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

Abstract

An adhesive composition for forming an adhesive layer that temporarily bonds a semiconductor substrate or electronic device to a light-transmitting support, the adhesive composition comprising: (a) a light absorber, a polyisocyanate, and a polyol; or (b) a light absorber, a polyurethane resin comprising polymeric carbon-carbon unsaturated bonds, and a polymerization initiator.

Description

Technical Field

[0001] This invention relates to adhesive compositions, laminates, methods for manufacturing laminates, and methods for manufacturing electronic components.

[0002] This application claims priority based on Japanese Patent Application No. 2019-238291 filed in Japan on December 27, 2019, and Japanese Patent Application No. 2020-110426 filed in Japan on June 26, 2020, the contents of which are incorporated herein by reference. Background Technology

[0003] In semiconductor packages (electronic components) that contain semiconductor elements, there are various forms depending on the corresponding size, such as WLP (Wafer Level Package) and PLP (Panel Level Package).

[0004] Examples of semiconductor packaging technologies include fan-in and fan-out technologies. As a semiconductor package based on fan-in technology, fan-in wafer-level packages (WLPs) are known, where terminals located at the ends of the bare die are repositioned within the chip area. As a semiconductor package based on fan-out technology, fan-out wafer-level packages (WLPs) are known, where the terminals are repositioned outside the chip area.

[0005] In recent years, fan-out technology has in particular gained attention as a method that enables further integration, thinning, and miniaturization of semiconductor packaging. For example, it has been applied to fan-out panel level packages (PLPs) that place semiconductor components on a panel and package them.

[0006] To achieve miniaturization of semiconductor packages, it is important to reduce the thickness of the substrate in the assembled components. However, reducing the substrate thickness reduces its strength, making it prone to breakage during semiconductor package manufacturing. To address this, a known technique involves temporarily bonding the substrate to a support using an adhesive, followed by substrate processing, and then separating the substrate from the support.

[0007] For adhesives used in temporary bonding between a substrate and a support, thermoplastic adhesives are generally used to facilitate the removal of the adhesive layer using solvents or the like. For example, Patent Document 1 discloses an adhesive composition containing a thermoplastic elastomer, a high-boiling-point solvent, and a low-boiling-point solvent.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: International Publication No. 2016 / 052315 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] On the other hand, in the manufacturing of semiconductor packages, high-temperature processes such as thin film formation, firing, and chip bonding are sometimes performed. If the adhesive has low heat resistance, the elastic modulus of the adhesive layer will decrease during high-temperature processing, raising concerns about substrate displacement and substrate sinking. On the other hand, increasing the heat resistance of the adhesive tends to reduce the coatability of the substrate or support.

[0013] When thermosetting adhesives are used to bond the support to the substrate, problems such as positional shift or sinking do not occur during high-temperature processing. However, it is difficult to remove the adhesive layer using solvents or the like. Even when a release layer is provided, it is still difficult to remove the adhesive layer attached to the substrate after separating the support from the substrate by modifying the release layer.

[0014] Furthermore, with conventional adhesives, a release layer is typically required to separate the support from the substrate after substrate processing. Therefore, forming the release layer and the adhesive layer separately is a cumbersome process.

[0015] The present invention was made in view of the above circumstances, and its object is to provide an adhesive composition that does not require a release layer, has high heat resistance, and allows for easy removal of the adhesive 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.

[0016] Methods for solving problems

[0017] To address the aforementioned issues, the present invention employs the following configuration.

[0018] That is, the first aspect of the present invention is an adhesive composition for forming an adhesive layer that temporarily bonds a semiconductor substrate or electronic device to a light-transmitting support, the adhesive composition comprising: (a) a light absorber, a polyisocyanate, and a polyol; or (b) a light absorber, a polyurethane resin comprising polymerizable carbon-carbon unsaturated bonds, and a polymerization initiator.

[0019] The second aspect of the present invention is a laminate, which is a laminate in which a light-transmitting support, an adhesive layer, and a semiconductor substrate or electronic device are sequentially stacked, wherein the adhesive layer is a cured body of the adhesive composition involved in the first aspect.

[0020] The third aspect of the present invention is a method for manufacturing a laminate, which is a method for manufacturing a laminate in which a light-transmitting support, an adhesive layer and a semiconductor substrate are sequentially laminated. The manufacturing method includes the following steps: a step of coating the adhesive composition involved in the first aspect onto the support or the semiconductor substrate to form an adhesive composition layer; a step of placing the semiconductor substrate on the support through the adhesive composition layer; and a step of curing the adhesive composition layer to form the adhesive layer.

[0021] The fourth aspect of the present invention is a method for manufacturing a laminate, wherein the laminate comprises a light-transmitting support, an adhesive layer, and an electronic device stacked sequentially. In the manufacturing method, after obtaining the laminate using the manufacturing method of the laminate described in the third aspect, there is an electronic device forming step for forming the electronic device, wherein the electronic device is a composite formed of a component made of metal or semiconductor and a resin that seals or insulates the component.

[0022] The fifth aspect of the present invention is a method for manufacturing an electronic component, wherein, after obtaining a laminate using the method for manufacturing a laminate according to the fourth aspect described above, the method includes the following steps: modifying the adhesive layer by irradiating the adhesive layer with light through the support, thereby separating the electronic device from the support; and removing the adhesive layer attached to the electronic device by decomposing the urethane bonds in the adhesive layer using an acid or alkali.

[0023] Invention Effects

[0024] According to the present invention, an adhesive composition that does not require a release layer, has high heat resistance, and allows for easy removal of the adhesive layer can be provided; 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. Attached Figure Description

[0025] [ Figure 1 This is a schematic diagram illustrating one embodiment of a laminated body to which the present invention is applied.

[0026] [ Figure 2 This is a schematic diagram illustrating one embodiment of a laminated body to which the present invention is applied.

[0027] [ Figure 3 This is a schematic diagram illustrating one embodiment of a laminated body to which the present invention is applied.

[0028] [ Figure 4 This is a schematic diagram illustrating one embodiment of a laminated body to which the present invention is applied.

[0029] [ Figure 5A ] Figures 5A-5BThis is a schematic process diagram illustrating one embodiment of a manufacturing method for a laminate 100' in which a support, an adhesive composition layer, and a semiconductor substrate are sequentially stacked. Figure 5A This diagram illustrates the process of forming an adhesive composition layer.

[0030] [ Figure 5B ] Figure 5B This diagram illustrates the semiconductor substrate placement process.

[0031] [ Figure 6 This is a diagram illustrating the process of forming the adhesive layer.

[0032] [ Figure 7A ] Figures 7A-7C A schematic process diagram illustrating one embodiment of a method for manufacturing a laminate 120. Figure 7A This diagram illustrates the sealing process.

[0033] [ Figure 7B ] Figure 7B This diagram illustrates the grinding process.

[0034] [ Figure 7C ] Figure 7C This diagram illustrates the wiring layer formation process.

[0035] [ Figure 8A ] Figures 8A-8C This is a schematic process diagram illustrating one embodiment of a method for manufacturing a semiconductor package (electronic component) from a laminate 120. Figure 8A A diagram illustrating the laminate 200.

[0036] [ Figure 8B ] Figure 8B This diagram illustrates the separation process.

[0037] [ Figure 8C ] Figure 8C This diagram illustrates the process of removing the adhesive layer. Detailed Implementation

[0038] In this specification and claims, "aliphatic" is a relative concept compared to aromatic, and is defined as non-aromatic groups, compounds, etc.

[0039] Unless otherwise specified, "alkyl" includes straight-chain, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to alkyl groups in alkoxy groups.

[0040] Unless otherwise specified, "alkylene" includes straight-chain, branched, and cyclic divalent saturated hydrocarbon groups.

[0041] "Halogenated alkyl" is a group obtained by replacing some or all of the hydrogen atoms of an alkyl group with halogen atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0042] "Fluoroalkyl" or "fluoroalkylene" refers to a group obtained by replacing some or all of the hydrogen atoms of an alkyl or alkylene group with fluorine atoms.

[0043] "Structural unit" refers to the monomer unit (monomer unit) that makes up a polymer compound (resin, polymer, copolymer).

[0044] When it is recorded as "may have substituents" or "may have substituents", it includes both cases where the hydrogen atom (-H) is replaced by a monovalent group and cases where the methylene group (-CH2-) is replaced by a divalent group.

[0045] "Exposure" is a concept that includes the irradiation of the entire body by radiation.

[0046] "Structural units derived from hydroxystyrene" refers to structural units formed by the breaking of the olefinic double bonds in hydroxystyrene. "Structural units derived from hydroxystyrene derivatives" refers to structural units formed by the breaking of the olefinic double bonds in hydroxystyrene derivatives.

[0047] "Hydroxystyrene derivatives" refers to compounds formed by replacing the α-hydrogen atom of hydroxystyrene with other substituents such as alkyl or haloalkyl groups, as well as their derivatives. Examples of their derivatives include: compounds formed by replacing the hydrogen atom of the hydroxyl group in hydroxystyrene, where the α-hydrogen atom can be replaced by a substituent, with an organic group; compounds in which a substituent other than the hydroxyl group is bonded to the benzene ring of hydroxystyrene, where the α-hydrogen atom can be replaced by a substituent; and so on. It should be noted that unless otherwise specified, the α-position (α-carbon atom) refers to the carbon atom bonded to the benzene ring.

[0048] As a substituent that replaces the α-hydrogen atom of hydroxystyrene, examples can be made of the same substituents as those mentioned above for α-substituted acrylates.

[0049] The alkyl group used as the α-substituent is preferably a straight-chain or branched alkyl group. Specifically, examples include alkyl groups with 1 to 5 carbon atoms (methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc.).

[0050] Furthermore, the alkyl halogroup that serves as the α-position substituent can specifically be a group obtained by replacing some or all of the hydrogen atoms of the aforementioned alkyl halogroup with a halogen atom. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being particularly preferred.

[0051] Furthermore, the hydroxyalkyl group that serves as the α-substituent can specifically be a group obtained by replacing some or all of the hydrogen atoms of the aforementioned "alkyl group that serves as the α-substituent" with a hydroxyl group. The number of hydroxyl groups in this hydroxyalkyl group is preferably 1 to 5, and most preferably 1.

[0052] In this specification and claims, depending on the structure represented by the chemical formula, a chiral carbon is present, and sometimes enantiomers and diastereomers may be present. In such cases, these isomers are represented by a single formula. These isomers may be used alone or in mixtures.

[0053] (Adhesive composition)

[0054] For the adhesive composition according to the first aspect of the present invention, which is used to form an adhesive layer for temporarily bonding a semiconductor substrate or electronic device to a light-transmitting support, the adhesive composition is characterized in that it contains: (a) a light absorber, a polyisocyanate, and a polyol; or (b) a light absorber, a polyurethane resin containing polymerizable carbon-carbon unsaturated bonds, and a polymerization initiator.

[0055] <Objects temporarily glued>

[0056] The adhesive composition described in this embodiment can be used to form an adhesive layer that temporarily bonds a semiconductor substrate or electronic device to a support. In this specification, "temporary bonding" means that the objects being bonded are temporarily bonded (e.g., during any operational process). More specifically, for purposes such as device thinning, semiconductor substrate handling, or mounting to a semiconductor substrate, the semiconductor substrate or electronic device is temporarily bonded to and fixed (temporarily bonded) to the support, and then separated from the support after the process is completed.

[0057] Semiconductor Substrates

[0058] The semiconductor substrate to which the adhesive composition of this embodiment is applied is not particularly limited, and can be any substrate commonly used as a semiconductor substrate. The semiconductor substrate (bare die) is supplied for thinning, mounting, and other processes in a state supported by a support. Structures such as integrated circuits and metal bumps can be mounted on the semiconductor substrate.

[0059] As a semiconductor substrate, silicon wafer substrates are a typical example, but not limited to them; ceramic substrates, thin film substrates, flexible substrates, etc. can also be used.

[0060] Electronic Components

[0061] In this specification, "electronic device" refers to a component that constitutes at least a part of an electronic component. There are no particular limitations on the type of electronic device; it can be a device with various mechanical structures and circuits formed on the surface of a semiconductor substrate. Preferably, the electronic device is a composite formed of a component made of metal or semiconductor and a resin that seals or insulates the aforementioned component. The electronic device can be a redistribution layer (described later), and / or a semiconductor element or other component sealed or insulated by a sealing or insulating material, and can have a single-layer or multi-layer structure.

[0062] Support

[0063] A support is a component that supports a semiconductor substrate or electronic device. As described below, a support is composed of a component that supports a semiconductor substrate and has the property of allowing light to pass through.

[0064] The adhesive composition of this embodiment contains any one of the following components (a) or (b).

[0065] (a) Light absorbers, polyisocyanates, and polyols.

[0066] (b) A light absorber, a polyurethane resin containing polymeric carbon-carbon unsaturated bonds, and a polymerization initiator.

[0067] For convenience, the adhesive composition containing the component (a) above will also be referred to as "adhesive composition (a)" and the adhesive composition containing the component (b) above will also be referred to as "adhesive composition (b)".

[0068] Both adhesive compositions (a) and (b) are curable adhesive compositions that form a cross-linked structure and cure by heating or the like. Therefore, an adhesive layer that temporarily bonds the semiconductor substrate or the like to the support can be formed by forming an adhesive composition layer between the semiconductor substrate or electronic device (hereinafter also collectively referred to as "semiconductor substrate, etc.") and the support and then curing it.

[0069] On the other hand, the adhesive layer formed by the adhesive composition (a) or the adhesive composition (b) contains a light absorber. Therefore, when light is irradiated onto the adhesive layer through a light-transmitting support, the light absorber in the adhesive layer absorbs the light, and the adhesive layer is modified. As a result, the semiconductor substrate or device temporarily bonded through the aforementioned adhesive layer can be separated from the light-transmitting support.

[0070] Furthermore, the adhesive layer formed by adhesive composition (a) or adhesive composition (b) contains polyurethane resin, and therefore, the adhesive layer can be decomposed by using an acid or alkali to break down the urethane bonds. This allows for the removal of residues from the adhesive layer adhering to the semiconductor substrate or device after separation from the light-transmitting support.

[0071] <Adhesive Composition (a)>

[0072] The adhesive composition (a) contains a light absorber, a polyisocyanate, and a polyol. In adhesive composition (a), upon heating, the polyisocyanate and polyol crosslink via urethane bonds. This causes the adhesive composition layer to cure, forming an adhesive layer that temporarily bonds the support and the semiconductor substrate. On the other hand, if the adhesive layer is irradiated with light such as a laser, the light absorber absorbs the light, and the adhesive layer is modified. This allows the support and the semiconductor substrate to be separated. Furthermore, residues of the adhesive layer adhering to the semiconductor substrate can be removed by decomposing the urethane bonds using an acid or alkali.

[0073] Light absorber: (B) component

[0074] The adhesive composition (a) contains a light absorber (hereinafter also referred to as "component (B)"). By containing component (B) in the adhesive composition (a), the adhesive layer can be modified by irradiation with light.

[0075] (B) is not particularly limited as long as it is a material with light absorption capabilities. For (B), depending on the wavelength of the light irradiated during the separation of the support and the semiconductor substrate, a component capable of absorbing that wavelength can be used. For example, (B) can be a component capable of absorbing light in the wavelength range of 300–800 nm. (B) is preferably a component capable of absorbing light in the wavelength range of 400–700 nm, more preferably a component capable of absorbing light in the wavelength range of 450–600 nm, and even more preferably a component capable of absorbing light in the wavelength range of 500–550 nm.

[0076] As a component (B), for example, pigments and dyes can be cited.

[0077] ·pigment

[0078] Pigments can be organic or inorganic. Pigments can be any type of pigment, including black pigments and colored pigments.

[0079] Examples of black organic pigments include perylene black (perylene-based black pigments), cyanine black, aniline black, and lactam black. Examples of black inorganic pigments include carbon black (lampblack, acetylene black, thermal cracking carbon black, channel black, furnace black, etc.), chromium oxide, iron oxide, titanium black, titanium oxynitride, titanium nitride, strontium titanate, chromium oxide, and cerium dioxide.

[0080] As coloring pigments, for example, compounds classified as pigments in the Dye Index (CI; published by The Society of Dyers and Colourists) can be cited, and more specifically, compounds assigned Dye Index (CI) numbers as described below can be cited.

[0081] CI Pigment Yellow 1 (hereinafter, also "CI Pigment Yellow", only the number is recorded), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185;

[0082] CI Pigment Orange 1 (hereinafter, also "CI Pigment Orange", only the number is recorded), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, 73;

[0083] CI Pigment Violet 1 (hereinafter, also "CI Pigment Violet", only the number is recorded), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;

[0084] CI Pigment Red 1 (hereinafter, also "CI Pigment Red", only the number is listed), 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 10 4, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265;

[0085] CI Pigment Blue 1 (hereinafter also "CI Pigment Blue", only the number is recorded), 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66;

[0086] CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37;

[0087] CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Brown 26, CI Pigment Brown 28;

[0088] CI Pigment Black 1, Pigment Black 7.

[0089] The particle size of the pigment can be appropriately set; for example, the volume average particle size is 10 nm to 1000 nm, preferably 10 nm to 500 nm, and more preferably 10 nm to 300 nm. The volume average particle size can be determined using dynamic light scattering.

[0090] Pigments can be used alone or in combination with two or more. Furthermore, multiple pigments that absorb light in different wavelength ranges can be combined; for example, black pigment can be combined with one or more colored pigments.

[0091] ·dye

[0092] Examples of dyes include, for instance, azo dyes (monoazo and polyazo dyes, metal-coordinated azo dyes, pyrazolone azo dyes, irazolone dyes, thiazo azo dyes), anthraquinone dyes (anthraquinone derivatives, anthrone derivatives), indigo dyes (indigo derivatives, thioindigo derivatives), phthalocyanine dyes, carbomonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthan dyes, acridine dyes), quinone imine dyes (azine dyes, oxazine dyes, thiazine dyes), methyl cyanide dyes (cyanide dyes, methyl imine dyes), quinoline dyes, nitroso dyes, benzoquinone and naphthoquinone dyes, naphthalene dicarboximide dyes, and violet ketone dyes.

[0093] Commercially available dyes can be used. Examples of commercially available dyes include PC-5857 (manufactured by Oriental Industrial Co., Ltd.).

[0094] A single dye can be used alone, or two or more can be used in combination. In addition, multiple dyes that absorb light in different wavelength regions can be combined for use.

[0095] (B) Components can be used alone or in combination with two or more.

[0096] The content of component (B) in adhesive composition (a) is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and even more preferably 3 to 15% by mass, relative to the total mass (100% by mass) of adhesive composition (a). If the content of component (B) is above the lower limit mentioned above, the light absorption efficiency in the adhesive layer is improved, and the modification of the adhesive layer becomes better. If the content of component (B) is below the upper limit mentioned above, it is easy to achieve balance with other components.

[0097] In addition, the content of component (B) in adhesive composition (a) may be 5% or more or 10% or more of mass relative to the total mass (100% by mass) of adhesive composition (a).

[0098] Polyisocyanate Compounds: (I) Components

[0099] The adhesive composition (a) contains a polyisocyanate compound (hereinafter also referred to as "component (I)"). In this specification, "polyisocyanate compound" means a compound having two or more isocyanate groups (-N=C=O) or a compound having two or more terminal isocyanate groups (terminated polyisocyanate). There are no particular limitations on the polyisocyanate used, and polyisocyanates commonly used in the manufacture of polyurethane resins may be used without particular restriction.

[0100] A capped polyisocyanate is a compound inactive by capping the isocyanate group of a polyisocyanate through a reaction with a capping agent. The capped polyisocyanate used as component (I) is preferably a substance obtained by capping the isocyanate group using a thermally dissociative capping agent. Examples of thermally dissociative capping agents include oximes, diketones, phenols, and caprolactams. For capped polyisocyanates obtained using thermally dissociative capping agents, the isocyanate group is inactive at room temperature; upon heating, the thermally dissociative capping agent dissociates, regenerating the isocyanate group.

[0101] 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 diphenylene diisocyanate, hydrogenated toluene diisocyanate, and dicyclohexylmethane-4,4'-diisocyanate; aromatic diisocyanates such as toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, diphenylene diisocyanate, dimethylbiphenyl diisocyanate, terephthalene diisocyanate, and naphthalene diisocyanate; and their biuret forms, isocyanurate forms, and trimethylolpropane adducts. A single polyisocyanate may be used alone, or two or more may be used in combination.

[0102] Commercially available polyisocyanates are permitted. Examples of commercially available polyisocyanates include, for instance, 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, 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). These products can be used alone or in combination with two or more.

[0103] Examples of end-capped isocyanates include compounds in which the isocyanate group of the aforementioned polyisocyanates is protected by reaction with an end-capping agent. As for the end-capping agent, any thermally dissociative end-capping agent—that is, a compound that adds to the isocyanate group and is stable at room temperature but becomes free upon heating above its dissociation temperature to form an isocyanate group—is acceptable; there are no particular limitations, and known compounds can be used without special restrictions.

[0104] Specific examples of end-capping agents include: lactam compounds such as γ-butyrolactam, ε-caprolactam, γ-pentanolactam, and propiolactam; oxime compounds such as methyl ethyl ketone oxime, methyl isopentyl ketone oxime, methyl isobutyl ketone oxime, formamide oxime, acetamide oxime, acetone oxime, 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 methanol, ethanol, isopropanol, tert-butanol, trimethylolpropane, and 2-ethylhexyl alcohol; ether compounds such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether; active methylene compounds such as alkyl malonate, dialkyl malonate, alkyl acetoacetate, and acetylacetone; and so on. One end-capping agent can be used alone, or two or more can be used in combination.

[0105] Terminally capped polyisocyanates can be manufactured by reacting polyisocyanates with a capping agent. The reaction of polyisocyanates with the capping agent can be carried out, for example, in a solvent without active hydrogen (1,4-dioxane, cellosol acetate, etc.), under heating at approximately 50–100°C, and in the presence of a capping catalyst added as needed. The ratio of polyisocyanate to capping agent is not particularly limited, but based on the equivalent ratio of isocyanate groups in the polyisocyanate to the capping agent, it is preferably 0.95:1.0 to 1.1:1.0, more preferably 1:1.05 to 1.15. As end-capping catalysts, known substances can be used, such as: metal alkoxides like sodium methoxide, sodium ethoxide, sodium phenoxide, and potassium methoxide; hydroxides of tetraalkylammonium such as tetramethylammonium, tetraethylammonium, and tetrabutylammonium; their acetates, octanoates, myristicates, benzoates, and other organic weak acid salts; and alkali metal salts of alkylcarboxylic acids such as acetic acid, hexanoic acid, octanoic acid, and myristic acid; etc. One end-capping catalyst can be used alone, or two or more can be used in combination.

[0106] Commercially available products can be used for end-capped polyisocyanates. Examples of commercially available end-capped polyisocyanates include Durnate MF-K60B, Durnate SBB-70P, Durnate SBN-70D, Durnate MF-B60B, Durnate17B-60P, Durnate TPA-B80E, and Durnate E402-B80B (these are trade names, manufactured by Asahi Kasei Corporation).

[0107] As component (I), a capped polyisocyanate obtained by capping isocyanate groups using a thermally dissociative capping agent is preferred.

[0108] (I) One ingredient may be used alone, or two or more ingredients may be used together.

[0109] The content of component (I) in adhesive composition (a) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 20 to 40% by mass, relative to the total mass (100% by mass) of adhesive composition (a). If the content of component (I) is above the lower limit mentioned above, the curing properties of adhesive composition (a) become good. If the content of component (I) is below the upper limit mentioned above, it is easy to achieve balance with other components.

[0110] Polyols: (O) Components

[0111] The adhesive composition (a) contains a polyol (hereinafter also referred to as "(O) component"). The polyol is a compound having two or more hydroxyl groups (-OH). There are no particular limitations on the polyol used; polyols commonly used in the manufacture of polyurethane resins can be used without particular restriction. The (O) component can be an aliphatic polyol or an aromatic polyol. The (O) component can be a low molecular weight polyol (e.g., with a molecular weight less than 500) or a high molecular weight polyol (e.g., with a molecular weight greater than 500).

[0112] Specific examples of low-molecular-weight polyols include: ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentanediol, alkane diols with 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 with 17 to 20 carbon atoms, 1,3-cyclohexanediol, 1 Diols such as 4-cyclohexanediol, 1,4-cyclohexanediol, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octen-3,8-diol, and bisphenol A; triols such as glycerol and trimethylolpropane; tetramethylol(tetrazol) and diglycerides; pentols such as xylitol; hexaols such as sorbitol, mannitol, allitol, idoteol, eurythritol, atroitol, inositol, and dipentaerythritol; septols such as mannitol and heptetol; and octols such as sucrose; etc.

[0113] Examples of high molecular weight polyols include phenolic resins, resins containing a hydroxystyrene backbone, polyester polyols, polyether polyols, polyether ester polyols, polyesteramide polyols, acrylic polyols, polycarbonate polyols, polyhydroxyalkane, polyurethane polyols, and vegetable oil-based polyols. The number average molecular weight of the high molecular weight polyol is preferably between 500 and 100,000.

[0114] [Phenolic resin]

[0115] Phenolic resins can be either Novolac or Resol type. Novolac type phenolic resins are obtained by adding and condensing aromatic compounds with phenolic hydroxyl groups (hereinafter referred to as "phenols") with aldehydes under an acid catalyst. Resol type phenolic resins are obtained by adding and condensing phenols with aldehydes under an alkaline catalyst.

[0116] Examples of the aforementioned phenols include: phenol; cresols such as m-cresol, p-cresol, and o-cresol; xylenephenols 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; and p-methoxyphenol, m-methoxyphenol, and p-ethoxyphenol. Alkoxyphenols such as phenol, m-ethoxyphenol, 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.

[0117] Examples of the aforementioned aldehydes include, for example, formaldehyde, paraformaldehyde, triformaldehyde, furfural, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropanaldehyde, β-phenylpropanaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, cinnamaldehyde, 4-isopropylbenzaldehyde, 4-isobutylbenzaldehyde, 4-phenylbenzaldehyde, etc.

[0118] There are no particular limitations on the acid catalyst for addition condensation reactions; for example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, and acetic acid can be used. There are also no particular limitations on the base catalyst for addition condensation reactions; sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonia, triethylamine, sodium carbonate, and hexamethylenetetramine can be used.

[0119] [Resins containing a hydroxystyrene backbone]

[0120] As a resin containing a hydroxystyrene backbone, it 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 the structural unit represented by the following general formula (a10-1).

[0121] [Chemical Formula 1]

[0122]

[0123] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms. Ya] x1It is a single bond or a divalent linker. Wa x1 For (n ax1 +1) valence aromatic hydrocarbon group. ax1 [Integers from 1 to 3.]

[0124] In the above formula (a10-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms.

[0125] The alkyl group having 1 to 5 carbon atoms in R is preferably a straight-chain or branched alkyl group having 1 to 5 carbon atoms. Examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl. The haloalkyl group having 1 to 5 carbon atoms in R is a group in which some or all of the hydrogen atoms of the aforementioned alkyl group having 1 to 5 carbon atoms are replaced by halogen atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms, with fluorine atoms being particularly preferred.

[0126] R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms. From the perspective of industrial availability, a hydrogen atom or a methyl group is most preferred.

[0127] In the above formula (a10-1), Ya x1 It is a single bond or a divalent linker.

[0128] As Ya x1 The divalent linking group in the group, for example, a divalent hydrocarbon group having a substituent, or a divalent linking group containing a heteroatom, can be cited as suitable groups.

[0129] • Divalent hydrocarbon groups that can have substituents:

[0130] Ya x1 When the hydrocarbon group is a divalent hydrocarbon group that can have substituents, the hydrocarbon group can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0131] ··Ya x1 aliphatic hydrocarbon groups

[0132] The aliphatic hydrocarbon group refers to a hydrocarbon group that is not aromatic. The aliphatic hydrocarbon group can be saturated or unsaturated, but is usually preferred to be saturated.

[0133] Examples of aliphatic hydrocarbon groups include straight-chain or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing rings in their structure.

[0134] ...straight-chain or branched aliphatic hydrocarbon groups

[0135] 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.

[0136] As a straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred. Specifically, examples include methylene [-CH2-], ethylene [-(CH2)2-], trimethylene [-(CH2)3-], tetramethylene [-(CH2)4-], pentamethylene [-(CH2)5-], etc.

[0137] 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.

[0138] As a branched aliphatic hydrocarbon group, a branched alkylene group is preferred. Specifically, examples include: alkylmethylene such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyltrimethylene such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkyl alkylene group is preferably a straight-chain alkyl group with 1 to 5 carbon atoms.

[0139] The aforementioned straight-chain or branched aliphatic hydrocarbon groups may or may not have substituents. Examples of substituents include fluorine atoms, fluoroalkyl groups with 1 to 5 carbon atoms substituted by fluorine atoms, and carbonyl groups.

[0140] ...aliphatic hydrocarbon groups containing rings in their structure

[0141] Examples of aliphatic hydrocarbon groups containing a ring in this structure include cyclic aliphatic hydrocarbon groups (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) whose ring structure may contain substituents containing heteroatoms, groups formed by bonding the aforementioned cyclic aliphatic hydrocarbon group to the end of a straight-chain or branched aliphatic hydrocarbon group, and groups in which the aforementioned cyclic aliphatic hydrocarbon group is located in the middle of a straight-chain or branched aliphatic hydrocarbon group. Examples of the aforementioned straight-chain or branched aliphatic hydrocarbon groups are similar to those described above.

[0142] The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms.

[0143] The cyclic aliphatic hydrocarbon group can be either a polycyclic or monocyclic group. As a monocyclic alicyclic hydrocarbon group, it is preferably a group obtained by removing two hydrogen atoms from a monocyclic alkane. The monocyclic alkane is preferably a monocyclic alkane with 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. As a polycyclic alicyclic hydrocarbon group, it is preferably a group obtained by removing two hydrogen atoms from a polycyclic alkane. The polycyclic alkane is preferably a polycyclic alkane with 7 to 12 carbon atoms, specifically adamantane, norbornene, isocamphene, tricyclodecane, tetracyclododecane, etc.

[0144] Cyclic aliphatic hydrocarbon groups may or may not have substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, haloalkyl groups, hydroxyl groups, and carbonyl groups.

[0145] Regarding the alkyl group used as the above-mentioned substituent, it is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably methyl, ethyl, propyl, n-butyl, or tert-butyl.

[0146] Regarding the alkoxy group used as the above-mentioned substituent, it is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, or tert-butoxy, and most preferably methoxy or ethoxy.

[0147] Regarding the halogen atom that can be used as a substituent, examples include fluorine atom, chlorine atom, bromine atom, iodine atom, etc., with fluorine atom being preferred.

[0148] Regarding the alkyl halogroups used as the above-mentioned substituents, examples can be given of groups obtained by replacing some or all of the hydrogen atoms of the alkyl halogroup with the halogen atoms.

[0149] In the case of cyclic aliphatic hydrocarbon groups, a portion of the carbon atoms constituting the ring structure may be replaced by substituents containing heteroatoms. Preferred substituents containing heteroatoms are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0150] ··Ya x1 aromatic hydrocarbon groups

[0151] The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.

[0152] The aromatic ring only needs to be a cyclic conjugated system with 4n+2 π electrons; there are no particular limitations, and it can be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. This number of carbon atoms does not include the carbon atoms in the substituents. Examples of aromatic rings include: aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles obtained by substituting some carbon atoms of the aforementioned aromatic hydrocarbon rings with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings.

[0153] Specifically, examples of aromatic hydrocarbon groups include: groups (aryl or heteroaryl) obtained by removing two hydrogen atoms from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle; groups obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups obtained by substituting one hydrogen atom of an aryl or heteroaryl group obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle with an alkylene group (e.g., groups obtained by further removing one hydrogen atom from an aryl group in arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.). The alkylene group bonded to the aforementioned aryl or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

[0154] With regard to the aforementioned aromatic hydrocarbon group, the hydrogen atoms present in the aromatic hydrocarbon group can be replaced by substituents. For example, the hydrogen atoms bonded to the aromatic ring in the aromatic hydrocarbon group can be replaced by substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, haloalkyl groups, hydroxyl groups, etc.

[0155] Regarding the alkyl group used as the above-mentioned substituent, it is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably methyl, ethyl, propyl, n-butyl, or tert-butyl.

[0156] Regarding the alkoxy, halogen atom, and haloalkyl groups that are the above-mentioned substituents, examples of substituents that replace the hydrogen atoms of the above-mentioned cyclic aliphatic hydrocarbon groups can be given.

[0157] • Divalent linking groups containing heteroatoms:

[0158] Ya x1When the linking group is a divalent group containing a heteroatom, preferred links include -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H can be substituted by alkyl, acyl, or other substituents), -S-, -S(=O)2-, -S(=O)2-O-, and 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 - represents a group [where Y is a group that represents ... 21 and Y 22 Each can be an independent divalent hydrocarbon group that may have substituents, where O is an oxygen atom and m” is an integer from 0 to 3.

[0159] When the aforementioned divalent linking group containing heteroatoms is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, or -NH-C(=NH)-, its H atoms can be replaced by substituents such as alkyl or acyl groups. The number of carbon atoms in this substituent (alkyl, acyl, etc.) is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5.

[0160] 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 22 Each can be a divalent hydrocarbon group that may have substituents. Examples of such divalent hydrocarbon groups include those mentioned in the description of divalent linking groups (which may have substituents).

[0161] As Y21 Preferably, it is a straight-chain aliphatic hydrocarbon group, more preferably a straight-chain alkylene group, even more preferably a straight-chain alkylene group with 1 to 5 carbon atoms, and particularly preferably methylene or ethylene.

[0162] As Y 22 Preferably, it is a straight-chain or branched aliphatic hydrocarbon group, more preferably methylene, ethylene, or alkylmethylene. The alkyl group in the alkylmethylene group is preferably a straight-chain alkyl group with 1 to 5 carbon atoms, more preferably a straight-chain alkyl group with 1 to 3 carbon atoms, and most preferably methyl.

[0163] Formula-[Y 21 -C(=O)-O] m” -Y 22 In the group represented by -, m” is an integer from 0 to 3, preferably an integer from 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, as in formula -[Y 21 -C(=O)-O] m” -Y 22 - represents a group, particularly preferably of the formula -Y 21 -C(=O)-OY 22 - represents a group. Preferably, it is of the formula -(CH2). a’ -C(=O)-O-(CH2) b’ - represents a group. In this formula, a' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, further preferably 1 or 2, and most preferably 1. b' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, further preferably 1 or 2, and most preferably 1.

[0164] As Ya x1 Preferably, it is a single bond, an ester bond [-C(=O)-O-], an ether bond (-O-), a -C(=O)-NH-, a straight-chain or branched alkylene group, or a combination thereof, wherein, especially more preferably, it is a single bond.

[0165] In the above formula (a10-1), Wa x1 For (n ax1 +1) valence aromatic hydrocarbon group.

[0166] As Wa x1 Aromatic hydrocarbon groups in the aromatic ring can be exemplified by those removed from the aromatic ring (n ax1The aromatic ring is obtained by adding (+1) hydrogen atoms. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system with 4n+2 π electrons; it can be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Examples of aromatic rings include: aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some carbon atoms of the aforementioned aromatic hydrocarbon rings are replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen, sulfur, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings.

[0167] In the above formula (a10-1), n ax1 It is an integer from 1 to 3, preferably 1 or 2, and more preferably 1.

[0168] The following are specific examples of the structural units represented by the above general formula (a10-1).

[0169] In the following formula, R α It represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0170] [Chemical Formula 2]

[0171]

[0172] The resin containing the hydroxystyrene backbone is preferably a polymer of hydroxystyrene or a hydroxystyrene derivative, more preferably a polymer of hydroxystyrene (polyhydroxystyrene).

[0173] [Polycarbonate polyols]

[0174] Examples of polycarbonate polyols include those obtained by reacting one or more diols selected from ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 1,8-nonanediol, neopentanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanediol, bisphenol A, or hydrogenated bisphenol A with dimethyl carbonate, diphenyl carbonate, ethylene carbonate, or carbonyl chloride.

[0175] The polycarbonate polyol is preferably a polycarbonate diol represented by the following general formula (PC-1).

[0176] [Chemical Formula 3]

[0177]

[0178] [In the formula, Rp] 1 and Rp 2Each is an independent divalent hydrocarbon group. np is an integer greater than or equal to 2.

[0179] In the above general formula (PC-1), Rp 1 and Rp 2 Each is an independent divalent hydrocarbon group. These divalent hydrocarbon groups can be aromatic or aliphatic. Examples of such divalent hydrocarbon groups include Ya, which shares the general formula (a10-1) mentioned above. x1 The same divalent hydrocarbon group cited in the example. As Rp 1 and Rp 2 The divalent hydrocarbon group in Rp is preferably an aliphatic hydrocarbon group, more preferably a straight-chain or branched alkylene group. For the aforementioned divalent hydrocarbon group, it is preferable to have 1 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 4 to 6 carbon atoms. 1 and Rp 2 Specific examples include -(CH2)6- or -(CH2)5-.

[0180] The weight-average molecular weight (Mw) of the polycarbonate polyol is preferably 500 to 5000, more preferably 500 to 3000, even more preferably 500 to 2000, and particularly preferably 500 to 1000.

[0181] [Other polyols]

[0182] Examples of polyester polyols include: polyester polyols obtained by reacting dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid, or their dialkyl esters or mixtures thereof with diols such as ethylene glycol, propylene glycol, diethylene glycol, butanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, or mixtures thereof; or polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, polyvalerol, and poly(β-methyl-γ-valerol).

[0183] Examples of polyether polyols include those obtained by polymerizing alkyl oxide compounds such as ethylene oxide, propylene oxide, butane oxide, and tetrahydrofuran using low-volume polyols such as water, ethylene glycol, propylene glycol, trimethylolpropane, and glycerol as initiators.

[0184] Examples of polyether ester polyols include those obtained by reacting dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid, or their dialkyl esters or mixtures thereof with the aforementioned polyether polyol.

[0185] Polyesteramide polyols can be exemplified by those obtained by combining aliphatic diamines with amino groups, such as ethylenediamine, propylenediamine, and 1,6-hexanediamine, as raw materials during the aforementioned esterification reaction.

[0186] Examples of acrylic polyols include polyesteramide polyols obtained by copolymerizing hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or their corresponding methacrylic acid derivatives, which contain one or more hydroxyl groups in one molecule, with, for example, acrylic acid, methacrylic acid, or their esters.

[0187] Examples of polyhydroxy alkane include liquid rubber obtained by copolymerizing butadiene or butadiene with acrylamide.

[0188] As a polyurethane polyol, it is a polyol having one or more urethane bonds in one molecule. Examples include polyether polyols, polyester polyols, polyether ester polyols with a number average molecular weight of 200 to 20,000, which are obtained by reacting polyisocyanates under conditions preferably with NCO / OH less than 1, more preferably 0.9 or less.

[0189] Examples of vegetable oil-based polyols include castor oil, castor oil-modified polyols, dimer acid-modified polyols, and soybean oil-modified polyols. Among these, castor oil-modified polyols are preferred, and castor oil-modified diols are more preferred.

[0190] Of the above, the (O) component is preferably a phenolic resin or a resin containing a hydroxystyrene backbone, more preferably a Novolac resin or a resin containing a hydroxystyrene backbone, even more preferably a polymer of hydroxystyrene or a hydroxystyrene derivative, and particularly preferably a polyhydroxystyrene resin.

[0191] As an (O) component, one type can be used alone, or two or more types can be used together.

[0192] The content of component (O) in adhesive composition (a) is preferably 50-90% by mass, more preferably 50-85% by mass, and even more preferably 60-85% by mass, relative to the total mass (100% by mass) of the adhesive composition (a). If the content of component (O) is above the lower limit mentioned above, the curing properties of adhesive composition (a) become good. If the content of component (I) is below the upper limit mentioned above, it is easy to achieve balance with other components.

[0193] The molar ratio (NCO / OH) of the hydroxyl groups (-OH) in the (O) component of the adhesive composition (a) relative to the isocyanate groups (-NCO) in the (I) component is preferably 0.1 to 1, more preferably 0.3 to 0.7.

[0194] In the adhesive composition (a), the mass ratio of the content of component (I) to component (O) is preferably in the range of ((I):(O)) = 1:10 to 10:1, more preferably 2:8 to 8:2, and even more preferably 2:8 to 5:5.

[0195] <Adhesive Composition (b)>

[0196] Adhesive composition (b) contains a light absorber, a polyurethane resin containing polymerizable carbon-carbon unsaturated bonds, and a polymerization initiator. In adhesive composition (b), the polyurethane resin containing polymerizable carbon-carbon unsaturated bonds is polymerized and crosslinked by heating or the like. As a result, the adhesive composition layer cures, forming an adhesive layer that temporarily bonds the support and the semiconductor substrate. On the other hand, if the adhesive layer is irradiated with light such as a laser, the light absorber absorbs the light, and the adhesive layer is modified. This allows the support to be separated from the semiconductor substrate. Furthermore, residues of the adhesive layer adhering to the semiconductor substrate can be removed by decomposing the urethane bonds using an acid or alkali.

[0197] Light absorber: (B) component

[0198] The adhesive composition (b) contains a light absorber (component (B)). As component (B), the same component as that in the adhesive composition (a) described above can be cited. In addition, component (B) may contain a compound (B1) that absorbs at least a portion of light in the wavelength range of 300 to 800 nm and contains polymeric carbon-carbon unsaturated bonds (hereinafter also referred to as "component (B1)").

[0199] • (B1) component

[0200] Component (B1) is a compound that absorbs at least a portion of light in the wavelength range of 300–800 nm and contains polymeric carbon-carbon unsaturated bonds. It should be noted that component (B1) is a compound that is not part of component (P1) described later.

[0201] Since component (B1) contains polymerizable carbon-carbon unsaturated bonds, it can react with and cure a polyurethane resin (P1) (hereinafter also referred to as "component (P1)") containing polymerizable carbon-carbon unsaturated bonds, thereby forming an adhesive layer together with component (P1). This allows for the temporary bonding of a semiconductor substrate or electronic device to a support. Furthermore, since component (B1) absorbs at least a portion of light in the wavelength range of 300–800 nm, irradiating the adhesive layer with light in the wavelength range of 300–800 nm causes component (B1) to absorb light and release heat. This allows for modification of the adhesive layer.

[0202] Component (B1) functions as a light absorber that absorbs light with wavelengths of 300–800 nm. Component (B1) can absorb light in the wavelength range of 300–800 nm and convert it into heat energy sufficient to modify the adhesive layer. Component (B1) is preferably a component capable of absorbing light in the wavelength region of 300–700 nm, more preferably a component capable of absorbing light in the wavelength region of 300–600 nm, even more preferably a component capable of absorbing light in the wavelength region of 300–550 nm, and particularly preferably a component capable of absorbing light in the wavelength region of 300–400 nm. Component (B1) preferably has an absorption peak in the aforementioned wavelength regions. For component (B1), a component capable of absorbing light of that wavelength can be used, depending on the wavelength of light used during the separation of the support and the semiconductor substrate, etc. For example, a component capable of absorbing light with a wavelength of 355 nm and converting it into heat energy to modify the adhesive layer can be cited as component (B1).

[0203] The polymerizable carbon-carbon unsaturated bonds contained in compound (B1) are not particularly limited, but are preferably free radical polymerizable. Examples of polymerizable carbon-carbon unsaturated bonds include polymerizable carbon-carbon double bonds and polymerizable carbon-carbon triple bonds. Examples of polymerizable carbon-carbon double bonds include vinyl, methacryl, and acryloyl groups, but are not limited to these. Examples of polymerizable carbon-carbon triple bonds include ethynyl and propargyl groups, but are not limited to these.

[0204] As a compound (B1), for example, compounds represented by the following general formula (b1) can be cited.

[0205] [Chemical Formula 4]

[0206]

[0207] [In the formula, W is a monovalent group containing a polymeric carbon-carbon unsaturated bond; Y is a single bond, or a divalent linking group selected from the group consisting of -O-, -CO-, -COO-, and -CONH-; n is an integer from 1 to 6; X is an n-valent group containing an aromatic fused-ring skeleton, benzophenone skeleton, benzoylmethane skeleton, benzoylbenzene skeleton, or benzotriazole skeleton in its structure. When n is 2 or more, there may be multiple W and Y groups, which may be the same or different from each other.]

[0208] In general formula (b1), W is a group containing a polymerizable carbon-carbon unsaturated bond. Examples of polymerizable carbon-carbon unsaturated bonds included in W include polymerizable carbon-carbon double bonds and polymerizable carbon-carbon triple bonds. Examples of W include alkenyl groups and alkynyl groups. For the alkenyl groups described above, a carbon number of 2 to 10 is preferred, a carbon number of 2 to 6 is more preferred, and a carbon number of 2 or 3 is even more preferred. Specific examples of alkenyl groups include vinyl groups and isopropenyl groups. For the alkynyl groups described above, a carbon number of 2 to 6 is preferred, a carbon number of 2 or 3 is more preferred, and a carbon number of 2 is even more preferred. Specific examples of alkynyl groups include ethynyl groups and 1-propynyl groups.

[0209] In general formula (b1), Y is a single bond, or a divalent linker selected from the group consisting of -O-, -CO-, -COO-, and -CONH-. Preferably, Y is a single bond, -COO-, or -CONH-, and more preferably a single bond or -CONH-.

[0210] In general formula (b1), n ​​is an integer from 1 to 6. n is preferably 1 to 5, more preferably 1 to 3, further preferably 1 or 2, and particularly preferably 1. When n is 2 or more, there are multiple Ws that may be the same or different from each other, but they are preferably the same. When n is 2 or more, there are multiple Ys that may be the same or different from each other, but they are preferably the same.

[0211] In general formula (b1), X is an n-valent group whose structure contains an aromatic fused ring skeleton, a benzophenone skeleton, a benzoylmethane skeleton, a benzoylbenzene skeleton, or a benzotriazole skeleton.

[0212] [Contains n-valent groups with aromatic fused-ring skeletons]

[0213] The aromatic fused-ring skeleton comprises 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; it can 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, further preferably 2 to 4, and particularly preferably 2 or 3. The fused ring can consist only of aromatic rings or can be a fused ring formed by an aromatic ring and an aliphatic hydrocarbon ring, but is preferably a fused ring consisting only of aromatic rings. Specific examples of fused rings include naphthalene, anthracene, phenanthrene, and pyrene. Among these, anthracene or phenanthrene are preferred.

[0214] As for X containing an aromatic fused-ring skeleton, structures represented by the following general formulas (Xa-1) or (Xa-2) can be cited. X represented by general formula (Xa-1) is a group with an anthracene skeleton, and X represented by general formula (Xa-2) is a group with a phenanthrene skeleton.

[0215] [Chemical Formula 5]

[0216]

[0217] [In the formula, L] a1 and L a2 Each independently represents a single bond or a divalent linker, R a1 and R a2 Each substituent is represented independently. n is the same as n in equation (b1) above. m represents an integer from 0 to 9, where m + n ≤ 10. When n is 2 or more, there are multiple L... a1 and L a2 They can be the same or different. When m is 2 or more, there can be multiple R. a1 and R a2 They can be the same or different. * represents the chemical bond that is bonded to Y in general formula (b1).

[0218] In general formulas (Xa-1) and (Xa-2), L a1 and L a2 Each can be represented independently as a single bond or a divalent linking group. Examples of divalent linking groups include hydrocarbon groups that may have substituents. These hydrocarbon groups can be aliphatic or aromatic.

[0219] The aforementioned aliphatic hydrocarbon groups can be saturated or unsaturated, but are preferably saturated. The aforementioned aliphatic hydrocarbon groups can be linear or branched, and may also contain rings in their structure. As a linear aliphatic hydrocarbon group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. As a branched aliphatic hydrocarbon group, the number of carbon atoms is preferably 2 to 10, more preferably 2 to 6, and even more preferably 2 or 3. As an aliphatic hydrocarbon group containing a ring structure, the number of carbon atoms is preferably 3 to 10, more preferably 3 to 6.

[0220] The aforementioned aliphatic hydrocarbon group may have substituents. These substituents may be substituents that replace hydrogen atoms or substituents that replace the methylene group (-CH2-) in the carbon chain. Examples of substituents that replace hydrogen atoms include hydroxyl, amino, alkoxy, halogen, carboxyl, and cyano groups, with hydroxyl or amino groups being preferred. Examples of substituents that replace the methylene group (-CH2-) in the carbon chain include -O-, -CO-, -NH-, -COO-, and -CONH-.

[0221] The aforementioned aromatic hydrocarbon group is a hydrocarbon group containing at least one aromatic ring. The aromatic ring contained in the aforementioned aromatic hydrocarbon group can be a monocyclic or polycyclic aromatic ring. The aromatic ring can 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, more preferably 1 or 2. The aromatic hydrocarbon group can be a group formed by linking an aromatic ring with an aliphatic hydrocarbon group.

[0222] The aforementioned aromatic hydrocarbon group may have substituents. These substituents may be substituents that substitute for hydrogen atoms in the aromatic ring, or substituents that substitute for carbon atoms constituting the aromatic ring with heteroatoms. Examples of substituents that substitute for hydrogen atoms include hydroxyl, amino, alkoxy, halogen, carboxyl, and cyano groups, with hydroxyl or amino groups being preferred. Examples of heteroatoms that substitute for the ring in the aromatic ring include nitrogen, oxygen, and sulfur atoms, with nitrogen atoms being preferred.

[0223] In general formulas (Xa-1) and (Xa-2), R a1 and R a2 Each substituent is represented independently. As R a1 and R a2Examples of alicyclic groups include alkyl, hydroxyl, amino, alkoxy, halogen, carboxyl, cyano, nitrile, cyanoalkyl, and alicyclic groups. Preferably, the alkyl, alkoxy, or cyanoalkyl groups have 1 to 5 carbon atoms, more preferably 1 to 3. Preferably, the alicyclic groups have 1 to 6 carbon atoms. For example, malonyl nitrile groups can be alkyl groups. The alicyclic groups can be alicyclic hydrocarbon rings or alicyclic heterocycles. Examples of alicyclic heterocycles include alicyclic heterocycles containing sulfur, nitrogen, or oxygen atoms. A specific example of an alicyclic heterocycle is dithiocyclopentane.

[0224] In general formulas (Xa-1) and (Xa-2), m represents an integer from 0 to 9. m is preferably 0 to 6, more preferably 0 to 5, even more preferably 0 to 3, and particularly preferably 0 to 2.

[0225] In general formulas (Xa-1) and (Xa-2), n is the same as n in formula (b1) above.

[0226] m and n have the relationship that m+n≤10.

[0227] [n-valent groups containing the benzophenone skeleton]

[0228] As X containing the benzophenone skeleton, the following general formula (Xb) can be used to represent the structure.

[0229] [Chemical Formula 6]

[0230]

[0231] [In the formula, L] b1 and L b2 Each independently represents a single bond or a divalent linker, R b1 and R b2 Each substituent can be represented independently. p and q can each independently represent an integer from 0 to 5, where p + q = n. n is the same as in equation (b1) above. m1 and m2 can each independently represent an integer from 0 to 5, where m1 + p ≤ 5 and m2 + q ≤ 5. When p is 2 or higher, there are multiple L... b1 They can be the same or different. When q is 2 or higher, there can be multiple Ls. b2 They can be the same or different. When m1 is 2 or more, there can be multiple R. b1 They can be the same or different. When m² is greater than 2, there can be multiple R. b2 They can be the same or different. * represents the chemical bond that is bonded to Y in general formula (b1).

[0232] In the general formula (Xb), L b1 and L b2Each can independently represent a single bond or a divalent linker. Examples of divalent linkers include L in formulas (Xa-1) and (Xa-2). a1 and L a2 The same group mentioned above. L b1 and L b2 Preferably, it is a single-bonded or substituent-containing aliphatic hydrocarbon group, and more preferably a single-bonded or substituent-containing alkyl group. As a substituent-containing alkyl group, it is preferred to have 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms. As a substituent-containing alkyl group, it is preferred to be an alkyl group, or an alkyl group obtained by substituting a portion of the methylene group (-CH2-) constituting the carbon chain with -O-, -CO-, -NH-, -COO-, or -CONH-.

[0233] In the general formula (Xb), R b1 and R b2 Each substituent is represented independently. As R b1 and R b2 Examples of R in equations (Xa-1) and (Xa-2) above can be cited. a1 and R a2 The same groups mentioned above.

[0234] In the general formula (Xb), p and q each independently represent integers from 0 to 5, and p + q = n. The n mentioned above is the same as the n in the above formula (b1).

[0235] In the general formula (Xb), m1 and m2 each independently represent integers from 0 to 5, m1+p≤5, m2+q≤5. m1 and m2 are preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1.

[0236] [n-valent groups containing the dibenzoylmethane skeleton]

[0237] As X containing a dibenzoylmethane skeleton, the following general formula (Xc) can be used to represent the structure.

[0238] [Chemical Formula 7]

[0239]

[0240] [In the formula, L] c1 and L c2 Each independently represents a single bond or a divalent linker, R c1 and R c2 Each substituent can be represented independently. p and q can each independently represent an integer from 0 to 5, where p + q = n. n is the same as in equation (b1) above. m1 and m2 can each independently represent an integer from 0 to 5, where m1 + p ≤ 5 and m2 + q ≤ 5. When p is 2 or higher, there are multiple L... c1They can be the same or different. When q is 2 or higher, there can be multiple Ls. c2 They can be the same or different. When m1 is 2 or more, there can be multiple R. c1 They can be the same or different. When m² is greater than 2, there can be multiple R. c2 They can be the same or different. * represents the chemical bond that is bonded to Y in general formula (b1).

[0241] In the general formula (Xc), L c1 and L c2 Each can independently represent a single bond or a divalent linker. Examples of divalent linkers include L in formulas (Xa-1) and (Xa-2). a1 and L a2 The same group mentioned above. L c1 and L c2 Preferably, it is a single-bonded or substituent-containing aliphatic hydrocarbon group, and more preferably a single-bonded or substituent-containing alkyl group. As a substituent-containing alkyl group, it is preferred to have 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms. As a substituent-containing alkyl group, it is preferred to be an alkyl group, or an alkyl group obtained by substituting a portion of the methylene group (-CH2-) constituting the carbon chain with -O-, -CO-, -NH-, -COO-, or -CONH-.

[0242] In the general formula (Xc), R c1 and R c2 Each substituent is represented independently. As R c1 and R c2 Examples of R in equations (Xa-1) and (Xa-2) above can be cited. a1 and R a2 The same groups mentioned above.

[0243] In the general formula (Xc), p and q each independently represent integers from 0 to 5, and p + q = n. The n mentioned above is the same as the n in the above formula (b1).

[0244] In the general formula (Xc), m1 and m2 each independently represent integers from 0 to 5, m1+p≤5, m2+q≤5. m1 and m2 are preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1.

[0245] [n-valent groups containing the dibenzoylbenzene skeleton]

[0246] As X containing a dibenzoylbenzene skeleton, the following general formula (Xd) can be used to represent the structure.

[0247] [Chemical Formula 8]

[0248]

[0249] [In the formula, L] d1 L d2 and L d3 Each independently represents a single bond or a divalent linker, R d1 R d2 and R d3 Each substituent is represented independently. p and q each independently represent integers from 0 to 5, r represents integers from 0 to 4, and p + q + r = n. n is the same as n in the above formula (b1). m1 and m2 each independently represent integers from 0 to 5, m3 represents integers from 1 to 4, m1 + p ≤ 5, m2 + q ≤ 5, m3 + r = 4. When p is 2 or more, there are multiple L. d1 They can be the same or different. When q is 2 or higher, there can be multiple Ls. d2 They can be the same or different. When r is 2 or higher, there can be multiple L. d3 They can be the same or different. When m1 is 2 or more, there can be multiple R. d1 They can be the same or different. When m² is greater than 2, there can be multiple R. d2 They can be the same or different. When m³ is 2 or more, there can be multiple R values. d3 They can be the same or different. * represents the chemical bond that is bonded to Y in general formula (b1).

[0250] In the general formula (Xd), L d1 L d2 and L d3 Each can independently represent a single bond or a divalent linker. Examples of divalent linkers include L in formulas (Xa-1) and (Xa-2). a1 and L a2 The same group mentioned above. L d1 L d2 and L d3 Preferably, it is a single-bonded or substituent-containing aliphatic hydrocarbon group, and more preferably a single-bonded or substituent-containing alkyl group. As a substituent-containing alkyl group, it is preferred to have 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms. As a substituent-containing alkyl group, it is preferred to be an alkyl group, or an alkyl group obtained by substituting a portion of the methylene group (-CH2-) constituting the carbon chain with -O-, -CO-, -NH-, -COO-, or -CONH-.

[0251] In the general formula (Xd), R d1 R d2 and R d3 Each substituent is represented independently. As R d1 R d2 and Rd3 Examples of R in equations (Xa-1) and (Xa-2) above can be cited. a1 and R a2 The same groups mentioned above.

[0252] In the general formula (Xd), p and q each independently represent integers from 0 to 5, r represents integers from 0 to 4, and p + q + r = n. The n mentioned above is the same as the n in the above formula (b1).

[0253] In the general formula (Xd), m1 and m2 each independently represent integers from 0 to 5, m3 represents integers from 1 to 4, m1+p≤5, m2+q≤5, and m3+r=4. m1, m2, and m3 are preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1.

[0254] [n-valent groups containing a benzotriazole framework]

[0255] As X containing a benzotriazole skeleton, the following general formula (Xe) can be used to represent structures.

[0256] [Chemical Formula 9]

[0257]

[0258] [In the formula, L] e R represents a single bond or a divalent linker. e This represents a substituent. n is the same as n in equation (b1) above. m represents an integer from 0 to 4, where m + n ≤ 5. When n is 2 or more, there are multiple L... e They can be the same or different. When m is 2 or more, there can be multiple R. e They can be the same or different. * represents the chemical bond that is bonded to Y in general formula (b1).

[0259] In the general formula (Xe), L e This represents a single bond or a divalent linker. Examples of divalent linkers include L in formulas (Xa-1) and (Xa-2). a1 and L a2 The same group mentioned above. L e Preferably, it is a single bond or a substituent-containing hydrocarbon group, more preferably a single bond, a substituent-containing alkyl group, or a group in which one hydrogen atom of the benzene ring is replaced by an alkyl group. As a substituent-containing alkyl group and an alkyl group bonded to the benzene ring, it is preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms.

[0260] In the general formula (Xe), R e Indicates a substituent. As R e Examples of R in equations (Xa-1) and (Xa-2) above can be cited.a1 and R a2 The same groups mentioned above.

[0261] In the general formula (Xe), m represents an integer from 0 to 4. m is preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1.

[0262] In the general formula (Xe), n is the same as n in the above formula (b1). In this case, n is an integer from 1 to 5.

[0263] m and n have the relationship that m+n≤5.

[0264] The compound (B1) is preferably a compound represented by the following general formula (b1-1) or (b1-2).

[0265] [Chemical Formula 10]

[0266]

[0267] [In the formula, R] 11 R 12 and R 13 Each is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; Y 1 It is a single bond, or a divalent linker selected from the group consisting of -O-, -CO-, -COO-, and -CONH-, n 1 X is an integer from 1 to 6; 1 n is an aromatic fused-ring skeleton, benzophenone skeleton, dibenzoylmethane skeleton, dibenzoylbenzene skeleton, or benzotriazole skeleton in its structure. 1 Valence group. n 1 When the value is 2 or higher, there are multiple R values. 11 R 12 and R 13 and Y 1 They can be the same or different.

[0268] [Chemical Formula 11]

[0269]

[0270] [In the formula, R] 21 Y is an alkyl group having 1 to 3 carbon atoms or hydrogen atoms; 2 It is a single bond, or a divalent linker selected from the group consisting of -O-, -CO-, -COO-, and -CONH-; n 2 X is an integer from 1 to 6; 2 n is an aromatic fused-ring skeleton, benzophenone skeleton, dibenzoylmethane skeleton, dibenzoylbenzene skeleton, or benzotriazole skeleton in its structure. 2Valence group. n 2 When the value is 2 or higher, there are multiple R values. 21 and Y 2 They can be the same or different.

[0271] In general formula (b1-1), R 11 R 12 and R 13 Each is independently an alkyl group having 1 to 3 hydrogen atoms or carbon atoms. R 11 and R 12 Each of the following is preferably a hydrogen atom, a methyl group, or an ethyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom. R 13 Preferably, it is a hydrogen atom, a methyl group, or an ethyl group, more preferably a hydrogen atom or a methyl group.

[0272] In general formula (b1-1), Y 1 The same applies to Y in the above general formula (b1).

[0273] In general formula (b1-1), X 1 The same applies to X in the above general formula (b1).

[0274] In general formula (b1-1), n 1 The same applies to n in the general formula (b1) above. 1 When the value is 2 or higher, there are multiple R values. 11 R 12 and R 13 They can be the same or different. 1 When the value is 2 or higher, there are multiple Y values. 1 They can be the same or different. 1 When the value is 2 or higher, there are multiple X values. 1 They can be the same or different.

[0275] In general formula (b1-2), R 21 It is an alkyl group having 1 to 3 hydrogen atoms or carbon atoms. R 21 Preferably, it is a hydrogen atom, methyl or ethyl, more preferably a hydrogen atom or methyl, and even more preferably a hydrogen atom.

[0276] In general formula (b1-2), Y 2 The same applies to Y in the above general formula (b1).

[0277] In general formula (b1-2), X 2 The same applies to X in the above general formula (b1).

[0278] In general formula (b1-2), n 2 The same applies to n in the general formula (b1) above. 2When the value is 2 or higher, there are multiple R values. 21 They can be the same or different. 2 When the value is 2 or higher, there are multiple Y values. 2 They can be the same or different. 2 When the value is 2 or higher, there are multiple X values. 2 They can be the same or different.

[0279] The following are specific examples of compounds (B1) containing aromatic fused-ring skeletons, but are not limited to these.

[0280] [Chemical Formula 12]

[0281]

[0282] [Chemical Formula 13]

[0283]

[0284] [Chemical Formula 14]

[0285]

[0286] The following are specific examples of compounds (B1) containing the benzophenone skeleton, but are not limited to these.

[0287] [Chemical Formula 15]

[0288]

[0289] The following are specific examples of compounds (B1) containing the dibenzoylmethane skeleton, but are not limited to these.

[0290] [Chemical Formula 16]

[0291]

[0292] The following are specific examples of compounds (B1) containing the dibenzoylbenzene skeleton, but are not limited to these.

[0293] [Chemical Formula 17]

[0294]

[0295] The following are specific examples of compounds (B1) containing the benzotriazole skeleton, but are not limited to these.

[0296] [Chemical Formula 18]

[0297]

[0298] (B1) Components can be used alone or in combination with two or more.

[0299] Regarding the content of component (B1) in the adhesive composition, it is preferably 1 part by weight or more, more preferably 3 parts by weight or more, and even more preferably 5 parts by weight or more, and may also be 10 parts by weight or more, or 15 parts by weight or more, relative to 100 parts by weight of polyurethane resin (P1) described later. There is no particular upper limit to the content of component (B1), and examples include 30 parts by weight or less, or 20 parts by weight or less, relative to 100 parts by weight of polyurethane resin (P1) described later. As for the range of component (B1) content, it is preferably 1 to 30 parts by weight, more preferably 3 to 20 parts by weight, and even more preferably 5 to 15 parts by weight, relative to 100 parts by weight of polyurethane resin (P1) described later. If the content of component (B1) is at or above the aforementioned lower limit, the light absorption efficiency in the adhesive layer is improved, and the modification of the adhesive layer becomes better. If the content of component (B1) is below the aforementioned upper limit, it is easier to achieve balance with other components.

[0300] (B) Components can be used alone or in combination with two or more.

[0301] The content of component (B) in adhesive composition (b) is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and even more preferably 3 to 15% by mass, relative to the total mass (100% by mass) of adhesive composition (b). If the content of component (B) is above the lower limit mentioned above, the light absorption efficiency in the adhesive layer is improved, and the modification of the adhesive layer becomes better. If the content of component (B) is below the upper limit mentioned above, it is easier to achieve balance with other components.

[0302] In addition, the content of component (B) in adhesive composition (b) may be 5% or more by mass or 10% or more by mass relative to the total mass (100% by mass) of adhesive composition (b).

[0303] Polyurethane resins containing polymeric carbon-carbon unsaturated bonds: (P1) composition

[0304] The adhesive composition (b) contains a polyurethane resin comprising polymerizable carbon-carbon unsaturated bonds (hereinafter also referred to as "(P1) component"). The (P1) component can be polymerized and cured through the polymerizable carbon-carbon unsaturated bonds to form an adhesive layer. This allows for the temporary bonding of a semiconductor substrate or electronic device to a support. Furthermore, the urethane bonds in the (P1) component have the property of being decomposed by acids or alkalis. Therefore, the adhesive layer can be easily removed using a treatment solution containing an acid or alkali.

[0305] The polymerizable carbon-carbon unsaturated bonds contained in component (P1) are not particularly limited, but are preferably free radical polymerizable. The polymerizable carbon-carbon unsaturated bonds can be polymerizable carbon-carbon double bonds or polymerizable carbon-carbon triple bonds, but are preferably polymerizable carbon-carbon double bonds. Examples of polymerizable carbon-carbon double bonds include methacryloyl and acryloyl groups. Component (P1) can contain one type or two or more types of polymerizable carbon-carbon unsaturated bonds.

[0306] The equivalent amount of polymeric carbon-carbon unsaturated bonds contained in component (P1) is preferably 200 to 2000 g / eq. or more, more preferably 300 to 1500 g / eq. or more, even more preferably 400 to 1200 g / eq. or more, and particularly preferably 500 to 1000 g / eq. If the equivalent amount of polymeric carbon-carbon unsaturated bonds is at or above the lower limit of the above preferred range, the elastic modulus, heat resistance, etc. of the adhesive layer are further improved. If the equivalent amount of polymeric carbon-carbon unsaturated bonds is below the upper limit of the above preferred range, the adhesive layer will not become too hard, and the cleanability becomes good. The above equivalent amounts are the molecular weight of the polyurethane resin per equivalent amount of polymeric carbon-carbon unsaturated bonds.

[0307] The weight-average molecular weight (Mw) of component (P1) is preferably 5,000 to 100,000, more preferably 1,000 to 50,000, even more preferably 12,000 to 30,000, and particularly preferably 13,000 to 25,000.

[0308] Component (P1) can be synthesized by a polymerization addition reaction of a polyisocyanate compound (component (I)) and a polyol (component (O)). That is, component (P1) can be the reaction product of component (I) and component (O). Preferably, at least one of component (I) and component (O) contains a polymerizable carbon-carbon unsaturated bond.

[0309] • Polyisocyanate compounds: (I) components

[0310] As a component (I) used to synthesize component (P1), the same components as those mentioned as component (I) in the adhesive composition (a) described above can be cited.

[0311] (I) Component (I) may be used alone or in combination with two or more. For example, (I) may be a mixture of aliphatic and aromatic diisocyanates. Hydrogenated xylene diisocyanate is preferred as the aliphatic diisocyanate. 4,4-Diphenylmethane diisocyanate is preferred as the aromatic diisocyanate.

[0312] • Polyols: (O) components

[0313] Examples of (O) components used in the synthesis of (P1) components include polyols containing polymerizable carbon-carbon unsaturated bonds (hereinafter also referred to as "(O1) components") and other polyols (hereinafter also referred to as "(O2) components").

[0314] Polyols containing polymeric carbon-carbon unsaturated bonds ((O1) component)

[0315] As a component (O1), examples include at least one polyol selected from the group consisting of methacryloyl and acryloyl groups. The component (O1) may have one or more polymerizable carbon-carbon unsaturated bonds.

[0316] As an (O1) component, examples include esters formed from polyols with three or more constituents and methacrylic acid, acrylic acid, or their derivatives. Among the aforementioned polyols with three or more constituents, low molecular weight polyols with three or more constituents are preferred. Examples of such low molecular weight polyols with three or more constituents include: glycerol, trimethylolpropane, and other tertiary alcohols; tetramethylolpropane (pentaerythritol), diglycerides, and other tetrahydric alcohols; xylitol, and other pentadiols; sorbitol, mannitol, allitol, idotitol, eurythritol, atroitol, inositol, dipentaerythritol, and other hexahydric alcohols; mannitol, and other succinylheptanitol; and sucrose, and other octylhydrols; etc.

[0317] Specific examples of (O1) components include glycerol mono(meth)acrylate, diglycerol tri(meth)acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, diglycerol 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, sorbitol tetra(meth)acrylate, etc.

[0318] "(Meth)acrylate" is a concept that includes both methacrylate and acrylate, referring to either methacrylate or acrylate.

[0319] (O1) Components can be used alone or in combination with two or more.

[0320] The (O1) component is preferably a diol containing methacryloyl or acryloyl groups, more preferably glycerol mono(meth)acrylate or pentaerythritol di(meth)acrylate.

[0321] Other polyols (O2 components)

[0322] The (O2) component is a polyol other than the (O1) component mentioned above. The (O2) component is not particularly limited and can be an aliphatic polyol or an aromatic polyol. The (O2) component can be a low molecular weight polyol (e.g., with a molecular weight less than 500) or a high molecular weight polyol (e.g., with a molecular weight greater than 500).

[0323] As a low molecular weight polyol, the same low molecular weight polyols mentioned in the description of component (O) in the adhesive composition (a) above can be cited. A diol (diol) is preferred as the low molecular weight polyol.

[0324] When using low molecular weight polyols as the (O2) component, the ratio of low molecular weight polyols to (O1) components (low molecular weight polyols / (O1) components (mass ratio)) is preferably 0.01 to 0.1, more preferably 0.03 to 0.08.

[0325] As a polymeric polyol, the same polymeric polyols as those mentioned in the description of the (O) component in the above-described adhesive composition (a) can be cited (wherein, polymeric polyols belonging to the (O1) component are not included).

[0326] The preferred high-molecular-weight polyols are polycarbonate polyols and vegetable oil-based polyols. Among polycarbonate polyols, aliphatic polycarbonate polyols are preferred, and aliphatic polycarbonate diols are more preferred. Among vegetable oil-based polyols, castor oil-modified polyols are preferred, and castor oil-modified diols are more preferred.

[0327] When polycarbonate polyol is used as the (O2) component, the ratio of polycarbonate polyol to (O1) component (polycarbonate polyol / (O1) component (mass ratio)) is preferably 0.1 to 5, more preferably 0.3 to 3, and even more preferably 0.4 to 3.

[0328] When using plant oil-based polyols as the (O2) component, the ratio of plant oil-based polyols to (O1) components (plant oil-based polyols / (O1) components (mass ratio)) is preferably 0.1 to 5, more preferably 0.3 to 3, and even more preferably 0.4 to 2.5.

[0329] (O2) can be used alone or in combination with two or more ingredients.

[0330] Of the above, from the viewpoint of adjusting the viscosity of the adhesive composition (b) and the hardness of the adhesive layer, polycarbonate polyols and low molecular weight polyols are preferred as the (O2) component. Furthermore, from the viewpoint of improving the heat resistance of the adhesive layer, castor oil-modified polyols can be used as the (O2) component.

[0331] From the viewpoint of adjusting the viscosity of the adhesive composition (b) and the heat resistance of the adhesive layer, the (O) component is preferably a combination of the (O1) component and the (O2) component. The (O2) component is preferably a low-molecular-weight polyol, a polycarbonate polyol, a castor oil-modified polyol, or a combination thereof. Specific examples of the (O2) component combined with the (O1) component include: a combination of polycarbonate polyol, castor oil-modified polyol, and a low-molecular-weight polyol; a combination of polycarbonate polyol and castor oil-modified polyol; and polycarbonate polyol, etc.

[0332] The preferred mass ratio of (O1) component to (O2) component is (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 keeping the mass ratio of (O1) component to (O2) component within the above range, the elastic modulus and heat resistance of the adhesive layer can be improved.

[0333] Component (P1) can be synthesized by mixing components (I) and (O) and copolymerizing them according to known methods for synthesizing polyurethane 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. Furthermore, to prevent the polymerization of polymerizable carbon-carbon unsaturated bonds in component (O1), a polymerization inhibitor can be added to the reaction system.

[0334] The mass ratio (I):(O) of the component used to synthesize (P1) is 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 hydroxyl group (-OH) in the (O) component to the isocyanate group (-NCO) in the (I) component is preferably 60:40 to 40:60, more preferably 55:45 to 45:55.

[0335] (P1) Components can be used alone or in combination with two or more.

[0336] The content of component (P1) in adhesive composition (b) is not particularly limited as long as it is a concentration sufficient for application to a support or the like. The content of component (P1) in adhesive composition (b) is preferably 10-60% by mass, more preferably 20-60% by mass, and even more preferably 30-60% by mass, relative to the total mass (100% by mass) of adhesive composition (b).

[0337] Polymerization Initiator: Component (A)

[0338] The adhesive composition (b) contains a polymerization initiator (hereinafter also referred to as component (A)). A polymerization initiator is a component that has the function of promoting polymerization reactions. Examples of component (A) include thermal polymerization initiators, photopolymerization initiators, etc.

[0339] Examples of thermal polymerization initiators include peroxides and azo polymer initiators.

[0340] Examples of peroxides used as thermal polymerization initiators include ketone peroxides, peroxy ketals, hydroperoxides, dialkyl peroxides, and peroxy esters. Specifically, examples of such peroxides include acetyl peroxide, dicumyl peroxide, tert-butyl peroxide, tert-butyl cumyl 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 peroxide, tetrahydronaphthalene hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, tert-butyl pertriphenylacetate, tert-butyl hydroperoxide, tert-butyl performate, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl perphenylacetate, tert-butyl per4-methoxyacetate, and tert-butyl perN-(3-tolyl)carbamate.

[0341] Among the aforementioned peroxides, commercially available products manufactured by Nippon Yushu Co., Ltd., under the trade names "Percumyl (registered trademark)," "Perbutyl (registered trademark)," "Peroyl (registered trademark)," and "Perocta (registered trademark)," can be used, for example.

[0342] Examples of azo-based polymerization initiators used in thermal polymerization include 2,2'-azobispropane, 2,2'-dichloro-2,2'-azobispropane, 1,1'-azo(methylethyl)diacetate, 2,2'-azobis(2-amidinylpropane) hydrochloride, 2,2'-azobis(2-aminopropane) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutylamide, and 2,2'-azobisisobutyronitrile. 2,2'-Azobis-2-methylpropionate, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-2-methylbutyronitrile, dimethyl 2,2'-azobisisobutyrate, 1,1'-azobis(1-methylbutyronitrile-3-sulfonate), 2-(4-methylphenylazo)-2-methylmalonadionitrile 4,4'-azobis-4-cyanopentanoic acid, 3,5-dihydroxymethylphenylazo-2-allylmalonadionitrile, 2 2'-Azobis-2-methylpentanilonitrile, 4,4'-Azobis-4-cyanopentanoic acid dimethyl ester, 2,2'-Azobis-2,4-dimethylpentanilonitrile, 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-cyclohexaneformitrile, 1,1'-Azobis... 1-Cycloheptanenitrile, 1,1'-Azobis-1-phenylethane, 1,1'-Azobisisopropylbenzene, ethyl 4-nitrophenylazobenzylcyanoacetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrophenylazotriphenylmethane, 1,1'-Azobis-1,2-diphenylethane, poly(bisphenol A-4,4'-azobis-4-cyanovalerate), poly(tetraethylene glycol-2,2'-azobisisobutyrate), etc.

[0343] Examples of photopolymerization initiators include: 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis(4-dimethylaminophenyl)one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one, 1-[9- Ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]acetone-1-(o-acetyl oxime), 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 4-benzoyl-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isopentylbenzoic acid, benzyl-β-methoxyethyl ketal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanone, 2-chlorothioxanone, 2,4-dimethylthioxanone Tonone, 1-chloro-4-propoxythioxanone, thioxanth, 2-chlorothioxanth, 2,4-diethylthioxanth, 2-methylthioxanth, 2-isopropylthioxanth, 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-diphenylimidazolium dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazolium dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazolium dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazolium dimer 2,4,5-Triarylimidazolium dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bis(dimethylamino)benzophenone (i.e., michalcone), 4,4'-bis(diethylamino)benzophenone (i.e., ethyl michalcone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzoin, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin tert-butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminoacetophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-Dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzocycloheptanone, pentyl 4-dimethylaminobenzoate, 9-phenylacridinium, 1,7-bis-(9-acridyl)heptane, 1,5-bis-(9-acridyl)pentane, 1,3-bis-(9-acridyl)propane, p-methoxytriazine, 2,4,6-tris(trichloromethyl)triazine, 2-methyl-4,6-bis(trichloromethyl)triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)triazine, 2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)triazine Examples of triazine compounds include 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)triazine, 2-(4-butoxyphenyl)-4,6-bis(trichloromethyl)triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyltriazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyltriazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyltriazine, and 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyltriazine.

[0344] Among the aforementioned photopolymerization initiators, commercially available products such as "IRGACURE OXE02", "IRGACURE OXE01", "IRGACURE 369", "IRGACURE 651", "IRGACURE 907" (all trade names, manufactured by BASF) and "NCI-831" (trade name, manufactured by ADEKA Co., Ltd.) can be used.

[0345] Component (A) can be used alone or in combination of two or more. Component (A) is preferably a thermal polymerization initiator, more preferably a peroxide. The amount of component (A) used can be adjusted according to the amount of component (P1). The content of the polymerization initiator in the adhesive composition (b) is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of component (P1), more preferably 0.5 to 5 parts by mass.

[0346] <Optional Ingredients>

[0347] Without impairing the effects of the present invention, adhesive compositions (a) and (b) may contain optional components in addition to the components described above. Optional components are not particularly limited, and examples include polymerization inhibitors, solvents, plasticizers, adhesive aids, stabilizers, colorants, surfactants, etc.

[0348] Polymer Inhibitors

[0349] Polymerization inhibitors are components that prevent free radical polymerization reactions caused by heat or light. Polymerization inhibitors exhibit high reactivity towards free radicals.

[0350] As a polymerization inhibitor, a phenolic backbone is preferred. For example, hindered phenolic antioxidants can be used as polymerization inhibitors, such as pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, pentoquinone, pentooxyhydroquinone, 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”-ethylidene tris(2-methylphenol), 4,4',4”-ethylidene triphenol, 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'-Butylidene bis(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-methyl) Examples of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, octyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetratetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name IRGANOX 1010, manufactured by BASF), tris(3,5-di-tert-butylhydroxybenzyl)isocyanurate, and thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], etc.

[0351] Polymerization inhibitors can be used alone or in combination of two or more.

[0352] The content of polymerization inhibitors should be appropriately determined based on the type of resin components, the intended use of the adhesive composition, and the application environment.

[0353] Surfactants

[0354] Examples of surfactants include fluorinated surfactants and organosilicon surfactants.

[0355] Examples of commercially available fluorinated surfactants include BM-1000, BM-1100 (both manufactured by BM Chemie), MEGAFACE F142D, MEGAFACE F172, MEGAFACE F173, MEGAFACE F183 (all manufactured by DIC), FLUORAD FC-135, FLUORAD FC-170C, FLUORAD FC-430, FLUORAD FC-431 (all manufactured by Sumitomo 3MLimited), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145 (all manufactured by Asahi Glass), SH-28PA, SH-190, SH-193, SZ-6032, and SF-8428 (all manufactured by Toray Silicon).

[0356] Examples of silicone-based surfactants include, for example, unmodified silicone surfactants, polyether-modified silicone surfactants, polyester-modified silicone surfactants, alkyl-modified silicone surfactants, aralkyl-modified silicone surfactants, and reactive silicone surfactants. Commercially available silicone surfactants can be used. Specific examples of commercially available silicone surfactants include, for example, Paintad M (manufactured by Dow Corning Toray Co., Ltd.), Topika K1000, Topika K2000, Topika K5000 (all manufactured by Takachiho Sangyo Co., Ltd.), XL-121 (polyether-modified silicone surfactant, manufactured by Clariant), and BYK-310 (polyester-modified silicone surfactant, manufactured by BYK Chemie).

[0357] The surfactant can be used alone or in combination of two or more. As a surfactant, an organosilicon surfactant is preferred, and a polyester-modified organosilicon surfactant is more preferred. When the adhesive composition (a) contains a surfactant, the surfactant content is preferably 0.01 to 1 part by mass, more preferably 0.5 to 0.5 parts by mass, relative to the total mass (100 parts by mass) of components (I) and (O). When the adhesive composition (b) contains a surfactant, the surfactant content is preferably 0.01 to 1 part by mass, more preferably 0.5 to 0.5 parts by mass, relative to 100 parts by mass of component (P1).

[0358] Solvent composition

[0359] Examples of solvent components include hydrocarbon solvents, petroleum-based solvents, and other solvents besides those mentioned above. Hereinafter, hydrocarbon solvents and petroleum-based solvents will be collectively referred to as "(S1) component". Solvent components other than "(S1) component" will be referred to as "(S2) component".

[0360] Examples of hydrocarbon solvents include straight-chain, branched, or cyclic hydrocarbons. Examples of straight-chain hydrocarbon solvents include: hexane, heptane, octane, nonane, methyl octane, decane, undecane, dodecane, and tridecane; branched hydrocarbons include: isooctane, isononane, and isododecane; alicyclic hydrocarbons include: p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpenoid diol, 1,8-terpenoid diol, camphene, norbornene, pinane, thujone, terpenoids, longifolene, α-terpinene, β-terpinene, γ-terpinene, α-pinene, β-pinene, α-thujone, β-thujone, cyclohexane, cycloheptane, and cyclooctane; and aromatic hydrocarbons include: toluene, xylene, indene, pentanene, indene, tetrahydroindene, naphthalene, tetrahydronaphthalene (tetrahydronaphthalene), and decahydronaphthalene (decahydronaphthalene).

[0361] Petroleum-based solvents refer to solvents obtained from the purification of heavy oil, such as white kerosene, paraffin-based solvents, and isoparaffin-based solvents.

[0362] As a component (S2), terpene solvents with polar groups such as oxygen atoms, carbonyl groups, or acetoxy groups can be cited, for example, geraniol, nerol, linalool, citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinene-1-ol, terpinene-4-ol, dihydrorosinol acetate, 1,4-cineole, 1,8-cineole, borneol, carvone, ionone, thujone, camphor, etc.

[0363] Additionally, as components of (S2), examples 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; polyols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds containing ester bonds such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; monoalkyl ethers or monomethyl ethers, monoethyl ethers, monopropyl ethers, monobutyl ethers, etc., of the above polyols or compounds containing ester bonds. Derivatives of polyols such as phenyl ethers and other compounds with ether bonds (among which 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; aromatic organic solvents such as anisole, ethyl benzyl ether, tolyl methyl ether, diphenyl ether, dibenzyl ether, phenethyl ether, and butylphenyl ether.

[0364] The solvent component can be used alone or in combination of two or more. Preferably, the solvent component is inactive relative to components (B), (I), and (O), or components (B) and (P1). Examples of preferred solvent components include ester solvents, ketone solvents, aromatic hydrocarbon solvents, PGMEA, PGME, and mixtures thereof.

[0365] The adhesive composition (a) can be prepared by appropriately adding optional components to components (B), (I) and (O) and mixing them.

[0366] The adhesive composition (b) can be prepared by dissolving and mixing components (B), (P1), and (A), as well as optional components to be added as needed, in a solvent component.

[0367] The solvent content in the adhesive composition (b) can be appropriately adjusted according to the thickness of the adhesive composition layer. For example, the solvent content is preferably in the range of 40% to 90% by mass relative to the total mass (100% by mass) of the adhesive composition. That is, for the adhesive composition of this embodiment, the concentration of solid components (the total amount of compounding components after removing the solvent) is preferably in the range of 10% to 80% by mass. If the solvent content is within the above-mentioned preferred range, the viscosity can be easily adjusted.

[0368] When using a polymerization initiator, the initiator can be formulated using known methods before use in the adhesive composition. The polymerization initiator or inhibitor can be formulated in the form of a solution pre-dissolved in the aforementioned component (S2). The amount of component (S2) used can be appropriately adjusted according to the type of polymerization initiator or inhibitor, for example, preferably 1 to 50 parts by mass relative to 100 parts by mass of component (S1), more preferably 5 to 30 parts by mass. If the amount of component (S2) used is within the above-mentioned preferred range, the polymerization initiator or inhibitor can be sufficiently dissolved.

[0369] According to the adhesive composition of this embodiment, when temporarily bonding a semiconductor substrate or the like to a support, an adhesive composition layer is formed between the semiconductor substrate or the support and the support, and then cured. This forms an adhesive layer that temporarily bonds the semiconductor substrate or the like to the support. This adhesive layer cures through a cross-linked structure, therefore exhibiting high heat resistance; even at high temperatures (e.g., above 200°C), the elastic modulus does not decrease. Therefore, even when high-temperature processing is performed during the fabrication of semiconductor substrates or electronic devices, defects such as positional shift or sinking are less likely to occur.

[0370] On the other hand, if the adhesive layer is irradiated with light such as a laser, component (B) in the adhesive layer absorbs the light, and the adhesive layer is modified. As a result, the adhesive strength of the adhesive layer is reduced, and the semiconductor substrate or the like can be separated from the support. Therefore, a separation layer is not required.

[0371] Furthermore, since the adhesive layer contains polyurethane resin, the adhesive layer can be decomposed by using acid or alkali to break down the urethane bonds. Therefore, even if residues of the adhesive layer adhere to the semiconductor substrate or the like after separation from the support, the residues can be easily removed by cleaning with acid or alkali.

[0372] (Layered structure)

[0373] Regarding the laminate according to the second aspect of the present invention, it is a laminate in which a light-transmitting support, an adhesive layer, and a semiconductor substrate or electronic device are sequentially laminated, characterized in that the adhesive layer is a cured body of the adhesive composition according to the first aspect.

[0374] Figure 1 An embodiment of the laminate involved in the second method is shown.

[0375] Figure 1 The laminate 100 shown includes a support 1 that allows light to pass through, an adhesive layer 3, and a semiconductor substrate 4. The support 1, adhesive layer 3, and semiconductor substrate 4 are sequentially stacked in the laminate 100.

[0376] Figure 2 Another embodiment of the laminate involved in the second method is shown.

[0377] At once Figure 2 As for the laminate 200 shown, it has the same structure as the laminate 100, except that the electronic device 456 formed by the semiconductor substrate 4, the sealing material layer 5 and the wiring layer 6 is laminated on the adhesive layer 3.

[0378] Figure 3 Another embodiment of the laminate involved in the second method is shown.

[0379] At once Figure 3 The laminate 300 shown has the same configuration as the laminate 100, except that the electronic devices are formed by the wiring layer 6.

[0380] Figure 4 Another embodiment of the laminate involved in the second method is shown.

[0381] At once Figure 4 As for the laminate 400 shown, it has the same structure as the laminate 100, except that the electronic device 645 formed by the wiring layer 6, the semiconductor substrate 4 and the sealing material layer 5 is laminated on the adhesive layer 3.

[0382] <Support Body>

[0383] A support is a component that supports a semiconductor substrate or electronic device. The support has the property of allowing light to pass through. The support is attached to the semiconductor substrate or electronic device via an adhesive layer. Therefore, as a support, it is preferable to have the strength required to prevent damage or deformation of the semiconductor substrate during device thinning, semiconductor substrate handling, and mounting to the semiconductor substrate.

[0384] Materials used as the support body include, for example, glass, silicone, acrylic resin, etc. The shape of the support body can be, for example, rectangular, circular, etc., but is not limited to these. To further achieve high-density integration and improve production efficiency, supports that are larger in size than circular supports, or large panels with a quadrilateral shape when viewed from above, can also be used as the support body.

[0385] <Adhesive Layer>

[0386] The adhesive layer is provided for temporarily bonding a semiconductor substrate or electronic device to a support. The adhesive layer is a cured form of the adhesive composition according to the first embodiment described above. The curing of the adhesive composition according to the first embodiment can be performed by heating the adhesive composition. The thickness of the adhesive layer is preferably 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.

[0387] As described above, the adhesive layer is a cured body of the adhesive composition, and the material constituting the adhesive layer (cured body) preferably satisfies the following characteristics.

[0388] That is, when determining the complex elastic modulus of the cured body under the following conditions, the complex elastic modulus at 200°C is preferably 1.0 × 10⁻⁶. 4 Pa or higher, more preferably 5.0 × 10 Pa. 4 Pa or higher, more preferably 1.0 × 10 Pa 5 Pa or higher. Furthermore, the complex elastic modulus at 200°C is more preferably 1.0 × 10⁻⁶. 6 Pa or higher, more preferably 5.0 × 10 Pa. 6 Pa or higher, particularly preferably 1.0 × 10 Pa 7 Pa or higher. This serves as the upper limit for the complex modulus of elasticity at 200℃, for example, 1.0 × 10⁻⁶ Pa. 10 Below Pa.

[0389] Furthermore, when measuring the complex elastic modulus of the cured body under the following conditions, the preferred complex elastic modulus at 250°C is 5.0 × 10⁻⁶. 6 Pa or higher, more preferably 1.0 × 10 Pa 7 Pa or higher. This serves as the upper limit for the complex modulus of elasticity at 250°C, for example, 1.0 × 10⁻⁶ Pa. 10 Below Pa.

[0390] The complex elastic modulus of the cured body can be measured using a dynamic viscoelasticity measuring device, Rheogel-E4000 (manufactured by UBM Corporation). Specifically, the adhesive composition can be coated onto a PET film containing a release agent, and heated in an oven under a nitrogen atmosphere at 180°C for 1 hour to form a test piece with a thickness of 50 μm. Then, the test piece (5 mm × 40 mm in size, 50 μm thick) peeled off from the PET film is measured using the aforementioned measuring device. The measurement conditions are as follows: a tensile condition at a frequency of 1 Hz, with a heating rate of 5°C / min from an initial temperature of 50°C to 300°C.

[0391] <Semiconductor substrates or electronic devices>

[0392] Semiconductor substrates or electronic devices are temporarily bonded to a support through an adhesive layer.

[0393] Semiconductor Substrates

[0394] There are no particular limitations on the semiconductor substrate; examples can be made of the same semiconductor substrate as those shown in the above-described "(adhesive composition)". The semiconductor substrate can be a semiconductor element or other element, and can have a single-layer or multi-layer structure.

[0395] Electronic Components

[0396] There are no particular limitations on the electronic device; examples can be made of the same type of electronic device as those shown in the above-described "(adhesive composition)". The electronic device is preferably a composite formed of a component made of metal or semiconductor and a resin that seals or insulates the component. Specifically, the electronic device includes at least one of a sealing material layer and a wiring layer, and may further include a semiconductor substrate.

[0397] Figure 2 In the stack 200 shown, the electronic device 456 is composed of a semiconductor substrate 4, a sealing material layer 5, and a wiring layer 6. Figure 3 In the stack 300 shown, the electronic device 6 is composed of a wiring layer 6. Figure 4 In the stack 400 shown, the electronic device 645 is composed of a wiring layer 6, a semiconductor substrate 4, and a sealing material layer 5.

[0398] [Sealing material layer]

[0399] The sealing material layer is provided to seal the semiconductor substrate and is formed using a sealing material. The sealing material uses components that can insulate or seal components made of metal or semiconductor.

[0400] As a sealing material, a resin composition can be used, for example. The sealing material layer 5 is preferably disposed in such a way that it completely covers the semiconductor substrate 4 on the adhesive layer 3, rather than being disposed on each of the individual semiconductor substrates 4. The resin used in the sealing material is not particularly limited as long as it is capable of sealing and / or insulating metals or semiconductors; examples include epoxy resins and silicone resins.

[0401] Sealing materials may contain other components besides resin, such as fillers. Examples of fillers include, for instance, spherical silica particles.

[0402] Wiring Layer

[0403] A wiring layer, also known as a Redistribution Layer (RDL), is a thin film that forms the wiring that connects to the substrate. It can have a single-layer or multi-layer structure. The wiring layer can be based on a dielectric material (silicon oxide (SiO2)). x A layer is formed by wiring between photosensitive resins such as photosensitive epoxy resins, etc., using a conductor (e.g., metals such as aluminum, copper, titanium, nickel, gold and silver, and alloys such as silver-tin alloys), but is not limited to this.

[0404] It should be noted that, Figures 1-4In the laminate, the support 1 is adjacent to the adhesive layer 3, but is not limited thereto; other layers may also be formed between the support 1 and the adhesive layer 3. In this case, the other layers can be made of a material that allows light to pass through. Thus, layers that impart suitable properties to the laminate 100 to 400 can be appropriately added without hindering the incidence of light onto the adhesive layer 3. Depending on the type of material constituting the adhesive layer 3, different wavelengths of light can be used. Therefore, the materials constituting the other layers do not need to transmit all wavelengths of light; appropriate materials can be selected from those that transmit wavelengths of light that can modify the material constituting the adhesive layer 3.

[0405] (Manufacturing method of laminated body (1))

[0406] Regarding the manufacturing method of the laminate according to the third aspect of the present invention, it is a method for manufacturing a laminate in which a light-transmitting support, an adhesive layer and a semiconductor substrate are sequentially laminated. The manufacturing method is characterized by comprising the following steps: a step of coating the adhesive composition according to the first aspect onto the support or the semiconductor substrate to form an adhesive composition layer (hereinafter also referred to as the "adhesive composition layer forming step"); a step of placing the semiconductor substrate on the support through the adhesive composition layer (hereinafter also referred to as the "semiconductor substrate placement step"); and a step of curing the adhesive composition layer by the polymerization reaction of the polyurethane resin to form the adhesive layer (hereinafter also referred to as the "adhesive layer forming step").

[0407] Figures 5 and 6 are schematic process diagrams illustrating one embodiment of the manufacturing method of the laminated body according to this embodiment.

[0408] Figures 5A-5B This figure illustrates the manufacturing process of a laminate 100' in which a support 1, an adhesive composition layer 3', and a semiconductor substrate 4 are sequentially stacked. Figure 5A This diagram illustrates the process of forming an adhesive composition layer. Figure 5B This diagram illustrates the semiconductor substrate placement process.

[0409] Figure 6 This diagram illustrates the adhesive layer formation process. The adhesive composition layer 3' in the laminate 100' is thermally cured to form the adhesive layer 3, resulting in the laminate 100.

[0410] [Adhesive composition layer formation process]

[0411] The method for manufacturing a laminate according to this embodiment includes an adhesive composition layer formation step. The adhesive composition layer formation step is a step of forming an adhesive composition layer by coating an adhesive composition onto a support or semiconductor substrate.

[0412] Figure 5A In this process, an adhesive composition layer 3' is formed on the support 1 using an adhesive composition.

[0413] The method of forming the adhesive composition layer 3' on the support 1 is not particularly limited. For example, methods such as spin coating, dipping, roller coating, spraying, and slot coating can be used.

[0414] The adhesive composition layer can also be formed on the semiconductor substrate 4 using the same method.

[0415] After the adhesive composition layer is formed, a baking process can be performed. The baking temperature is set to a temperature lower than the heating temperature in the adhesive layer formation process described later. The baking conditions can vary depending on the type of curing component contained in the adhesive composition; for example, baking at a temperature of 70–100°C for 1–10 minutes may be used.

[0416] [Semiconductor substrate mounting process]

[0417] The method for manufacturing a laminate according to this embodiment includes a semiconductor substrate placement step. The semiconductor substrate placement step is a process of placing a semiconductor substrate on a support through an adhesive composition layer. This allows the laminate 100' to be obtained.

[0418] In Figure 5(c), the semiconductor substrate 4 is placed on the support 1 via an adhesive composition layer 3' formed on the support 1.

[0419] The method of placing the semiconductor substrate 4 on the support 1 through the adhesive composition layer 3' is not particularly limited, and the method commonly used as a method of placing the semiconductor substrate in a specified position can be adopted.

[0420] [Adhesive layer formation process]

[0421] The method for manufacturing a laminate according to this embodiment includes an adhesive layer forming step. The adhesive layer forming step is a step of curing an adhesive composition layer to form an adhesive layer. Thus, a laminate 100 can be obtained.

[0422] Figure 6 In the process, adhesive layer 3 is formed by the curing of adhesive composition layer 3'.

[0423] The curing reaction of the adhesive composition layer can be carried out by selecting an appropriate method depending on the type of curing component.

[0424] When the curing component is one of the components described in (a) above, the curing reaction can be carried out by heating. The heating temperature can be set above the temperature at which the crosslinking reaction of components (I) and (O) can begin. For example, if component (I) contains a capped polyisocyanate, the heating temperature can be set above the dissociation temperature of the thermally dissociative capping agent that caps the isocyanate group in the capped polyisocyanate. The heating temperature can vary depending on the type of thermally dissociative capping agent, and examples include 80°C or higher, 100°C or higher, 130°C or higher, or 150°C or higher. There is no particular upper limit to the heating temperature, and from an energy consumption point of view, examples include 350°C or lower, 300°C or lower, or 250°C or lower. Examples of heating temperature ranges include 80–350°C, 100–300°C, 130–300°C, or 150–300°C.

[0425] The heating time is not particularly limited, as long as it is sufficient for the (I) and (O) components to undergo heat curing. For example, the heating time can be set to 15 minutes or more, 30 minutes or more, or 45 minutes or more. There is no particular upper limit to the heating time; from the perspective of operational efficiency, it can be set to less than 120 minutes, less than 100 minutes, less than 80 minutes, or less than 60 minutes. Examples of heating time ranges include 15–120 minutes, 30–120 minutes, or 45–120 minutes.

[0426] When the curing component is the component described in (b) above, and component (P1) contains a methacrylamide or acryloyl group, the curing reaction can be carried out by heating. Examples of heating temperatures include 80–350°C, 100–300°C, 130–300°C, or 150–300°C. The heating time is not particularly limited, as long as it is sufficient for component (P1) to polymerize and cure. A preferred heating time is 30–180 minutes, more preferably 45–120 minutes, and even more preferably 60–120 minutes. The curing reaction can be carried out, for example, under a nitrogen atmosphere.

[0427] Through this process, the (I) and (O) components, or (P1) components, in the adhesive composition layer 3' crosslink and cure, forming an adhesive layer 3 as a cured body of the adhesive composition layer 3'. Thus, the support 1 and the semiconductor substrate 4 are temporarily bonded. As a result, a laminate 100 can be obtained.

[0428] Furthermore, when the curing component is the component described in (b) above, and component (B1) is included as component (B), components (P1) and (B1) in the adhesive composition layer 3' crosslink and cure, forming an adhesive layer 3 as a cured body of the adhesive composition layer 3'. Thus, the support 1 and the semiconductor substrate 4 are temporarily bonded. As a result, a laminate 100 can be obtained.

[0429] [Optional Process]

[0430] The method for manufacturing the laminate according to this embodiment may include other processes in addition to those described above. Examples of other processes include various mechanical or chemical treatments (such as grinding, chemical mechanical polishing (CMP) and other thin-film treatments, high-temperature / vacuum treatments such as chemical vapor deposition (CVD) and physical vapor deposition (PVD), treatments using chemicals such as organic solvents, acidic treatment solutions, and alkaline treatment solutions, electroplating, irradiation with active light, heating and cooling treatments, etc.).

[0431] (Manufacturing method of laminated body (2))

[0432] The method for manufacturing a laminate according to the fourth aspect of the present invention is characterized in that, after obtaining the laminate using the method for manufacturing a laminate according to the third aspect described above, it further includes an electronic device forming step for forming an electronic device, wherein the electronic device is a composite formed of a component made of metal or semiconductor and a resin that seals or insulates the component.

[0433] The laminate obtained by the manufacturing method of this embodiment is a laminate in which a support, an adhesive layer, and electronic devices are sequentially stacked. This laminate can be obtained by performing an electronic device forming process on the laminate obtained by the manufacturing method of the third embodiment described above.

[0434] [Electronic Device Forming Process]

[0435] The method for manufacturing a laminate according to this embodiment includes an electronic device forming process. The electronic device forming process is a process for forming an electronic device that is a composite formed of a component made of metal or semiconductor and a resin that seals or insulates the component.

[0436] The electronic device forming process may include any one of a sealing process, a grinding process, and a wiring layer forming process. In one embodiment, the electronic device forming process includes a substrate fixing process and a sealing process. In this case, the electronic device forming process may further include a grinding process and a wiring layer forming process.

[0437] Regarding the sealing process

[0438] The sealing process is the process of sealing the substrate fixed to the support body using sealing materials.

[0439] Figure 7A In this process, a laminate 110 is obtained, which is formed by sealing the entire semiconductor substrate 4, which is temporarily bonded to the support body 1 through an adhesive layer 3, with a sealing material layer 5.

[0440] In the sealing process, for example, a sealing material heated to 130-170°C is supplied to the adhesive layer 3 while maintaining a high viscosity, in a manner that covers the semiconductor substrate 4. Through compression molding, a laminate 110 with a sealing material layer 5 disposed on the adhesive layer 3 is produced.

[0441] At this time, the temperature conditions are, for example, 130–170°C.

[0442] The pressure applied to the semiconductor substrate 4 is, for example, 50 to 500 N / cm. 2 .

[0443] The sealing material layer 5 is preferably provided in such a way that it completely covers the semiconductor substrate 4 on the adhesive layer 3, rather than being provided on each of the semiconductor substrates 4.

[0444] • Regarding the grinding process

[0445] The grinding process is a process performed after the sealing process to grind the sealing material portion (sealing material layer 5) in the sealing body in a manner that exposes a portion of the semiconductor substrate.

[0446] For example, such as Figure 7B As shown, the grinding of the sealing material portion is performed in the following manner: the sealing material layer 5 is ground to a thickness approximately equal to that of the semiconductor substrate 4.

[0447] • Regarding the wiring layer formation process

[0448] The wiring layer formation process is a process of forming a wiring layer on the exposed semiconductor substrate after the above-mentioned grinding process.

[0449] Figure 7C In this process, a wiring layer 6 is formed on the semiconductor substrate 4 and the sealing material layer 5. This results in a laminate 120. In the laminate 120, the semiconductor substrate 4, the sealing material layer 5, and the wiring layer 6 constitute an electronic device 456.

[0450] As a method for forming wiring layer 6, the following methods can be cited, for example.

[0451] First, silicon oxide (SiO) is formed on the sealing material layer 5. xA dielectric layer, such as a photosensitive resin, is formed. A dielectric layer formed of silicon oxide can be formed, for example, by sputtering or vacuum evaporation. A dielectric layer formed of photosensitive resin can be formed, for example, by coating the sealing material layer 5 with photosensitive resin using methods such as spin coating, dipping, roller coating, spraying, or slot coating.

[0452] Next, wiring is formed on the dielectric layer using a conductor such as a metal. As a method for forming the wiring, known semiconductor processes such as photolithography (resist photolithography) and etching can be used. Examples of such photolithography processes include those using a positive resist material and those using a negative resist material.

[0453] In the method for manufacturing the laminate according to this embodiment, bumps can be formed or components can be mounted on the wiring layer 6. Component mounting on the wiring layer 6 can be performed, for example, using a pick-and-place machine.

[0454] (Manufacturing method of laminated body (3))

[0455] The method for manufacturing a laminate according to the fifth aspect of the present invention is a method for manufacturing a laminate in which a support body, an adhesive layer, and an electronic device are sequentially laminated. The method is characterized by comprising the following steps: a step of coating the support body with the adhesive composition according to the first aspect to form a layer of the adhesive composition (adhesive composition layer forming step); an electronic device forming step of forming an electronic device on the adhesive composition layer, wherein the electronic device is a composite of a component made of metal or semiconductor and a resin that seals or insulates the component (electronic device forming step); and a step of curing the adhesive composition layer to form an adhesive layer (adhesive layer forming step).

[0456] Similar to the manufacturing method described in the fourth method above, the laminate obtained by the manufacturing method of this embodiment is a laminate in which a support, an adhesive layer and electronic devices are sequentially stacked.

[0457] In the manufacturing method of this embodiment, the adhesive composition layer forming process can be performed in the same way as the adhesive composition layer forming process in the manufacturing method of the laminate according to the third aspect described above.

[0458] In the manufacturing method of this embodiment, an electronic device forming process is performed after the adhesive composition layer forming process. This electronic device forming process may include a wiring layer forming process. The electronic device forming process may also include a semiconductor substrate placement process, a sealing process, and a grinding process. Alternatively, the electronic device forming process may be a process of placing a sealant (which is formed by sealing a semiconductor substrate with a sealing material) onto a support through the adhesive composition layer.

[0459] The adhesive layer formation process can be performed in the same way as the adhesive layer formation process in the manufacturing method of the laminate involved in the third aspect described above.

[0460] After the adhesive layer formation process, further electronic device formation processes can be performed as needed. These electronic device formation processes may include, for example, semiconductor substrate placement, sealing, and grinding processes.

[0461] According to the manufacturing method of the laminate described in methods 3 to 5 above, since the support body and the semiconductor substrate or electronic device are temporarily bonded together by an adhesive layer with high heat resistance, a laminate consisting of a support body, an adhesive layer, and a semiconductor substrate or electronic device can be stably manufactured by sequentially stacking the support body, the adhesive layer, and the semiconductor substrate or electronic device. The laminate is manufactured using a fan-out technique (in which terminals disposed on the semiconductor substrate are mounted on a wiring layer extending outwards from the chip region).

[0462] (Manufacturing methods for electronic components)

[0463] The method for manufacturing an electronic component according to the sixth aspect of the present invention is characterized in that, after obtaining a laminate using the manufacturing method of the laminate according to any of the third to fifth aspects described above, the method includes the following steps: modifying the adhesive layer by irradiating the adhesive layer with light through the support, thereby separating the electronic device from the support (hereinafter also referred to as the "separation step"); and removing the adhesive layer by decomposing the urethane bonds in the adhesive layer using an acid or alkali (hereinafter also referred to as the "adhesive layer removal step").

[0464] Figure 8 is a schematic process diagram illustrating one embodiment of a method for manufacturing a semiconductor package (electronic component). Figure 8A To illustrate the diagram of the laminate 120, Figure 8B This diagram illustrates the separation process. Figure 8C This diagram illustrates the adhesive removal process.

[0465] [Separation Process]

[0466] The separation process is as follows: the adhesive layer 3 is modified by irradiating light (arrow) onto the support 1, thereby separating the electronic device 456 from the support 1.

[0467] like Figure 8A As shown, in the separation process, light (arrow) is irradiated onto the adhesive layer 3 through the support 1 that allows light to pass through, thereby modifying the adhesive layer 3.

[0468] The wavelength of light used in the separation process can be selected based on the wavelength of light that can be absorbed by component (B) contained in adhesive layer 3. For example, light in the wavelength range of 300–800 nm can be used.

[0469] The type of irradiated light can be appropriately selected based on the transmittance of the support 1. For example, solid-state lasers such as YAG laser, ruby ​​laser, glass laser, YVO4 laser, LD laser, and fiber laser, liquid lasers such as pigment lasers, gas lasers such as CO2 laser, excimer laser, Ar laser, and He-Ne laser, semiconductor lasers, free-electron lasers, and non-laser lasers can be used. This modifies the adhesive layer 3, enabling it to be easily separated from the electronic device 456.

[0470] In the case of laser irradiation, the following conditions can be cited as an example of laser irradiation conditions.

[0471] The average output value of the laser is preferably 1.0W or more and 5.0W or less, more preferably 3.0W or more and 4.0W or less. The repetition frequency of the laser is preferably 20kHz or more and 60kHz or less, more preferably 30kHz or more and 50kHz or less. The scanning speed of the laser is preferably 100mm / s or more and 10000mm / s or less.

[0472] After the adhesive layer 3 is modified by irradiating it with light (arrow), such as Figure 8B As shown, the support 1 is separated from the electronic device 456.

[0473] For example, the support 1 and the electronic device 456 can be separated by applying force along the direction in which they separate. Specifically, with either the support 1 or the electronic device 456 side (wiring layer 6) fixed to the worktable, the other can be lifted while being held in place by adsorption using a separation plate equipped with an adsorption pad (corrugated pad, etc.), thereby separating the support 1 from the electronic device 456.

[0474] The force applied to the laminate 200 can be adjusted appropriately according to the size of the laminate 200, and there is no particular limitation. For example, if the laminate has a diameter of about 300 mm, the support body 1 can be properly separated from the electronic device 456 by applying a force of about 0.1 to 5 kgf (0.98 to 49 N).

[0475] [Adhesive layer removal process]

[0476] The method for manufacturing electronic components according to this embodiment includes an adhesive layer removal step. The adhesive layer removal step involves using an acid or alkali to decompose the urethane bonds in the adhesive layer, thereby removing the adhesive layer.

[0477] Figure 8B In the process, after the separation step, an adhesive layer 3 is attached to the electronic component 456. In this step, the adhesive layer 3 is decomposed using an acid or alkali, thereby removing the adhesive layer 3 and obtaining the electronic component 50.

[0478] In this process, the urethane bonds in the adhesive layer 3 are decomposed using an acid or alkali. The adhesive layer 3 contains a polyurethane resin formed by copolymerizing the above-mentioned components (I) and (O), or a cross-linked polyurethane resin formed by polymerizing the above-mentioned component (P1). For these polyurethane resins, the urethane bonds are cleaved and decomposed by treatment with an acid or alkali. Thus, the adhesive layer 3 can be decomposed, thereby removing residues from the adhesive layer 3 adhering to the electronic device 456.

[0479] The acid or base used in this process can be any substance capable of breaking down carbamate bonds; there are no particular limitations. Examples of acids capable of breaking down carbamate bonds include hydrochloric acid, sulfuric acid, and nitric acid, but these are not limited to these. Examples of bases capable of breaking down carbamate bonds include inorganic bases such as potassium hydroxide and sodium hydroxide; and organic amines such as tetramethylammonium hydroxide and monoethanolamine, but these are not limited to these.

[0480] The aforementioned acid or base can be dissolved in a solvent and used as a treatment solution for removing the adhesive layer. Polar solvents are preferred, for example, dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), diethylene glycol monobutyl ether, diethylene glycol, ethylene glycol, propylene glycol, etc.

[0481] The adhesive removal treatment solution may contain known additives such as surfactants in addition to the above-mentioned components.

[0482] The content of acid or alkali in the above-mentioned treatment solution is not particularly limited, and for example, 1 to 50% by mass can be cited. Furthermore, the content of polar solvent in the above-mentioned treatment solution can be cited as 50 to 99% by mass.

[0483] Commercially available alkaline or acidic treatment solutions can be used to remove the adhesive layer. Examples of commercially available treatment solutions include ST-120 and ST-121 (both manufactured by Tokyo Ohka Kogyo Co., Ltd.).

[0484] By contacting the adhesive layer 3 with a treatment solution containing acid or alkali as described above, the urethane bonds in the adhesive layer 3 are broken down, and the adhesive layer 3 can be removed.

[0485] In the manufacturing method of the electronic component of this embodiment, after the above-mentioned adhesive layer removal process, the electronic component 50 can be further processed by solder ball formation, cutting, or oxide film formation.

[0486] According to the manufacturing method of the electronic component according to this embodiment, an adhesive composition containing (a) a light absorber, a polyisocyanate, and a polyol, or an adhesive composition containing (b) a light absorber, a polyurethane resin containing polymerizable carbon-carbon unsaturated bonds, and a polymerization initiator, is used to temporarily bond a semiconductor substrate or the like to a support by curing the adhesive composition. Therefore, an adhesive layer with high heat resistance (able to withstand high-temperature processing in electronic device fabrication processes, etc.) can be formed.

[0487] Furthermore, since the adhesive composition contains a light absorber, the adhesive layer is modified and the adhesive strength is reduced when light is irradiated. Therefore, even without a release layer, the temporarily bonded semiconductor substrate and the like can be easily separated from the support.

[0488] Furthermore, by using acid or alkali to decompose the urethane bonds in the adhesive layer, residues of the adhesive layer attached to the semiconductor substrate or the like after separation from the support can be easily removed.

[0489] Example

[0490] The present invention will be described in more detail below through examples, but the present invention is not limited to these examples.

[0491] <Example of synthesis of polyurethane resin ((P1) component)>

[0492] Propylene glycol monomethyl ether acetate (PGMEA), 36 parts castor oil-modified diol, 17 parts polycarbonate diol (Mw 1,000), 18 parts pentaerythritol diacrylate, 1 part neopentyl glycol, 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, 7 parts diphenylmethane diisocyanate (MDI) and 21 parts hydrogenated dimethyl phenylene diisocyanate (H6XDI) were added to the dropping funnel and added dropwise at a uniform rate over 30 minutes. After the addition was complete, the mixture was allowed to mature for 30 minutes. Then, a bismuth catalyst was added, the temperature was raised to 65°C, and the mixture was matured for 4–5 hours. Next, 2HEA (2-hydroxyethyl acrylate) was added, and the mixture was matured for 1 hour, ending the reaction at the point where the isocyanate groups (NCO) disappeared. The resulting polyurethane resin (P1)-1 had a weight-average molecular weight (Mw) of 20,000. The C=C equivalent (molecular weight of polyurethane resin per equivalent of polymerizable carbon-carbon double bond) of polyurethane resin (P1)-1 is 600 g / eq.

[0493] The polycarbonate diol (Mw1,000) used in the synthesis of the polyurethane resin (P1)-1 is a polycarbonate diol represented by the following formula (PC-1-1) (R = -(CH2)6-, -(CH2)5-).

[0494] [Chemical Formula 19]

[0495]

[0496] <Preparation of Adhesive Composition (1)>

[0497] (Examples 1-6, Comparative Example 1)

[0498] Adhesive compositions for each example were prepared by mixing the components shown in Table 1. More specifically, they were prepared as follows. First, components (P1), (A), (Ad), and (S) were mixed in the proportions described in Table 1. Then, component (B) was added in the proportions described in Table 1, and the mixture was mixed until the composition became homogeneous.

[0499] [Table 1]

[0500]

[0501] In Table 1, each abbreviation has the following meaning. The value in [] is the amount (parts by mass). It should be noted that the value in () wt% is the proportion (by mass) of the pigment solid component relative to the total mass (100% by mass) of the adhesive composition.

[0502] (P1)-1: The polyurethane resin (P1)-1 synthesized in the above synthesis example.

[0503] (A)-1: Peroxide (Percumyl D, Nippon Oils & Fats Co., Ltd.).

[0504] (Ad)-1: Polyester-modified polydimethylsiloxane (BYK-310 (trade name), BYK Chemie).

[0505] (S)-1: PGMEA (propylene glycol monomethyl ether acetate).

[0506] (B)-1: Carbon black (acrylic resin dispersion with an average particle size of less than 150 nm).

[0507] (B)-2: Perylene black pigment (volume average particle size 150 nm).

[0508] <Evaluation>

[0509] Measurement of Light Transmittance

[0510] The adhesive compositions of each example were applied to bare glass supports using a spin coating method. The supports were then cured in an oven under a nitrogen atmosphere at 180°C for 1 hour, forming adhesive layers with the film thicknesses described in Table 2. The transmittance of these adhesive layers was evaluated by irradiating them with light of wavelengths from 380 to 780 nm using a UV-3600 spectrophotometer (manufactured by Shimadzu Corporation), and the results are shown in Table 2.

[0511] [Table 2]

[0512]

[0513] The results shown in Table 2 confirm that the transmittance of the adhesive layer formed using the adhesive compositions of Examples 1 to 6 was significantly reduced, and light with a wavelength of 532 nm was absorbed.

[0514] Evaluation of Cleanliness

[0515] The adhesive composition of Example 6 was applied to a glass substrate (30 cm in diameter and 700 μm thick) using a spin-coating method. The substrate was cured in a nitrogen-atmospheric oven at 180°C for 1 hour to form an adhesive layer (18 μm thick). The substrate with the adhesive layer was then treated at 50°C with a treatment solution (a treatment solution obtained by diluting tetramethylammonium hydroxide (TMAH) with a mixture of N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), and propylene glycol (PG) at a concentration of 2% by mass (NMP:DMS:PG = 10:78:12 (mass ratio)). The time required for complete dissolution was measured. The dissolution rate of the adhesive layer was calculated relative to the film thickness. A dissolution rate of 50 nm / sec or higher was considered to indicate good cleanability.

[0516] The dissolution rate of the adhesive layer described above is 70 nm / sec. Therefore, it has been confirmed that the adhesive layer formed using the adhesive composition of Example 6 has good cleanability.

[0517] <Preparation of Adhesive Compositions (2)>

[0518] (Examples 7-9, Comparative Example 2)

[0519] The components shown in Table 3 were mixed to prepare adhesive compositions for each example.

[0520] [Table 3]

[0521]

[0522] In Table 3, each abbreviation has the following meaning. The value in [] is the amount of the mixture (parts by mass).

[0523] (P1)-1: The polyurethane resin (P1)-1 synthesized in the above synthesis example.

[0524] (A)-1: Peroxide (Percumyl D, Nippon Oils & Fats Co., Ltd.).

[0525] (Ad)-1: Polyester-modified polydimethylsiloxane (BYK-310 (trade name), BYK Chemie).

[0526] (S)-1: PGMEA (propylene glycol monomethyl ether acetate).

[0527] (B1)-1: The following compound (B1-1).

[0528] [Chemical Formula 20]

[0529]

[0530] <Evaluation>

[0531] Measurement of Light Transmittance

[0532] The adhesive compositions of each example were applied to bare glass supports using a spin coating method. The supports were then cured in an oven under a nitrogen atmosphere at 180°C for 1 hour, forming adhesive layers with the film thicknesses described in Table 2. The transmittance of this adhesive layer at a wavelength of 355 nm was measured using a UV-3600 spectrophotometer (manufactured by Shimadzu Corporation) irradiated with light of wavelengths from 300 to 800 nm. The results are shown in Table 4 below.

[0533] [Table 4]

[0534]

[0535] The results shown in Table 4 confirm that for the adhesive layers formed using the adhesive compositions of Examples 7-9, the transmittance at the measured wavelength was low, indicating that light in that wavelength range was absorbed.

[0536] Evaluation of Laser Reactivity

[0537] Under the same conditions as described above in the "Measurement of Transmittance," an adhesive layer was formed using the adhesive compositions of Example 9 and Comparative Example 2. This adhesive layer was irradiated with a 355 nm laser using Talon (registered trademark) 355-12 manufactured by Spectra Physics. The adhesive layer was observed, and the indentation was confirmed. The results, along with the transmittance at 355 nm, are shown in Table 5.

[0538] [Table 5]

[0539]

[0540] The results shown in Table 5 confirm that the adhesive layer formed using the adhesive composition of Example 9 exhibits laser reactivity of 355 nm. On the other hand, laser reactivity was not observed in the adhesive layer formed using the adhesive composition of Comparative Example 2.

[0541] Explanation of reference numerals in the attached figures

[0542] 1 Support body

[0543] 3. Adhesive layer

[0544] 3' Adhesive composition layer

[0545] 4. Semiconductor substrate

[0546] 5. Sealing material layer

[0547] 6 Wiring Layer

[0548] 20-layer stack

[0549] 50 Electronic Components

[0550] 100-layer stack

[0551] 100' laminate

[0552] 110-layer stack

[0553] 120-layer stack

[0554] 200-layer stack

[0555] 300-layer stack

[0556] 400-layer stack

[0557] 456 Electronic Components

[0558] 645 Electronic Components

Claims

1. An adhesive composition for forming an adhesive layer temporarily bonding a semiconductor substrate or electronic device to a light-transmitting support, said adhesive composition comprising (b) a light absorber, a polyurethane resin containing polymerizable carbon-carbon unsaturated bonds, a thermal polymerization initiator, a surfactant, and a solvent component. The polyurethane resin is a reaction product of a polyol and a polyisocyanate, wherein at least one of the polyol and the polyisocyanate contains the polymerizable carbon-carbon unsaturated bond. The polyol is composed of polyols containing polymerizable carbon-carbon unsaturated bonds and other polyols, wherein the other polyols are selected from one or more of the group consisting of low molecular weight polyols with a molecular weight of less than 500, polycarbonate polyols, and vegetable oil-based polyols. The polyisocyanate is selected from the group consisting of aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, biuret forms of these diisocyanates, isocyanurate forms of these diisocyanates, and adducts of these diisocyanates with trimethylolpropane. The aliphatic diisocyanate is hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, or lysine diisocyanate. The alicyclic diisocyanate is dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, hydrogenated dimethyl phthalate diisocyanate, hydrogenated toluene diisocyanate, or dicyclohexylmethane-4,4'-diisocyanate. The aromatic diisocyanate is toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, phenylene diisocyanate, dimethylbiphenyl diisocyanate, terephthalene diisocyanate, or naphthalene diisocyanate. The content of the light absorber is 1 to 20% by mass relative to the total mass of the adhesive composition. The light absorber contains a compound (B1) that absorbs at least a portion of light in the wavelength range of 300–800 nm and includes polymeric carbon-carbon unsaturated bonds (wherein, (excluding compounds belonging to the polyurethane resin), The compound (B1) is represented by the following general formula (b1). In the formula, W is a monovalent group containing a polymerizable carbon-carbon unsaturated bond; Y is a single bond, or a divalent linking group selected from the group consisting of -O-, -CO-, -COO-, and -CONH-; n is an integer from 1 to 6; X is an n-valent group containing an aromatic fused ring skeleton, benzophenone skeleton, benzoylmethane skeleton, benzoylbenzene skeleton, or benzotriazole skeleton in its structure; when n is 2 or more, there are multiple W and Y groups, which can be the same or different from each other.

2. The adhesive composition according to claim 1, characterized in that, A composite of a metal or semiconductor component of the electronic device and a resin that seals or insulates the component is laminated onto the support via the adhesive layer.

3. A laminate, which is a laminate consisting of a light-transmitting support, an adhesive layer, and a semiconductor substrate or electronic device stacked sequentially. The adhesive layer is a cured form of the adhesive composition according to claim 1 or 2.

4. A method for manufacturing a laminate, comprising a method for sequentially stacking a light-transmitting support, an adhesive layer, and a semiconductor substrate, wherein the manufacturing method includes the following steps: The process of forming an adhesive composition layer by coating the adhesive composition of claim 1 or 2 onto the support or semiconductor substrate; The process of placing the semiconductor substrate onto the support via the adhesive composition layer; and The process of heat-curing the adhesive composition layer to form the adhesive layer.

5. A method for manufacturing a laminate, wherein the laminate comprises a light-transmitting support, an adhesive layer, and an electronic device stacked sequentially, wherein the manufacturing method further comprises a step of forming an electronic device after obtaining the laminate using the manufacturing method of claim 4, wherein the electronic device is a composite formed of a component made of metal or semiconductor and a resin that seals or insulates the component.

6. Manufacturing methods for electronic components, wherein, After obtaining the laminate using the manufacturing method of the laminate according to claim 4, the following steps are performed: The process of separating the electronic device from the support by modifying the adhesive layer through light irradiation of the support; and A process of removing the adhesive layer attached to the electronic device by using an acid or alkali to break down the urethane bonds in the adhesive layer.

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