive composition layer to form an adhesive layer. This allows the laminate 100 to be obtained. In FIG. 6, an adhesive layer 3 is formed by curing an adhesive composition layer 3'.

[0183] When the component (P1) contains a polymerizable carbon-carbon double bond, the polymerization reaction can be carried out by selecting an appropriate method depending on the type of the polymerizable carbon-carbon double bond, and the curing reaction of the component (P1) can proceed. For example, when the component (P1) contains a methacryloyl group or an acryloyl group, the polymerization reaction of the component (P1) can be promoted by heating.

[0184] The heating temperature may be, for example, 80 to 350°C, 100 to 300°C, 130 to 300°C, or 150 to 300°C. The heating time is not particularly limited as long as it is sufficient for component (P1) to polymerize and harden. The heating time is, for example, preferably 5 to 180 minutes, more preferably 10 to 120 minutes, and even more preferably 15 to 60 minutes. The hardening reaction can be carried out, for example, under a nitrogen atmosphere.

[0185] This step hardens the component (P1) in the adhesive composition layer 3', forming an adhesive layer 3, which is a hardened product of the adhesive composition layer 3'. This temporarily bonds the support 12 and the semiconductor substrate 4. As a result, the laminate 100 can be obtained.

[0186] [Optional process] The method for producing a laminate according to this embodiment may include other steps in addition to the steps described above, such as various mechanical or chemical treatments (thinning treatments such as grinding or chemical mechanical polishing (CMP), high-temperature / vacuum treatments such as chemical vapor deposition (CVD) or physical vapor deposition (PVD), treatments using chemicals such as organic solvents, acidic treatment solutions, or basic treatment solutions, plating treatments, irradiation with actinic rays, heating / cooling treatments, etc.).

[0187] (Laminate manufacturing method (2)) A method for producing a laminate according to a fourth aspect of the present invention is characterized in that, after obtaining a laminate by the method for producing a laminate according to the third aspect, it further comprises an electronic device formation step of forming an electronic device which is a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member.

[0188] The laminate obtained by the laminate manufacturing method of the present embodiment is a laminate in which a support, an adhesive layer, and an electronic device are laminated in this order, and can be obtained by subjecting the laminate obtained by the laminate manufacturing method according to the third aspect to an electronic device forming step.

[0189] [Electronic device formation process] The method for producing a laminate according to this embodiment includes an electronic device formation step, which is a step of forming an electronic device that is a composite of a member made of a metal or semiconductor and a resin that seals or insulates the member. The electronic device forming process can include any one of an encapsulating process, a grinding process, and a wiring layer forming process. In one embodiment, the electronic device forming process includes a substrate fixing process and an encapsulating process. In this case, the electronic device forming process may further include a grinding process and a wiring layer forming process.

[0190] About the sealing process The sealing step is a step of sealing the substrate fixed on the support with a sealing material. In FIG. 7(a), a stacked body 110 is obtained in which the semiconductor substrate 4 is temporarily bonded to the support 1 via the adhesive layer 3 and the entirety of the semiconductor substrate 4 is sealed with the sealing material layer 5.

[0191] In the sealing process, the sealing material heated to, for example, 130 to 170°C is supplied onto the adhesive layer 3 so as to cover the semiconductor substrate 4 while maintaining a high viscosity, and is compression molded to produce a laminate 110 in which the sealing material layer 5 is provided on the adhesive layer 3. At this time, the temperature condition is, for example, 130 to 170°C. The pressure applied to the semiconductor substrate 4 is, for example, 50 to 500 N / cm 2 is.

[0192] It is preferable that the sealing material layer 5 is not provided for each individual semiconductor substrate 4, but is provided so as to cover the entire semiconductor substrate 4 on the adhesive layer 3.

[0193] About the grinding process The grinding step is a step of grinding the sealant portion (sealant layer 5) in the sealant after the sealing step so as to expose a part of the semiconductor substrate. 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 semiconductor substrate 4, for example, as shown in FIG. 7(b).

[0194] About the wiring layer formation process The wiring layer forming step is a step of forming a wiring layer on the exposed semiconductor substrate after the grinding step. 7(c), a wiring layer 6 is formed on the semiconductor substrate 4 and the encapsulant layer 5. This results in a stacked body 120. In the stacked body 120, the semiconductor substrate 4, the encapsulant layer 5, and the wiring layer 6 constitute an electronic device 456.

[0195] The wiring layer 6 may be formed, for example, by the following method. First, 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.

[0196] Subsequently, wiring is formed on the dielectric layer using a conductor such as a metal. Methods for forming the wiring include known semiconductor processing techniques such as lithography processes such as photolithography (resist lithography) and etching processes. Examples of such lithography processes include lithography processes using a positive resist material and lithography processes using a negative resist material.

[0197] In the method for manufacturing a laminate according to this embodiment, it is further possible to form bumps or mount elements on the wiring layer 6. Mounting elements on the wiring layer 6 can be performed using, for example, a chip mounter.

[0198] (Laminate manufacturing method (3)) A method for producing a laminate according to a fifth aspect of the present invention is a method for producing a laminate in which a support, an adhesive layer, and an electronic device are laminated in this order, and is characterized by comprising the steps of: applying the adhesive composition according to the first aspect onto the support to form a layer of the adhesive composition (adhesive composition layer forming step); forming an electronic device, which is a composite of a member made of a metal or semiconductor and a resin that seals or insulates the member, on the adhesive composition layer (electronic device forming step); and curing the adhesive composition layer to form an adhesive layer (adhesive layer forming step).

[0199] The laminate obtained by the laminate manufacturing method of this embodiment is a laminate in which a support, an adhesive layer, and an electronic device are laminated in this order, as in the manufacturing method according to the fourth aspect.

[0200] In the manufacturing method of this embodiment, the adhesive composition layer forming step can be carried out in the same manner as in the manufacturing method of the laminate according to the third aspect.

[0201] In the manufacturing method of this embodiment, an electronic device forming step is performed after the adhesive composition layer forming step. Such an electronic device forming step may include a wiring layer forming step. The electronic device forming step may further include a semiconductor substrate mounting step, a sealing step, a grinding step, etc. Furthermore, the electronic device forming step may be a step of mounting a sealed body, in which a semiconductor substrate is sealed with a sealant, on a support via an adhesive composition layer.

[0202] The adhesive layer forming step can be carried out in the same manner as in the method for producing a laminate according to the third embodiment.

[0203] After the adhesive layer forming step, an electronic device forming step may be carried out as necessary. The electronic device forming step may include, for example, a semiconductor substrate mounting step, a sealing step, a grinding step, and the like.

[0204] According to the laminate manufacturing methods of the third to fifth aspects, the support and the semiconductor substrate or electronic device are temporarily bonded via a highly heat-resistant adhesive layer, so that a laminate can be stably manufactured in which the support, the adhesive layer, and the semiconductor substrate or electronic device are stacked in this order. Such a laminate is manufactured in a process based on fan-out technology, in which terminals provided on the semiconductor substrate are mounted on a wiring layer extending outside the chip area.

[0205] (Electronic component manufacturing method) A sixth aspect of the present invention relates to a method for manufacturing an electronic component, characterized in that it comprises a step of obtaining a laminate by a method for manufacturing a laminate according to any one of the third to fifth aspects, followed by a step of separating the electronic device from the support by irradiating the adhesive layer with light through the support to alter the adhesive layer (hereinafter also referred to as the "separation step"), and a step of removing the adhesive layer by decomposing the urethane bond in the adhesive layer with an acid or alkali (hereinafter also referred to as the "adhesive layer removal step").

[0206] 8A and 8B are schematic process diagrams illustrating one embodiment of a method for manufacturing a semiconductor package (electronic component). Fig. 8A shows a laminate 120, Fig. 8B illustrates a separation step, and Fig. 8C illustrates an adhesive layer removal step.

[0207] [Separation process] The separation step is a step in which adhesive layer 3 is irradiated with light (arrow) through support 1 to alter adhesive layer 3, thereby separating electronic device 456 from support 1. As shown in FIG. 8(a), in the separation step, adhesive layer 3 is irradiated with light (arrow) through support 1 that transmits light, thereby altering adhesive layer 3.

[0208] The wavelength of the light used in the separation step may be selected from the wavelength range of 300 to 800 nm according to the wavelength of light absorbed by the structure X contained in the adhesive layer 3. The type of light to be irradiated may be appropriately selected depending on the transmittance of the support 1, and may be, for example, a laser beam or a non-laser beam, 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, or a free electron laser. This alters the adhesive layer 3, making it possible to easily separate the support 1 and the electronic device 456.

[0209] 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 5.0 W or less, and more preferably 3.0 W or more and 4.0 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.

[0210] After the adhesive layer 3 is irradiated with light (arrow) to change the properties of the adhesive layer 3, the support 1 is separated from the electronic device 456 as shown in FIG. 8(b). For example, the support 1 and the electronic device 456 are separated by applying a force in a direction that moves the support 1 and the electronic device 456 away from each other. Specifically, the support 1 and the electronic device 456 can be separated by fixing one of the support 1 and the electronic device 456 side (wiring layer 6) 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 1 and the electronic device 456 can be suitably separated by applying a force of approximately 0.1 to 5 kgf (0.98 to 49 N).

[0211] [Adhesive layer removal process] The method for manufacturing an electronic component according to this embodiment includes an adhesive layer removal step. The adhesive layer removal method is not particularly limited and can be selected appropriately depending on the type of component (P1). For example, when component (P1) is a urethane resin, the adhesive layer can be removed by decomposing the urethane bond with an acid or alkali. Alternatively, the adhesive layer may be removed using an appropriate adhesive remover. 8(b), after the separation step, the adhesive layer 3 is attached to the electronic device 456. In this step, the adhesive layer 3 is removed by decomposition and / or peeling, etc., to obtain the electronic component 50.

[0212] When the (P1) component is a urethane resin, the adhesive layer 3 contains a urethane resin formed by copolymerization of the (I) component and the (O) component, or a cross-linked urethane resin formed by polymerization of the (P1) component. These urethane resins are decomposed by treating them with an acid or alkali, resulting in cleavage of the urethane bonds. This decomposes the adhesive layer 3, allowing the residue of the adhesive layer 3 adhering to the electronic device 456 to be removed.

[0213] The acid or alkali used to decompose the urethane bond is not particularly limited. Examples of acids capable of decomposing urethane bonds include, but are not limited to, hydrochloric acid, sulfuric acid, and nitric acid. Examples of alkalis capable of decomposing urethane bonds include, but are not limited to, inorganic bases such as potassium hydroxide and sodium hydroxide; and organic amines such as tetramethylammonium hydroxide and monoethanolamine.

[0214] The acid or alkali can be dissolved in a solvent and used as a treatment liquid for removing the adhesive layer. The solvent is preferably a polar solvent, such as dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), diethylene glycol monobutyl ether, diethylene glycol, ethylene glycol, or propylene glycol. The adhesive layer removal treatment liquid may contain known additives such as surfactants in addition to the above components. The content of acid or alkali in the treatment liquid is not particularly limited, but may be, for example, 1 to 50% by mass, and the content of polar solvent in the treatment liquid may be, for example, 50 to 99% by mass. The treatment liquid for removing the adhesive layer may be a commercially available alkaline treatment liquid or acid treatment liquid, such as ST-120 or ST-121 (both manufactured by Tokyo Ohka Kogyo Co., Ltd.). By bringing the adhesive layer 3 into contact with the above-mentioned treatment liquid containing an acid or alkali, the urethane bonds in the adhesive layer 3 are decomposed, and the adhesive layer 3 can be removed.

[0215] In the method for manufacturing an electronic component of this embodiment, after the adhesive layer removal step, electronic component 50 may be further subjected to processes such as solder ball formation, dicing, or oxide film formation.

[0216] According to the method for producing an electronic component of this embodiment, the resin (P1) contains a structural unit (u1) including a structure (structure X) that absorbs at least a portion of light within a wavelength range of 300 to 800 nm. Therefore, irradiation with light of this wavelength alters the adhesive layer, reducing its adhesive strength. Therefore, even without a separation layer, the temporarily bonded semiconductor substrate or the like can be easily separated from the support. Because structure X is incorporated as a structural unit of the resin (P1), the content of structure X can be increased while maintaining good adhesiveness. This allows for both good adhesiveness and separability. Furthermore, when component (P1) is a urethane resin, residues of the adhesive layer adhering to the semiconductor substrate or the like after separation from the support can be easily removed by decomposing the urethane bonds with an acid or alkali. [Example]

[0217] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0218] <Urethane Resin Synthesis Example 1: Urethane Resin (P1-1)> Propylene glycol monomethyl ether acetate (PGMEA), 16 parts of polycarbonate diol (long chain), 16 parts of polycarbonate diol (short chain), 13 parts of glycerin monoacrylate, 20 parts of monomer (T-33), and an inhibitor were added to a flask equipped with a stirrer, dropping funnel, condenser, and thermometer, and mixed uniformly under a nitrogen stream. Next, 35 parts of isophorone diisocyanate were added to the dropping funnel and added dropwise 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, 2HEA (2-hydroxyethyl acrylate) was added, and the mixture was aged for 1 hour. The reaction was terminated when the isocyanate groups (NCO) disappeared. The weight-average molecular weight (Mw) of the resulting urethane resin (P1-1) was 15,800. The C═C equivalent (molecular weight of the urethane resin per equivalent of polymerizable carbon-carbon double bond) of the urethane resin (P1-1) was 1230 g / eq.

[0219] <Urethane Resin Synthesis Example 2: Urethane Resin (P1-2)> Urethane resin (P1-2) was synthesized in the same manner as in Synthesis Example 1, except that the monomer composition was as shown in Table 1. The weight average molecular weight (Mw) of the resulting urethane resin (P1-2) was 32,000. The C=C equivalent (molecular weight of the urethane resin per equivalent of polymerizable carbon-carbon double bonds) of the urethane resin (P1-2) was 1,230 g / eq.

[0220] <Urethane Resin Synthesis Example 3: Urethane Resin (P1-3)> Urethane resin (P1-3) was synthesized in the same manner as in Synthesis Example 1, except that the monomer composition was as shown in Table 1. The weight average molecular weight (Mw) of the resulting urethane resin (P1-3) was 33,200. The C=C equivalent (molecular weight of the urethane resin per equivalent of polymerizable carbon-carbon double bonds) of the urethane resin (P1-3) was 1,230 g / eq.

[0221] <Urethane Resin Synthesis Example 4: Urethane Resin (P2-1)> Urethane resin (P2-1) was synthesized in the same manner as in Synthesis Example 1, except that the monomer composition was as shown in Table 1. The weight average molecular weight (Mw) of the resulting urethane resin (P2-1) was 16,000. The C=C equivalent (molecular weight of the urethane resin per equivalent of polymerizable carbon-carbon double bonds) of the urethane resin (P2-1) was 1,230 g / eq.

[0222] [Table 1]

[0223] Details of each component in Table 1 are as follows: Isophorone diisocyanate (IPDI).

[0224] [ka]

[0225] Polycarbonate diol (long chain): Polycarbonate diol represented by the following formula (PC-1-1) (R=-(CH2)6-, -(CH2)5-), Mw=1,000. Polycarbonate diol (short chain): Polycarbonate diol represented by the following formula (PC-1-1) (R=-(CH2)6-, -(CH2)5-), Mw=500.

[0226] [ka]

[0227] Glycerin monoacrylate (GLMA).

[0228] [ka]

[0229] Monomer (U1-1): A compound represented by the following formula (U1-1). Monomer (U1-2): A compound represented by the following formula (U1-2).

[0230] [ka]

[0231] <Preparation of Adhesive Composition> (Examples 1 to 3, Comparative Examples 1 and 2) The components shown in Table 2 were mixed to prepare the adhesive compositions of each example.

[0232] [Table 2]

[0233] In Table 2, the abbreviations have the following meanings: The numbers in brackets [ ] are the blend amounts (parts by mass). (P1)-1 to (P1)-3: Urethane resins (P1-1) to (P1-3) synthesized in Synthesis Examples 1 to 3 above. (P2)-1: The urethane resin (P2-1) synthesized in Synthesis Example 4 above. (P2)-2: Septon 8004 (trade name), manufactured by Kuraray Co., Ltd. Styrene content: 12 mol %, weight average molecular weight: 98,000; elastomer having multiple structural units represented by the following chemical formula.

[0234] [ka]

[0235] (A)-1: Peroxide (Percumyl (registered trademark) D, NOF Corporation). Bis(1-methyl-1-phenylethyl) peroxide (Ad)-1: Polymerization inhibitor. IRGANOX1010 (trade name), manufactured by BASF. Pentaerythryl tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (S)-1:PGMEA. (S)-2: Decahydronaphthalene.

[0236] [Storage modulus (G') measurement] The adhesive composition of each example was applied to a PET film with a release agent and heated in an atmospheric oven at 50°C and 100°C for 60 minutes each to form an adhesive composition layer (0.5 mm thick). The adhesive composition layer was then peeled off from the PET film and its storage modulus (G') at 150°C was measured using a dynamic viscoelasticity measuring device (Rheogel-E4000, manufactured by UBM Inc.). The measurement conditions were as follows: the adhesive composition layer had a sample shape of 2.5 mm x 2.5 mm x 0.5 mm, and the temperature was raised from room temperature to 215°C at a rate of 5°C / min under shear conditions at a frequency of 1 Hz, and the storage modulus (G') was measured.

[0237] <Production of laminate> The adhesive composition of each example was spin-coated onto a bare silicon chip (5 mm x 5 mm) and baked at 100°C for 10 minutes to form an adhesive layer with a thickness of 25 µm. Next, using a die bonder (manufactured by TRESKY Corporation), the plate of the die bonder was heated to 50°C, and the bare chip was pressure-bonded to a bare glass support (thickness: 0.7 mm, E-XG, CORNING) via the adhesive layer at a pressure of 350 g for 90 seconds. Next, the adhesive layer was cured by heating at 180°C for 15 minutes, and a laminate was obtained.

[0238] [Adhesion evaluation] The laminate was prepared as described above, and the adhesion between the bare chip and the bare glass support was evaluated. The adhesion was evaluated based on the following evaluation criteria. The evaluation results are shown in Table 3. Evaluation criteria ◯: The bare chip and the bare glass support were successfully attached. ×: The bare chip and the bare glass support could not be attached to each other.

[0239] [Separability evaluation] Using IPEX848 (308 nm XeCl, Light Machinery), the adhesive layer of the laminate was irradiated with a 308 nm laser beam from the bare glass support side under the conditions of a scanning speed of 15.6 mm / s (overlap 80%), a frequency of 60 kHz, and a beam size of 2 × 14 mm. Then, an attempt was made to peel off the bare glass. Separability was evaluated based on the following evaluation criteria. The evaluation results are shown in Table 3. Evaluation criteria ○: Laser light irradiation dose 300 mJ / cm 2 It was peeled off as follows: ×: Laser light irradiation dose 300 mJ / cm 2 It did not peel off at the following temperature.

[0240] [Table 3]

[0241] The results shown in Table 3 confirm that the adhesive layers formed using the adhesive compositions of Examples 1 to 3 have good adhesive properties and also function as separation layers. [Explanation of symbols]

[0242] 1 Support 3 Adhesive layer 3' adhesive composition layer 4. Semiconductor substrate 5 Encapsulant layer 6 wiring layer 20 laminate 50 Electronic Components 100 laminate 100' laminate 110 Laminate 120 laminate 200 laminate 300 laminate 400 laminate 456 Electronic Devices 645 Electronic Devices

Claims

1. An adhesive composition used to form an adhesive layer that temporarily bonds a semiconductor substrate or an electronic device to a light-transmitting support, Resin (P1), A polymerization initiator (A), The resin (P1) is a urethane resin containing a polymerizable carbon-carbon unsaturated bond, and has a structural unit (u1) containing a structure (X) that absorbs at least a portion of light in a wavelength range of 300 to 800 nm, and the structural unit (u1) is derived from a polymerizable monomer containing a structure (X). The adhesive composition layer formed from the adhesive composition has a storage modulus (G') at 150°C of 1.5 x 10 ５ Pa or less, Adhesive composition.

2. The adhesive composition according to claim 1, wherein the structural unit (u1) comprises a fused ring skeleton having aromaticity, a benzophenone skeleton, a dibenzoylmethane skeleton, a dibenzoylbenzene skeleton, or a benzotriazole skeleton.

3. 3. The adhesive composition according to claim 1, wherein the electronic device is a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member, and the composite is laminated on the support via the adhesive layer.

4. A laminate in which a light-transmitting support, an adhesive layer, and a semiconductor substrate or an electronic device are laminated in this order, The adhesive layer is a cured product of the adhesive composition according to any one of claims 1 to 3. Laminate.

5. A method for producing a laminate in which a light-transmitting support, an adhesive layer, and a semiconductor substrate are laminated in this order, comprising: A step of applying the adhesive composition according to any one of claims 1 to 4 to the support or semiconductor substrate to form an adhesive composition layer; placing the semiconductor substrate on the support via the adhesive composition layer; curing the adhesive composition layer to form the adhesive layer; A method for producing a laminate comprising the steps of:

6. A method for producing a laminate in which a light-transmitting support, an adhesive layer, and an electronic device are laminated in this order, comprising the steps of: After obtaining a laminate by the laminate manufacturing method according to claim 5, a step of forming an electronic device which is a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member is further included. A method for manufacturing a laminate.

7. After obtaining a laminate by the laminate manufacturing method according to claim 6, a step of irradiating the adhesive layer with light through the support to alter the adhesive layer, thereby separating the electronic device from the support; removing the adhesive layer attached to the electronic device; The method for manufacturing an electronic component includes the steps of:

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