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

Abstract

To provide an adhesive composition that can suppress the occurrence of delamination due to a high temperature process, and ensures good washability of an adhesion layer, a laminate produced using the adhesive composition, a method for producing the laminate, and a method for producing an electronic component using the adhesive composition.SOLUTION: An adhesive composition is used to form an adhesion layer that temporarily bonds a semiconductor substrate or an electronic device to a light-transmitting support. The adhesive composition includes a urethane resin including a polymerizable carbon-carbon unsaturated bond (P1), a caprolactone modified urethane acrylate (M1), and a polymerization initiator (A).SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Semiconductor packages (electronic components) containing semiconductor elements come in various forms depending on the size they require, such as WLP (Wafer Level Package) and PLP (Panel Level Package). Semiconductor packaging technologies include fan-in technology and fan-out technology. Examples of semiconductor packages using fan-in technology include fan-in WLP (Fan-in Wafer Level Package), which rearranges terminals located at the edges of the bare chip into the chip area. Examples of semiconductor packages using fan-out technology include fan-out WLP (Fan-out Wafer Level Package), which rearranges these terminals outside the chip area.

[0003] In recent years, fan-out technology, in particular, has attracted attention as a method that can achieve even higher integration, thinner designs, and smaller sizes in semiconductor packages, such as in the application of fan-out panel-level packages (PLPs) which arrange semiconductor elements on a panel and then package them.

[0004] To miniaturize semiconductor packages, it is important to reduce the thickness of the substrate in the components that are incorporated. However, reducing the thickness of the substrate reduces its strength, making it more susceptible to damage during semiconductor package manufacturing. To address this, a technique is known in which the substrate is temporarily bonded to a support using an adhesive, processed, and then separated from the support.

[0005] Thermoplastic adhesives are often used as adhesives for temporary bonding between a substrate and a support, because the adhesive layer can be easily removed with a solvent 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. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] International Publication No. 2016 / 052315 [Overview of the project] [Problems that the invention aims to solve]

[0007] Incidentally, high-temperature processes such as thin-film formation, firing, and die bonding are sometimes performed in semiconductor package manufacturing. If the heat resistance of the adhesive is low, the elastic modulus of the adhesive layer may decrease during high-temperature processing, potentially causing delamination. On the other hand, adding a crosslinking agent to the adhesive increases the elastic modulus of the adhesive layer, improving its heat resistance. However, after separating the substrate from the support, the cleanability of the adhesive layer adhering to the substrate is significantly reduced. The present invention has been made in view of the above circumstances, and aims to provide an adhesive composition that can suppress delamination due to high-temperature processes and has good cleanability 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. [Means for solving the problem]

[0008] To solve the above problems, the present invention employs the following configuration. In other words, a first aspect of the present invention is an adhesive composition used to form an adhesive layer for temporarily bonding a semiconductor substrate or electronic device to a light-transmitting support, comprising a polymerizable carbon-carbon unsaturated urethane resin (P1) and a caprolactone-modified urethane (meta)This is an adhesive composition containing acrylate (M1) and polymerization initiator (A).

[0009] A second aspect of the present invention is a laminate comprising a support, an adhesive layer, and a semiconductor substrate or electronic device stacked in that order, wherein the adhesive layer is a cured form of the adhesive composition according to the first aspect.

[0010] A third aspect of the present invention is a method for manufacturing a laminate in which a support, an adhesive layer, and a semiconductor substrate are stacked in this order, comprising the steps of: applying an adhesive composition according to the first aspect to the support or the semiconductor substrate to form an adhesive composition layer; placing the semiconductor substrate on the support via the adhesive composition layer; and curing the adhesive composition layer to form the adhesive layer.

[0011] A fourth aspect of the present invention is a method for manufacturing a laminate in which a support, an adhesive layer, and an electronic device are laminated in this order, further comprising an electronic device forming step of forming an electronic device which is a composite of a member made of metal or semiconductor and a resin that seals or insulates the member, after obtaining a laminate by the method for manufacturing a laminate according to the third aspect.

[0012] A fifth aspect of the present invention is a method for manufacturing an electronic component, comprising the step of removing the adhesive layer by decomposing the urethane bonds of the urethane resin with an acid or alkali after obtaining a laminate by the method for manufacturing a laminate according to the fourth aspect. [Effects of the Invention]

[0013] The present invention provides an adhesive composition that can suppress delamination caused by high-temperature processes and has good cleanability 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. [Brief explanation of the drawing]

[0014] [Figure 1] This is a schematic diagram showing one embodiment of a laminate to which the present invention is applied. [Figure 2] This is a schematic diagram showing one embodiment of a laminate to which the present invention is applied. [Figure 3] This is a schematic diagram showing one embodiment of a laminate to which the present invention is applied. [Figure 4] This is a schematic diagram showing one embodiment of a laminate to which the present invention is applied. [Figure 5] This is a schematic process diagram illustrating one embodiment of a method for manufacturing a laminate 100' in which a support, an adhesive composition layer, and a semiconductor substrate are stacked in that order. Figure 5(a) shows a support consisting of a support substrate and a separation layer, Figure 5(b) illustrates the adhesive composition layer formation process, and Figure 5(c) illustrates the semiconductor substrate placement process. [Figure 6] This is a diagram illustrating the adhesive layer formation process. [Figure 7] This is a schematic process diagram illustrating one embodiment of a method for manufacturing a laminate 120. Figure 7(a) illustrates the sealing process, Figure 7(b) illustrates the grinding process, and Figure 7(c) illustrates the wiring layer formation process. [Figure 8] This is a schematic process diagram illustrating one embodiment of a method for manufacturing a semiconductor package (electronic component) from a laminate 120. Figure 8(a) shows the laminate 200, Figure 8(b) illustrates the separation process, and Figure 8(c) illustrates the adhesive layer removal process. [Modes for carrying out the invention]

[0015] In this specification and in the claims, "aliphatic" is defined as a concept relative to aromatic, meaning a group, compound, etc., that does not possess aromaticity. Unless otherwise specified, "alkyl group" includes linear, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to alkyl groups within alkoxy groups. Unless otherwise specified, the term "alkylene group" includes linear, branched, and cyclic divalent saturated hydrocarbon groups. A "halogenated alkyl group" is a group in which some or all of the hydrogen atoms of an alkyl group are replaced by halogen atoms, and examples of such halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. A "fluorinated alkyl group" or "fluorinated alkylene group" refers to a group in which some or all of the hydrogen atoms of an alkyl group or alkylene group are replaced with fluorine atoms. "Constituent unit" refers to the monomer unit (monomer unit) that makes up a polymer compound (resin, polymer, copolymer). When it is stated that "may have substituents" or "may have substituents," this includes both cases where a hydrogen atom (-H) is substituted with a monovalent group and cases where a methylene group (-CH2-) is substituted with a divalent group. "Exposure" is a concept that includes all forms of radiation exposure.

[0016] "Constituent units derived from hydroxystyrene" refers to constituent units formed by the cleavage of the ethylenic double bond of hydroxystyrene. "Constituent units derived from hydroxystyrene derivatives" refers to constituent units formed by the cleavage of the ethylenic double bond of a hydroxystyrene derivative. The term "hydroxystyrene derivative" refers to a compound in which the α-hydrogen atom of hydroxystyrene is replaced by another substituent such as an alkyl group or an alkyl halide, as well as derivatives thereof. Examples of such derivatives include those in which the hydrogen atom of the hydroxyl group of hydroxystyrene, which may have its α-hydrogen atom replaced by a substituent, is replaced by an organic group; and those in which a substituent other than a hydroxyl group is bonded to the benzene ring of hydroxystyrene, which may have its α-hydrogen atom replaced by a substituent. Unless otherwise specified, the α-position (the carbon atom at the α-position) refers to the carbon atom to which the benzene ring is bonded. Examples of substituents that substitute for the α-position hydrogen atom of hydroxystyrene include those similar to those listed as substituents at the α-position in the α-substituted acrylic acid esters.

[0017] The alkyl group used as the substituent at the α-position is preferably a linear or branched alkyl group. Specifically, examples include alkyl groups having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc.). Furthermore, the halogenated alkyl group as the α-substituent specifically refers to a group in which some or all of the hydrogen atoms of the "alkyl group as the α-substituent" described above are replaced with halogen atoms. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being particularly preferred. Furthermore, the hydroxyalkyl group as the α-substituent specifically refers to a group in which some or all of the hydrogen atoms of the "alkyl group as the α-substituent" described above are replaced with hydroxyl groups. The number of hydroxyl groups in the hydroxyalkyl group is preferably 1 to 5, with 1 being the most preferred.

[0018] In this specification and the claims, some structures represented by chemical formulas may contain a chiral carbon, and may have enantioisomers or diastereomers; however, in such cases, a single formula will represent all of these isomers. These isomers may be used individually or as a mixture.

[0019] (Adhesive composition) An adhesive composition according to a first aspect of the present invention is an adhesive composition used to form an adhesive layer for temporary bonding between a semiconductor substrate or electronic device and a support, comprising a polymerizable carbon-carbon unsaturated urethane resin (P1) and a caprolactone-modified urethane (meta) It is characterized by containing acrylate (M1) and polymerization initiator (A).

[0020] <Items to be temporarily bonded> The adhesive composition according to this embodiment is used to form an adhesive layer for temporarily bonding a semiconductor substrate or electronic device to a support. In this specification, "temporary bonding" means that the objects to be bonded are temporarily bonded (for example, during any work process). More specifically, the semiconductor substrate or electronic device is temporarily bonded to a support and fixed on the support (temporary bonding) for purposes such as thinning the device, transporting the semiconductor substrate, or mounting the semiconductor substrate, and is separated from the support after the completion of the process.

[0021] ≪Semiconductor Substrates≫ The semiconductor substrate to which the adhesive composition according to this embodiment is applied is not particularly limited and may be any semiconductor substrate commonly used. The semiconductor substrate (bare chip) is subjected to processes such as thinning and mounting while supported on a support. Structures such as integrated circuits and metal bumps may be mounted on the semiconductor substrate. Typical semiconductor substrates include silicon wafers, but are not limited to these; ceramic substrates, thin film substrates, flexible substrates, etc., may also be used.

[0022] Electronic Devices In this specification, "electronic device" means a component that constitutes at least a part of an electronic component. An electronic device is not particularly limited and may have various mechanical structures or circuits formed on the surface of a semiconductor substrate. Preferably, an electronic device may be a composite of a component made of metal or semiconductor and a resin that seals or insulates the component. An electronic device may have a single-layer or multi-layer structure in which a redistribution layer and / or semiconductor elements or other elements described later are sealed or insulated with a sealing material or insulating material.

[0023] ≪Support≫ The support is a component that supports a semiconductor substrate or an electronic device. As described later, the support may consist of a support base, which has light-transmitting properties and supports the semiconductor substrate, and a separation layer that is altered by light irradiation.

[0024] <Polymerizable carbon-carbon double bond-containing urethane resin: (P1) component> The adhesive composition according to this embodiment contains a urethane resin containing polymerizable carbon-carbon double bonds (hereinafter also referred to as "component (P1)"). Component (P1) can polymerize and harden via the polymerizable carbon-carbon double bonds to form an adhesive layer. This allows for temporary bonding of a semiconductor substrate or electronic device to a support. Furthermore, the urethane bonds in component (P1) are decomposed by acids or alkalis. Therefore, the adhesive layer can be easily removed by a treatment solution containing an acid or alkali. Components corresponding to component (M) described later are excluded from component (P1).

[0025] The polymerizable carbon-carbon double bond contained in component (P1) is not particularly limited, but is preferably radically polymerizable. Examples of polymerizable carbon-carbon double bonds include methacryloyl groups and acryloyl groups. Component (P1) may contain one polymerizable carbon-carbon double bond or two or more. The equivalent amount of polymerizable carbon-carbon double 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 polymerizable carbon-carbon double bonds is 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 polymerizable carbon-carbon double bonds is below the upper limit of the above preferred range, the adhesive layer does not become too hard and has good washability. The above equivalent number is the molecular weight of the urethane resin per equivalent of polymerizable carbon-carbon double bonds.

[0026] 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.

[0027] Component (P1) can be synthesized by a polymerization addition reaction between a polyisocyanate compound (hereinafter also referred to as "component (I)") and a polyol (hereinafter also referred to as "component (O)"). Preferably, at least one of components (I) and (O) contains a polymerizable carbon-carbon double bond.

[0028] ≪Polyisocyanate compound: (I) component≫ In this specification, "polyisocyanate compound" means a compound having two or more isocyanate groups (-N=C=O) (polyisocyanate) or a compound having two or more blocked isocyanate groups (blocked polyisocyanate). The polyisocyanate is not particularly limited, and any polyisocyanate commonly used in the manufacture of urethane resins can be used without any particular restriction. Blocked polyisocyanates are compounds in which the isocyanate groups of polyisocyanates are blocked and inactivated by reaction with a blocking agent. It is preferable that the blocked polyisocyanate used as component (I) has its isocyanate groups blocked by a thermally dissociable blocking agent. Examples of thermally dissociable blocking agents include oximes, diketones, phenols, and caprolactams. Blocked polyisocyanates with a thermally dissociable blocking agent are inactive at room temperature, and upon heating, the thermally dissociable blocking agent dissociates, regenerating the isocyanate groups.

[0029] Specific examples of polyisocyanates include, for example, aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate; and alicyclic diisocyanates such as dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, and dicyclohexylmethane-4,4'-diisocyanate. Examples include isocyanates; and aromatic diisocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, and naphthylene diisocyanate; as well as their biuret derivatives, isocyanurates, and adduct derivatives of trimethylolpropane. Polyisocyanates may be used individually or in combination of two or more.

[0030] Commercially available polyisocyanates may be used. Examples of commercially available polyisocyanates include Duranate® 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 Examples include Duranate TLA-100, Duranate TSA-100, Duranate TSS-100, Duranate TSE100, Duranate E402-80B, Duranate E405-70B, Duranate AS700-100, Duranate D101, Duranate D201, and Duranate A201H (all product names, manufactured by Asahi Kasei Chemicals). These products may be used individually or in combination of two or more types.

[0031] Examples of blocked isocyanates include compounds in which the isocyanate group of a polyisocyanate, as described above, is protected by reaction with a blocking agent. The blocking agent is not particularly limited as long as it is a thermally dissociable blocking agent, that is, a compound that adds to the isocyanate group, is stable at room temperature but is liberated and generates an isocyanate group when heated above its dissociation temperature. Known blocking agents can be used without any particular restrictions. Specific examples of blocking agents include, for example, lactam compounds such as γ-butyrolactam, ε-caprolactam, γ-valerolactam, and propiolactam; oxime compounds such as methyl ethyl ketoxime, methyl isoamyl ketoxime, methyl isobutyl ketoxime, formamide oxime, acetamide oxime, acetooxime, diacetyl monooxime, benzophenone oxime, and cyclohexanone oxime; monocyclic phenol compounds such as phenol, cresol, catechol, and nitrophenol; polycyclic phenol compounds such as 1-naphthol; alcohol compounds such as methyl alcohol, ethyl alcohol, isopropyl alcohol, tert-butyl alcohol, trimethylolpropane, and 2-ethylhexyl alcohol; ether compounds such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether; and active methylene compounds such as alkyl malonates, dialkyl malonates, alkyl acetoacetate, and acetylacetone. Blocking agents may be used individually or in combination of two or more.

[0032] Blocked polyisocyanates can be produced by reacting a polyisocyanate with a blocking agent. The reaction between the polyisocyanate and the blocking agent is carried out, for example, in a solvent that does not contain active hydrogen (such as 1,4-dioxane or cellosolve acetate) under heating at approximately 50 to 100°C, and optionally in the presence of a blocking catalyst. The ratio of polyisocyanate to blocking agent used is not particularly limited, but preferably the equivalent ratio of isocyanate groups in the polyisocyanate to the blocking agent is 0.95:1.0 to 1.1:1.0, and more preferably 1:1.05 to 1.15. Known block catalysts can be used, such as metal alcohols like sodium methylate, sodium ethylate, sodium phenolate, and potassium methylate; tetraalkylammonium hydroxides like tetramethylammonium, tetraethylammonium, and tetrabutylammonium; organic weak salts of these, such as acetates, octylates, myristates, and benzoates; and alkali metal salts of alkyl carboxylic acids such as acetic acid, caproic acid, octylic acid, and myristic acid. The block catalyst may be used alone or in combination of two or more types.

[0033] Commercially available blocked polyisocyanates may be used. Examples of commercially available blocked polyisocyanates include Duranate MF-K60B, Duranate SBB-70P, Duranate SBN-70D, Duranate MF-B60B, Duranate 17B-60P, Duranate TPA-B80E, and Duranate E402-B80B (all are trade names, manufactured by Asahi Kasei Corporation).

[0034] (I) Component is preferably a blocked polyisocyanate in which the isocyanate group is blocked by a thermally dissociable blocking agent. Component (I) may be used alone or in combination of two or more. For example, component (I) may be a mixture of an aliphatic diisocyanate and an aromatic diisocyanate. Hydrogenated xylene diisocyanate is preferred as the aliphatic diisocyanate. 4,4-diphenylmethane diisocyanate is preferred as the aromatic diisocyanate.

[0035] ≪Polyol: (O) component≫ A polyol (component (O)) is a compound having two or more hydroxyl groups (-OH). The polyol is not particularly limited, and any polyol commonly used in the manufacture of urethane resins can be used without any particular restrictions. Examples of component (O) include polyols containing polymerizable carbon-carbon double bonds (hereinafter also referred to as "component (O1)") and other polyols (hereinafter also referred to as "component (O2)").

[0036] • Polyols containing polymerizable carbon-carbon double bonds (component (O1)) The (O1) component may include a polyol containing at least one selected from the group consisting of a methacryloyl group and an acryloyl group. The polymerizable carbon-carbon double bond in the (O1) component may be one or two or more.

[0037] (O1) component may include, for example, esters of a trivalent or higher polyol with methacrylic acid, acrylic acid, or derivatives thereof. A trivalent or higher low molecular weight polyol is preferred as the trivalent or higher polyol. Examples of the trivalent or higher low molecular weight polyol include trivalent alcohols such as glycerin and trimethylolpropane; tetravalent alcohols such as tetramethylolmethane (pentaerythritol) and diglycerin; pentavalent alcohols such as xylitol; hexavalent alcohols such as sorbitol, mannitol, allitol, isitol, dalcitol, althritol, inositol, and dipentaerythritol; heptavalent alcohols such as perceitol; and octavalent alcohols such as sucrose.

[0038] Specific examples of (O1) components include glycerin mono(meth)acrylate, diglycerin tri(meth)acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, diglycerin di(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, sorbitol mono(meth)acrylate, sorbitol di(meth)acrylate, sorbitol tri(meth)acrylate, sorbitol tetra(meth)acrylate, etc. "(Meth)acrylate" is a concept that encompasses both methacrylate and acrylate, and means either methacrylate or acrylate.

[0039] (O1) Component may be used alone or in combination of two or more types. In particular, the (O1) component is preferably a diol containing a methacryloyl group or an acryloyl group, and more preferably glycerin mono(meth)acrylate or pentaerythritol di(meth)acrylate.

[0040] • Other polyols ((O2) components) Component (O2) is a polyol other than component (O1) described above. Component (O2) is not particularly limited and may be an aliphatic polyol or an aromatic polyol. Component (O2) may be a low molecular weight polyol (e.g., molecular weight less than 500) or a high molecular weight polyol (e.g., molecular weight 500 or more).

[0041] Examples of low molecular weight polyols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, alkanediols with 7 to 22 carbon atoms, diethylene glycol, triethylene glycol, dipropylene glycol, 3-methyl-1,5-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, alkanediols with 17 to 20 carbon atoms, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol. Examples include dihydric alcohols such as 1,4-cyclohexanediol, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octen-3,8-diol, and bisphenol A; trihydric alcohols such as glycerin and trimethylolpropane; tetrahydric alcohols such as tetramethylolmethane (pentaerythritol) and diglycerin; pentahydric alcohols such as xylitol; hexahydric alcohols such as sorbitol, mannitol, allitol, isitol, dalcitol, althritol, inositol, and dipentaerythritol; heptahydric alcohols such as perceitol; and octahydric alcohols such as sucrose. Among these, dihydric alcohols (diols) are preferred as low molecular weight polyols.

[0042] Examples of polymeric polyols include phenolic resins, resins containing a hydroxystyrene skeleton, polyester polyols, polyether polyols, polyether ester polyols, polyesteramide polyols, acrylic polyols, polycarbonate polyols, polyhydroxyalkanes, polyurethane polyols, and vegetable oil-based polyols. The number-average molecular weight of the polymeric polyol is preferably 500 to 100,000.

[0043] When a low molecular weight polyol is used as the (O2) component, the ratio of the low molecular weight polyol to the (O1) component (low molecular weight polyol / (O1) component (mass ratio)) is preferably 0.01 to 0.1, and more preferably 0.03 to 0.08.

[0044] [Phenolic resin] The phenolic resin may be a novolac-type phenolic resin or a resol-type phenolic resin. Novolac-type phenolic resins can be obtained by addition-condensation of aromatic compounds having phenolic hydroxyl groups (hereinafter referred to as "phenols") and aldehydes under an acid catalyst. Resol-type phenolic resins can be obtained by addition-condensation of phenols and aldehydes under an alkaline catalyst.

[0045] Examples of the phenols include phenols; cresols such as m-cresol, p-cresol, and o-cresol; xylenols such as 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, and 3,4-xylenol; alkylphenols such as m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-4-methylphenol, and 2-tert-butyl-5-methylphenol; p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxy Examples include alkoxyphenols such as phenol, p-propoxyphenol, and m-propoxyphenol; isopropenylphenols such as o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, and 2-ethyl-4-isopropenylphenol; arylphenols such as phenylphenol; and polyhydroxyphenols such as 4,4'-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, pyrogallol, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, and 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane.

[0046] Examples of the aforementioned aldehydes include formaldehyde, paraformaldehyde, trioxane, furfural, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, cinnamaldehyde, 4-isopropylbenzaldehyde, 4-isobutylbenzaldehyde, and 4-phenylbenzaldehyde.

[0047] The acid catalyst used in the addition-condensation reaction is not particularly limited, and examples include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, and acetic acid. The alkali catalyst used in the addition-condensation reaction is not particularly limited, and examples include sodium hydroxide, lithium hydroxide, potassium hydroxide, aqueous ammonia, triethylamine, sodium carbonate, and hexamethylenetetramine.

[0048] [Resin containing a hydroxystyrene skeleton] The resin containing the hydroxystyrene skeleton is not particularly limited as long as it has structural units derived from hydroxystyrene or hydroxystyrene derivatives. Specific examples of structural units derived from hydroxystyrene or hydroxystyrene derivatives include the structural unit represented by the following general formula (a10-1).

[0049] [ka] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halogen having 1 to 5 carbon atoms. x1 Wa is a single bond or a divalent linking group. x1 is, (n ax1 It is a +1) valent aromatic hydrocarbon group. ax1 [This is an integer between 1 and 3.]

[0050] In the above formula (a10-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide having 1 to 5 carbon atoms. The alkyl group of R having 1 to 5 carbon atoms is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, specifically including methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl groups. The halogenated alkyl group of R having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms, with fluorine atoms being particularly preferred. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, with a hydrogen atom or a methyl group being the most preferred due to their industrial availability.

[0051] In the above formula (a10-1), Ya x1 It is a single bond or a divalent linking group. Ya x1 Suitable divalent linking groups in this context include, for example, divalent hydrocarbon groups which may have substituents, and divalent linking groups which contain heteroatoms.

[0052] • Divalent hydrocarbon groups which may have substituents: Ya x1 If is a divalent hydrocarbon group which may have substituents, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0053] ··Ya x1 Aliphatic hydrocarbon groups in The aliphatic hydrocarbon group refers to a hydrocarbon group that does not possess aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, but is usually preferred to be saturated. Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing a ring in their structure.

[0054] ...linear or branched aliphatic hydrocarbon groups The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As for the linear aliphatic hydrocarbon group, linear alkylene groups are preferred, specifically the methylene group [-CH2-], ethylene group [-(CH2)2-], trimethylene group [-(CH2)3-], tetramethylene group [-(CH2)4-], pentamethylene group [-(CH2)5-], etc. 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. Preferred branched aliphatic hydrocarbon groups include branched alkylene groups, specifically alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as alkyltetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. In the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferred.

[0055] The linear or branched aliphatic hydrocarbon group described above may or may not have substituents. Examples of substituents include fluorine atoms, fluorinated alkyl groups having 1 to 5 carbon atoms substituted with fluorine atoms, and carbonyl groups.

[0056] ...Aliphatic hydrocarbon groups containing a ring in their structure Examples of aliphatic hydrocarbon groups containing a ring in the structure include cyclic aliphatic hydrocarbon groups that may contain substituents containing heteroatoms in the ring structure (groups from which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring), groups in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and groups in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group are the same as those described above. The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms. The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. A preferred monocyclic alicyclic hydrocarbon group is a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. A preferred polycyclic alicyclic hydrocarbon group is a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

[0057] The cyclic aliphatic hydrocarbon group may or may not have substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, and carbonyl groups. The alkyl group used as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. As the alkoxy group used as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferred, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are more preferred, and a methoxy group and an ethoxy group are most preferred. Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferred. Examples of the halogenated alkyl group as the substituent include a group in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms. In the cyclic aliphatic hydrocarbon group, some of the carbon atoms constituting the ring structure may be substituted with a substituent containing a heteroatom. Preferred examples of the substituent containing a heteroatom include -O-, -C(=O)-O-, -S-, -S(=O)2-, -S(=O)2-O-.

[0058] ··Ya x1 The aromatic hydrocarbon group in The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, still more preferably 6 to 15, and particularly preferably 6 to 12. However, the number of carbon atoms does not include the number of carbon atoms in the substituent. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocyclic rings in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms, etc. Examples of the heteroatom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, a nitrogen atom, etc. Specific examples of the aromatic heterocyclic ring include a pyridine ring, a thiophene ring, etc. Specific examples of aromatic hydrocarbon groups include groups obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); groups obtained by removing two hydrogen atoms from aromatic compounds containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups in which one hydrogen atom of an aryl group or heteroaryl group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) is substituted with an alkylene group (e.g., groups obtained by removing one more hydrogen atom from an aryl group in an arylalkyl group such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0059] The aromatic hydrocarbon group may have its hydrogen atoms substituted with substituents. For example, the hydrogen atoms bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, and hydroxyl groups. The alkyl group used as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. Examples of the substituents include alkoxy groups, halogen atoms, and alkyl halogens that substitute for hydrogen atoms on the cyclic aliphatic hydrocarbon group.

[0060] • Divalent linking groups containing heteroatoms: Ya x1When is a divalent linking group containing a heteroatom, preferred linking groups include -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H may be substituted with substituents such as alkyl groups or acyl groups), -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 - is represented by the base [wherein Y 21 and Y 22 Each of these is a divalent hydrocarbon group which may have substituents independently, O is an oxygen atom, and m'' is an integer from 0 to 3. When the aforementioned divalent linking group containing the heteroatom is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, or -NH-C(=NH)-, the H may be substituted with substituents such as alkyl groups or acyl groups. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 5. 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 - Middle, Y 21 and Y 22These are, independently, divalent hydrocarbon groups which may have substituents. Examples of such divalent hydrocarbon groups are the same as those listed in the description of divalent linking groups (divalent hydrocarbon groups which may have substituents). Y 21 Preferably, the group is a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, even more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group. Y 22 The group is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group, or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. Formula - [Y 21 -C(=O)-O] m” -Y 22 In the base represented by -, m'' is an integer between 0 and 3, preferably between 0 and 2, more preferably 0 or 1, and particularly preferably 1. That is, in the formula -[Y 21 -C(=O)-O] m” -Y 22 As a base represented by -, formula -Y 21 -C(=O)-OY 22 Groups represented by - are particularly preferred. Among them, the group represented by formula -(CH2) a’ -C(=O)-O-(CH2) b’ A base represented by - is preferred. In the formula, a' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, even more 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, even more preferably 1 or 2, and most preferably 1.

[0061] Ya x1 Preferably, the group is a single bond, an ester bond [-C(=O)-O-], an ether bond (-O-), a -C(=O)-NH-, a linear or branched alkylene group, or a combination thereof, with single bonds being particularly preferred.

[0062] In the above formula (a10-1), Wa x1 is, (n ax1 It is a +1) valent aromatic hydrocarbon group. Wa x1 As for aromatic hydrocarbon groups in this context, (n ax1 Examples include groups with 1+1 hydrogen atoms removed. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system with 4n+2 π electrons, and may 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. Specific examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings.

[0063] In the above formula (a10-1), n ax1 is an integer between 1 and 3, preferably 1 or 2, and more preferably 1.

[0064] The following are specific examples of the constituent units represented by the general formula (a10-1). In the following formula, R α This represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0065] [ka]

[0066] The resin containing the hydroxystyrene skeleton is preferably a polymer of hydroxystyrene or a hydroxystyrene derivative, and more preferably a polymer of hydroxystyrene (polyhydroxystyrene).

[0067] [Polycarbonate polyol] Examples of polycarbonate polyols include polycarbonate polyols obtained by reacting one or more glycols, such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, or hydrogenated bisphenol A, with dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene, etc.

[0068] Among these, polycarbonate diols represented by the following general formula (PC-1) are preferred.

[0069] [ka] [In the formula, Rp 1 and Rp 2 Each of these is independently a divalent hydrocarbon group. np is an integer greater than or equal to 2.

[0070] In the general formula (PC-1), Rp 1 and Rp 2 Each of these is independently a divalent hydrocarbon group. The divalent hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. The divalent hydrocarbon group is Ya in the general formula (a10-1) above. x1 The same things as those listed above can be cited. Rp 1 and Rp 2 The divalent hydrocarbon group in is preferably an aliphatic hydrocarbon group, and more preferably a linear or branched alkylene group. The divalent hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 4 to 6 carbon atoms. Rp 1 and Rp 2Specific examples include -(CH2)6- or -(CH2)5-.

[0071] 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.

[0072] 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.

[0073] [Other polyols] Examples of polyester polyols include polyester polyols obtained by reacting dibasic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, and sebatic acid, or their dialkyl esters or mixtures thereof, with glycols such as ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, and polytetramethylene ether glycol, or mixtures thereof; or polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, polyvalerolactone, and poly(β-methyl-γ-valerolactone).

[0074] Examples of polyether polyols include polyether polyols obtained by polymerizing oxirane compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran using low molecular weight polyols such as water, ethylene glycol, propylene glycol, trimethylolpropane, and glycerin as initiators.

[0075] Examples of polyether ester polyols include polyether ester polyols obtained by reacting a dibasic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, or sebatic acid, or their dialkyl esters, or mixtures thereof, with the above-mentioned polyether polyol.

[0076] Examples of polyesteramide polyols include those obtained by using an aliphatic diamine having an amino group, such as ethylenediamine, propylenediamine, or hexamethylenediamine, as a raw material in the esterification reaction described above.

[0077] Examples of acrylic polyols include polyester amide polyols obtained by copolymerizing hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, etc., which contain one or more hydroxyl groups in one molecule, or their corresponding methacrylic acid derivatives, with, for example, acrylic acid, methacrylic acid, or their esters.

[0078] Examples of polyhydroxyalkanes include butadiene or liquid rubber obtained by copolymerizing butadiene with acrylamide or the like.

[0079] Polyurethane polyols are polyols having one or more urethane bonds in one molecule. Examples include polyurethane polyols obtained by reacting a polyether polyol, polyester polyol, polyether ester polyol, etc., with a number average molecular weight of 200 to 20,000 with a polyisocyanate, preferably with an NCO / OH ratio of less than 1, more preferably 0.9 or less.

[0080] 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. When a vegetable oil-based polyol is used as the (O2) component, the ratio of the vegetable oil-based polyol to the (O1) component (vegetable oil-based polyol / (O1) component (mass ratio)) is preferably 0.1 to 5, more preferably 0.3 to 3, and even more preferably 0.4 to 2.5.

[0081] The (O2) component may be used alone or in combination of two or more types. Among the above, polycarbonate polyols and low molecular weight polyols are preferred as the (O2) component from the viewpoint of adjusting the viscosity of the adhesive composition and the hardness of the adhesive layer. Furthermore, castor oil-modified polyols may be used as the (O2) component from the viewpoint of improving the heat resistance of the adhesive layer.

[0082] Component (O) is preferably a combination of component (O1) and component (O2) from the viewpoint of adjusting the viscosity of the adhesive composition and the heat resistance of the adhesive layer. The (O2) component is preferably a low molecular weight polyol, a polycarbonate polyol, or a castor oil modified polyol, or a combination thereof. Specific examples of component (O2) to be combined with component (O1) include a combination of polycarbonate polyol, castor oil modified polyol, and low molecular weight polyol; a combination of polycarbonate polyol and castor oil modified polyol; and polycarbonate polyol, etc. The mass ratio of component (O1) to component (O2) is preferably (O1):(O2)=1:5 to 5:1, more preferably 1:4 to 2:1, even more preferably 1:4 to 1:1, and particularly preferably 1:4 to 1:2. By setting the mass ratio of component (O1) to component (O2) within the above range, the elastic modulus and heat resistance of the adhesive layer can be improved.

[0083] Component (P1) can be synthesized by mixing components (I) and (O) and copolymerizing them according to known methods for synthesizing urethane resins. The copolymerization of components (I) and (O) is preferably carried out in the presence of a known urethane catalyst such as a bismuth catalyst. Furthermore, a polymerization inhibitor may be added to the reaction system to avoid polymerization of the polymerizable carbon-carbon double bond in component (O1).

[0084] The ratio (mass ratio) of component (I) to component (O) used in the synthesis of component (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 hydroxyl groups (-OH) in component (O) to isocyanate groups (-NCO) in component (I) is preferably 60:40 to 40:60, and more preferably 55:45 to 45:55.

[0085] (P1) Component may be used alone or in combination of two or more types. The content of component (P1) in the adhesive composition of this embodiment is not particularly limited as long as it is at a concentration that can be applied to a support or the like. The content of component (P1) in the adhesive composition is preferably 20 to 95% by mass, more preferably 30 to 90% by mass, even more preferably 40 to 80% by mass, and particularly preferably 50 to 70% by mass, based on the total amount (100% by mass) of the adhesive composition.

[0086] <Crosslinking agent component: (M) component> The adhesive composition of this embodiment contains, in addition to the above-mentioned (P1) component, a crosslinking agent component (hereinafter also referred to as "(M) component"). The adhesive composition of this embodiment contains caprolactone-modified urethane as the crosslinking agent component. (meta) It contains acrylate (hereinafter also referred to as "(M1) component").

[0087] Caprolactone-modified urethane (meta) Acrylate: (M1) component≫ (M1) Component is a polycaprolactone group (-[O(CH2)5CO] n -) Urethane containing (meta) It is an acrylate. The (M1) component is a urethane containing a group represented by the following general formula (c1). (meta) Acrylate is one example.

[0088] [ka] [In the formula, Rc 1 Rc represents a hydrogen atom or a methyl group; 2 [where n represents an alkylene group; n represents an integer from 1 to 20.]

[0089] In the above formula (c1), Rc 2 Rc represents an alkylene group. 2 The alkylene group in Rc may be linear, branched, or cyclic, but linear is preferred. 2 The alkylene group in is preferably having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms, or 1 or 2 carbon atoms. In formula (c1), n ​​is preferably an integer between 1 and 10, more preferably an integer between 1 and 8, and even more preferably an integer between 1 and 6.

[0090] The group represented by formula (c1) is preferably the group represented by the following formula (c1-1).

[0091] [ka] [In the formula, Rc 1 [where m represents a hydrogen atom or a methyl group; where m represents an integer from 1 to 10; where n represents an integer from 1 to 20.]

[0092] In the above formula (c1-1), m is preferably an integer between 1 and 8, more preferably an integer between 1 and 6, even more preferably an integer between 1 and 4, and particularly preferably an integer between 1 and 3. A specific example of m is 2. In the above formula (c1-1), n ​​is preferably an integer between 1 and 10, more preferably an integer between 1 and 8, and even more preferably an integer between 1 and 6.

[0093] (M1) The main skeleton of the urethane acrylate in the component is not particularly limited. The urethane acrylate may be a biuret type, an isocyanurate type, or an adduct type with an aliphatic polyol (e.g., trimethylolpropane). The (M1) component of the biuret type is exemplified by the following general formula (m1-1). The (M1) component of the isocyanurate type is exemplified by the following general formula (m1-2). The (M1) component of the adduct type is exemplified by the following general formula (m1-3).

[0094] [Chemical formula] [In the formula, Rx 1 ~Rx 3 each independently represents a group represented by the above formula (c1). Rm 1 , Rm 2 , and Rm 3 each independently represents a hydrocarbon group which may have a substituent. Rm 4 ~Rm 6 each independently represents a linear or branched alkylene group. Rm 7 represents a linear or branched alkyl group. ]

[0095] In the above formulas (m1-1) to (m1-3), Rm 1 , Rm 2 , and Rm 3 each independently represents a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group which may have a substituent include the same ones as those exemplified as the divalent hydrocarbon group which may have a substituent in Ya x1 in the above formula (a10-1). Rm 1 , Rm 2 , and Rm 3 may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Rm 1 , Rm 2 , and Rm 3The aliphatic hydrocarbon group in [description] preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 6 carbon atoms. The aliphatic hydrocarbon group may be linear, branched, or cyclic. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and even more preferably 2 to 6 carbon atoms. The cyclic aliphatic hydrocarbon group preferably has 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 3 to 6 carbon atoms. Rm 1 , Rm 2 , and Rm 3 The aromatic hydrocarbon group in [description] preferably has 4 to 12 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 10 carbon atoms. The aromatic ring contained in the aromatic hydrocarbon group may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring.

[0096] Rm 1 , Rm 2 , and Rm 3 The hydrocarbon group in [description] may or may not have a substituent. Rm 1 , Rm 2 , and Rm 3 Examples of the substituent that the hydrocarbon group in [description] may have include the same substituents as those exemplified for the divalent hydrocarbon group that may have a substituent in the above formula (a10-1) and Ya x1 in [description].

[0097] Rm 1 , Rm 2 , and Rm 3 are preferably linear or branched alkylene groups, more preferably linear alkylene groups, even more preferably linear alkylene groups having 1 to 10 carbon atoms, and particularly preferably linear alkylene groups having 1 to 6 carbon atoms.

[0098] In the above formula (m1-3), Rm 4 ~Rm 6 each independently represents a linear or branched alkylene group. Rm 4 ~Rm 6The linear alkylene group in Rm preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms. 4 ~Rm 6 The branched alkylene group in this product preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, even more preferably 2 to 6 carbon atoms, and particularly preferably 2 or 3 carbon atoms. In the above formula (m1-3), Rm 7 Rm represents a linear or branched alkyl group. 7 The linear alkyl group in Rm preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms. 7 The branched alkyl group in this compound preferably has 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, even more preferably 3 to 6 carbon atoms, and particularly preferably 3 or 4 carbon atoms.

[0099] Specific examples of the (M1) component are listed below, but are not limited to these.

[0100] [ka] [In the formula, Rx 11 ~Rx 13 This represents the group expressed by the following formula (c1-1-1).

[0101] [ka] [In the formula, n represents an integer between 1 and 20.]

[0102] Component (M1) can be obtained by known methods. For example, component (M1) can be obtained by reacting a polyisocyanate compound with a caprolactone-modified (meth)acrylate.

[0103] Polyisocyanate compounds include those similar to those listed as component (I) above. Examples of polyisocyanate compounds include the biuret form of diisocyanate, the isocyanurate form of diisocyanate, and the adduct form of diisocyanate with an aliphatic polyol (e.g., trimethylolpropane). Examples of the biuret form of diisocyanate include the compound represented by the following general formula (I-1). Examples of the isocyanurate form of diisocyanate include the compound represented by the following general formula (I-2). Examples of the adduct form of diisocyanate include the compound represented by the following general formula (I-3).

[0104] [ka] [In the formula, Rm 1 ~Rm 7 This is Rm in the above equations (m-1) to (m-3). 1 ~Rm 7 These are the same as above.

[0105] Examples of diisocyanates for forming the compounds of formulas (I-1) to (I-3) include, but are not limited to, 1,3-phenylenediisocyanate, 1,4-phenylenediisocyanate, tolylenediisocyanate, butane-1,4-diisocyanate, hexamethylenediisocyanate, isopropyldiisocyanate, methylenediisocyanate, 2,2,4-trimethylhexamethylenediisocyanate, 2,4,4-trimethylhexamethylenediisocyanate, cyclohexane-1,4-diisocyanate, xylylenediisocyanate, isophoronediisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, methylcyclohexanediisocyanate, m-tetramethylxylylenediisocyanate, etc. Among these, tolylene diisocyanate, hexamethylene diisocyanate, 1,3-bis(isocyanate-methyl)cyclohexane, and isophorone diisocyanate are preferred as diisocyanates.

[0106] Caprolactone-modified (meth)acrylates are compounds obtained by addition polymerization of ε-caprolactone to (meth)acrylate or hydroxyl group-containing (meth)acrylate. Hydroxyl group-containing (meth)acrylates are compounds having both a (meth)acryloyl group and a hydroxyl group. The (meth)acryloyl group is a concept that encompasses both methacryloyl and acryloyl groups, and means either a methacryloyl group or an acryloyl group. Examples of hydroxyl group-containing (meth)acrylates include hydroxyalkyl (meth)acrylates. Specific examples of hydroxyalkyl (meth)acrylates include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate.

[0107] Examples of commercially available caprolactone-modified (meth)acrylates include Praxel FA1, Praxel FA2D, and Praxel FA5 (all trade names, manufactured by Daicel Chemical Industries, Ltd.).

[0108] The (M1) component may be used alone or in combination of two or more types. The ratio of component (M1) to component (M) is preferably 40 to 100% by mass, more preferably 50 to 95% by mass, even more preferably 70 to 90% by mass, and particularly preferably 75 to 85% by mass, relative to the total amount (100% by mass) of component (M). Alternatively, the ratio of component (M1) to component (M) is preferably 40 to 100 mol%, more preferably 50 to 95 mol%, even more preferably 70 to 90 mol%, and particularly preferably 75 to 85 mol%, relative to the total amount (100 mol%) of component (M). By setting the ratio of component (M1) to component (M) within the above preferred range, it is possible to suppress the occurrence of delamination in high-temperature processes while maintaining cleanability.

[0109] <<Other crosslinking agent components: (M2) component>> Component (M) may include, in addition to component (M1) above, other crosslinking agent components (hereinafter also referred to as "component (M2)"). Examples of component (M2) include compounds having two or more (meth)acryloyl groups (excluding component (M1)). Examples of component (M2) include polyfunctional urethane (meth)acrylate, polyfunctional (meth)acrylate, polyfunctional caprolactone-modified (meth)acrylate, etc. If the adhesive composition of this embodiment contains component (M2), then component (P1) above is excluded if it corresponds to component (M2).

[0110] Polyfunctional urethane (meth)acrylate is a compound containing a urethane bond (-NCO-) and two or more (meth)acryloyl groups. Examples of polyfunctional urethane (meth)acrylate include compounds obtained by reacting the polyisocyanate compound with (meth)acrylate or a hydroxyl group-containing (meth)acrylate. Specific examples of polyfunctional urethane (meth)acrylate include compounds represented by any of the following general formulas (m2-1) to (m2-3).

[0111] [ka] [In the formula, Ry 1 ~Ry 3 These are, independently, -O-(CH2) k -OCOCH=CH2 represents a base (where k is an integer from 1 to 10). Rm 1 ~Rm 7 This is Rm in the above equations (m-1) to (m-3). 1 ~Rm 7 These are the same as above.

[0112] Preferred examples of polyfunctional urethane (meth)acrylates are shown below, but are not limited to these.

[0113] [ka] [In the formula, Ry11 ~Ry 13 This represents the group represented by -O-(CH2)2-OCOCH=CH2.

[0114] (Meth)acrylate compounds are compounds containing a (meth)acryloyl group. Examples of (meth)acrylate compounds as component (M2) are the same as those for component (O1) above.

[0115] Examples of polyfunctional (meth)acrylates include difunctional (meth)acrylates such as 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, and ethoxylated bisphenol A diacrylate; and trifunctional (meth)acrylates such as trimethylolpropane triacrylate, ethoxylated trimethylolpropane tri(meth)acrylate, ethoxylated glycerin tri(meth)acrylate, and pentaerythritol tri(meth)acrylate.

[0116] Examples of polyfunctional caprolactone-modified (meth)acrylates include caprolactone-modified tris-(2-(meth)acryloxyethyl)isocyanurate and other caprolactone-modified ((meth)acrylate alkyl) isocyanurates.

[0117] The (M2) component may be used alone or in combination of two or more types. The ratio of component (M2) to component (M) is preferably 0 to 60% by mass, more preferably 5 to 50% by mass, even more preferably 10 to 40% by mass, and particularly preferably 10 to 30% by mass, relative to the total amount of component (M) (100% by mass). Alternatively, the ratio of component (M2) to component (M) is preferably 0 to 60 mol%, more preferably 5 to 50 mol%, even more preferably 10 to 40 mol%, and particularly preferably 10 to 30 mol%, relative to the total amount of component (M) (100 mol%). When component (M) contains component (M2), the molar ratio of component (M1):component (M2) can be, for example, 99:1 to 20:80. The molar ratio of component (M1) to component (M2) is preferably 95:5 to 30:70, more preferably 90:10 to 40:60, even more preferably 90:10 to 50:50, and particularly preferably 90:10 to 60:40.

[0118] The proportion of component (M) in the adhesive composition of this embodiment is preferably 10 to 60% by mass, more preferably 10 to 50% by mass, even more preferably 20 to 40% by mass, and particularly preferably 25 to 35% by mass, based on the total mass (100% by mass) of the adhesive composition. The mass ratio of component (P1) to component (M) (component (P1):component (M)) is preferably 95:5 to 50:50, more preferably 90:10 to 60:40, and even more preferably 80:20 to 60:40.

[0119] <Polymerization initiator: (A) component> The adhesive composition of this embodiment contains a polymerization initiator (hereinafter also referred to as component (A)) in addition to the above-mentioned components (P1) and (M). A polymerization initiator is a component that has the function of promoting a polymerization reaction. Examples of component (A) include thermal polymerization initiators and photopolymerization initiators.

[0120] Examples of thermal polymerization initiators include peroxides and azo polymerization initiators.

[0121] Examples of peroxides used as thermal polymerization initiators include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, and peroxyesters. Examples of such peroxides include acetyl peroxide, dicumyl peroxide, tert-butyl peroxide, t-butylcumyl peroxide, propionyl peroxide, benzoyl peroxide (BPO), 2-chlorobenzoyl peroxide, 3-chlorobenzoyl peroxide, 4-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 4-bromomethylbenzoyl peroxide, lauroyl peroxide, potassium persulfate, diisopropyl peroxycarbonate, tetraline hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, pertriphenylacetate-tert-butyl, tert-butyl hydroperoxide, tert-butyl performate, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, 4-methoxyacetate-tert-butyl, and perN-(3-toluyl)carbamate-tert-butyl.

[0122] For example, commercially available peroxides such as "Parkmyl®", "Perbutyl®", "Perroyl®", and "Perocta®" manufactured by Nippon Oil & Fats Co., Ltd. can be used as the aforementioned peroxide.

[0123] Examples of azo polymerization initiators used in thermal polymerization initiators include 2,2'-azobispropane, 2,2'-dichloro-2,2'-azobispropane, 1,1'-azo(methylethyl)diacetate, 2,2'-azobis(2-amidinopropane) hydrochloride, 2,2'-azobis(2-aminopropane) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutylamide, 2,2'-azobisisobutyronitrile, and 2,2'-azobis-2-methylpropionic acid. Chil, 2,2'-Dichloro-2,2'-Azobisbutane, 2,2'-Azobis-2-methylbutyronitrile, 2,2'-Azobisisobutyrate dimethyl, 1,1'-Azobis(1-methylbutyronitrile-3-sodium sulfonate), 2-(4-methylphenylazo)-2-methylmalonodinitrile, 4,4'-Azobis-4-cyanovaleric acid, 3,5-Dihydroxymethylphenylazo-2-allylmanodinitrile, 2,2'-Azobis-2-methylvaleronitrile, 4 ,4'-Azobis-4-Cyanovalerate Dimethyl, 2,2'-Azobis-2,4-Dimethylvaleronitrile, 1,1'-Azobiscyclohexanenitrile, 2,2'-Azobis-2-Propylbutyronitrile, 1,1'-Azobiscyclohexanenitrile, 2,2'-Azobis-2-Propylbutyronitrile, 1,1'-Azobis-1-Chlorophenylethane, 1,1'-Azobis-1-Cyclohexanecarbonitride, 1,1'-Azobis-1-Cycloheptanenitrile Examples include 1,1'-azobis-1-phenylethane, 1,1'-azobiscumene, 4-nitrophenylazobenzylic acid ethyl acetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrophenylazotriphenylmethane, 1,1'-azobis-1,2-diphenylethane, poly(bisphenol A-4,4'-azobis-4-cyanopentanoate), poly(tetraethylene glycol-2,2'-azobiisobutyrate), etc.

[0124] Examples of photopolymerization initiators include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, and bis(4-dimethylaminophenyl) ketone. Ton, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, ethanolone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(o-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, 4-dimethylamino Ethyl benzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexyl benzoate, 4-dimethylamino-2-isoamyl benzoate, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, o-methyl benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxane Nten, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidal, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (i.e., Michla's ketone), 4,4'-bisdiethylaminobenzophenone (i.e., ethyl Michla's ketone), 4,4' -Dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin-t-butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, pt-butylacetophenone, p-dimethylaminoacetophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosverone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytriazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2- Tyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,Examples include 6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, and 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine.

[0125] The aforementioned photopolymerization initiators can be 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 Corporation).

[0126] Component (A) may be used alone or in combination of two or more types. A thermal polymerization initiator is preferred for component (A), and a peroxide is more preferred. The amount of component (A) used can be adjusted according to the amount of component (P1) used. The content of the polymerization initiator in the adhesive composition of this embodiment is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of component (P1).

[0127] <Optional ingredients> The adhesive composition of this embodiment may contain, in addition to the above-mentioned components (P1), (M), and (A), any other components, as long as they do not impair the effects of the present invention. The optional components are not particularly limited, but examples include polymerization inhibitors, solvent components, plasticizers, adhesion aids, stabilizers, colorants, surfactants, and the like.

[0128] Polymerization inhibitors Polymerization inhibitors are components that have the function of preventing radical polymerization reactions caused by heat or light. Polymerization inhibitors exhibit high reactivity to radicals.

[0129] As polymerization inhibitors, those having a phenol skeleton are preferred. For example, hindered phenol-based antioxidants can be used as such polymerization inhibitors, including pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, amyloxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4,4'-(1-methylethylidene)bis(2-methylphenol), 4,4'-(1-methylethylidene)bis(2,6- Dimethylphenol), 4,4'-[1-[4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl]ethylidene]bisphenol, 4,4',4”-ethylidenttris(2-methylphenol), 4,4',4”-ethylidenttrisphenol, 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-butylpheno) 4,4'-Butylidenebis(3-methyl-6-tert-butylphenol), 4,4'-Thiobis(3-methyl-6-tert-butylphenol), 3,9-Bis[2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)-propionyloxy)-1,1-dimethylethyl]-2,4,8,10-Tetraoxaspiro(5,5)undecane, Triethylene glycol-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy Examples include onates, n-octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythryltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name IRGANOX1010, manufactured by BASF), tris(3,5-di-tert-butylhydroxybenzyl)isocyanurate, and thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0130] Polymerization inhibitors may be used individually or in combination of two or more types. The amount of polymerization inhibitor should be determined appropriately depending on the type of resin component, the intended use of the adhesive composition, and the usage environment.

[0131] <<Surfactants>> Examples of surfactants include fluorine-based surfactants and silicone-based surfactants.

[0132] Examples of commercially available fluorine-based surfactants include BM-1000, BM-1100 (both manufactured by BM Chemie), Megafac F142D, Megafac F172, Megafac F173, Megafac F183 (all manufactured by DIC), Florard FC-135, Florard FC-170C, Florard FC-430, Florard FC-431 (all manufactured by Sumitomo 3M), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145 (all manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, and SF-8428 (all manufactured by Toray Silicone Co., Ltd.).

[0133] Examples of silicone-based surfactants include unmodified silicone-based surfactants, polyether-modified silicone-based surfactants, polyester-modified silicone-based surfactants, alkyl-modified silicone-based surfactants, aralkyl-modified silicone-based surfactants, and reactive silicone-based surfactants. Commercially available silicone-based surfactants can be used. Specific examples of commercially available silicone-based surfactants include Paintad M (manufactured by Toray Dow Corning), Topica K1000, Topica K2000, Topica K5000 (all manufactured by Takachiho Sangyo Co., Ltd.), XL-121 (polyether-modified silicone-based surfactant, manufactured by Clariant), and BYK-310 (polyester-modified silicone-based surfactant, manufactured by Bic Chemie).

[0134] The surfactant may be used alone or in combination of two or more types. Silicone-based surfactants are preferred, and polyester-modified silicone-based surfactants are more preferred. When a surfactant is used, the surfactant content in the adhesive composition of this embodiment is preferably 0.01 to 1 part by mass, and more preferably 0.05 to 0.5 parts by mass, per 100 parts by mass of component (P1).

[0135] <<Solvent components>> The adhesive composition of this embodiment can be prepared by dissolving and mixing components (P1), (M), and (A), along with optional components as needed, in a solvent component. Any solvent capable of dissolving the above components can be used.

[0136] Examples of solvent components include hydrocarbon solvents, petroleum-based solvents, and other solvents other than those mentioned above. Hereinafter, hydrocarbon solvents and petroleum-based solvents will be collectively referred to as "component (S1)". Solvent components other than component (S1) will be referred to as "component (S2)".

[0137] Examples of hydrocarbon solvents include linear, branched, or cyclic hydrocarbons. Examples of hydrocarbon solvents include linear hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, and tridecane; branched hydrocarbons such as isooctane, isononane, and isododecane; p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpine, 1,8-terpine, bornane, norbornane, pinan, thujon, karan, longifolene, α-terpinene, β-terpinene, γ-terpinene, α-pinene, β-pinene, α-thujone, β-thujone, cyclohexane, cycloheptane, and cyclooctane; and aromatic hydrocarbons such as toluene, xylene, indene, pentalene, indan, tetrahydroindene, naphthalene, tetrahydronaphthalene (tetralin), and decahydronaphthalene (decalin).

[0138] Petroleum-based solvents are solvents refined from heavy oil, and examples include white kerosene, paraffinic solvents, and isoparaffinic solvents.

[0139] (S2) Component includes terpene solvents having polar groups such as an oxygen atom, a carbonyl group, or an acetoxy group. Examples include geraniol, nerol, linalool, citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, terpinen-4-ol, dihydroterpinyl acetate, 1,4-cineole, 1,8-cineole, borneol, carvone, ionone, thujone, and camphor.

[0140] Furthermore, the (S2) component may include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds having ester bonds such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; monomethyl ethers, monoethyl ethers, monopropyl ethers, and monobutyl ethers of the above polyhydric alcohols or compounds having ester bonds. Examples include derivatives of polyhydric alcohols such as monoalkyl ethers or compounds having ether bonds such as monophenyl ethers (among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred); cyclic ethers such as dioxane; esters such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; and aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetol, and butylphenyl ether.

[0141] The solvent component may be used alone or in combination of two or more. Preferably, the solvent component is inert to component (P1). Preferred solvent components include, for example, ester solvents, ketone solvents, aromatic hydrocarbon solvents, PGMEA, PGME, and mixtures thereof.

[0142] The solvent content in the adhesive composition of this embodiment can be appropriately adjusted according to the thickness of the adhesive composition layer. Preferably, the solvent content is in the range of 40 to 90% by mass relative to the total amount (100% by mass) of the adhesive composition. That is, the solid content (total amount of blended components excluding the solvent) of the adhesive composition of this embodiment is preferably in the range of 10 to 80% by mass. When the solvent content is within the above preferred range, viscosity adjustment becomes easier.

[0143] The polymerization initiator can be added to the adhesive composition by known methods immediately before use. The polymerization initiator or polymerization inhibitor may be added in the form of a solution pre-dissolved in the above-mentioned component (S2). The amount of component (S2) used can be adjusted as appropriate depending on the type of polymerization initiator or polymerization inhibitor, for example, 1 to 50 parts by mass, and more preferably 5 to 30 parts by mass, per 100 parts by mass of component (S1). If the amount of component (S2) used is within the above preferred range, the polymerization initiator or polymerization inhibitor can be sufficiently dissolved.

[0144] According to the adhesive composition of this embodiment, a polymerizable carbon-carbon double bond-containing urethane resin (P1), and caprolactone-modified urethane are used. (meta)Because it contains acrylate (M1) and polymerization initiator (A), when the polymerization reaction is initiated by heating, components (P1) and (M1) polymerize to form a crosslinked structure and harden. The adhesive layer formed by the hardening of such an adhesive composition has high heat resistance and its elastic modulus does not decrease even at high temperatures (e.g., 200°C or higher) because it is hardened by a crosslinked structure. Furthermore, the adhesive layer is given flexibility by the ring-opened caprolactone structure in component (M1) and has high adhesion to the substrate. Therefore, after temporary bonding of a semiconductor substrate or the like to a support, the electronic device formation process can be carried out smoothly.

[0145] On the other hand, the urethane bonds in component (P1) can be decomposed by acid or alkali. Therefore, the adhesive layer adhering to the electronic device can be easily cleaned and removed after the electronic device formation process is completed. Furthermore, the inclusion of component (M1) in the adhesive composition also improves its cleanability.

[0146] (Laminated structure) A laminate according to a second aspect of the present invention is a laminate in which a support, an adhesive layer, and a semiconductor substrate or electronic device are laminated in this order, wherein the adhesive layer is a cured product of the adhesive composition according to the first aspect.

[0147] Figure 1 shows one embodiment of the laminate according to the second aspect. The laminate 100 shown in Figure 1 comprises a support 12 formed by laminating a support base 1 and a separation layer 2, an adhesive layer 3, and a semiconductor substrate 4. In the laminate 100, the support 12, the adhesive layer 3, and the semiconductor substrate 4 are laminated in this order. In the example shown in Figure 1, the support 12 consists of a support substrate 1 and a separation layer 2, but it is not limited to this, and the support may be constructed from the support substrate alone.

[0148] Figure 2 shows another embodiment of the laminate according to the second embodiment. The laminate 200 shown in Figure 2 has the same configuration as the laminate 100, except that an electronic device 456 consisting of a semiconductor substrate 4, a sealing layer 5, and a wiring layer 6 is laminated on an adhesive layer 3.

[0149] Figure 3 shows yet another embodiment of the laminate according to the second embodiment. The laminate 300 shown in Figure 3 has the same configuration as the laminate 100, except that the electronic devices consist of a wiring layer 6.

[0150] Figure 4 shows yet another embodiment of the laminate according to the second embodiment. The laminate 400 shown in Figure 4 has the same configuration as the laminate 100, except that an electronic device 645 consisting of a wiring layer 6, a semiconductor substrate 4, and a sealing material layer 5 is laminated on an adhesive layer 3.

[0151] <Support> A support is a component that supports a semiconductor substrate or an electronic device. In the examples shown in Figures 1 to 4, the support 12 comprises a support base 1 and an isolation layer 2 provided on the support base 1. In the laminate of this embodiment, the support may or may not have the isolation layer 2. If the support does not have the isolation layer 2, the support base 1 becomes the support.

[0152] ≪Supporting base≫ The support substrate is a member that transmits light and supports a semiconductor substrate or electronic component. When a separation layer is provided as shown in Figures 1 to 4, the support substrate is bonded to the semiconductor substrate or electronic device via the separation layer and the adhesive layer. When no separation layer is provided, the support substrate is bonded to the semiconductor substrate or electronic device via the adhesive layer. Therefore, it is preferable that the support substrate has sufficient strength to prevent damage or deformation of the semiconductor substrate during device thinning, semiconductor substrate transport, and mounting onto the semiconductor substrate. Furthermore, when the support has a separation layer, it is preferable that the support substrate transmits light of a wavelength that can alter the separation layer. Materials used for the support base include, for example, glass, silicon, and acrylic resin. The shape of the support base can be, for example, rectangular or circular, but is not limited to these. For further high-density integration and improved production efficiency, larger versions of the circular support base or large panels with a rectangular shape in plan view can also be used.

[0153] ≪Separation layer≫ The separation layer is adjacent to the adhesive layer and is altered by light irradiation, allowing the support substrate to be separated from the semiconductor substrate or electronic device fixed to the support via the adhesive layer. This separation layer can be formed using a separation layer-forming composition described later, for example, by calcining the components contained in the separation layer-forming composition, or by chemical vapor deposition (CVD). This separation layer is suitably altered by absorbing light irradiated through the supporting substrate. The separation layer is preferably formed solely from light-absorbing materials, but it may also be a layer containing materials that do not have a light-absorbing structure, as long as the essential properties of the present invention are not impaired.

[0154] The thickness of the separation layer is preferably in the range of 0.05 μm or more and 50 μm or less, and more preferably in the range of 0.3 μm or more and 1 μm or less. If the thickness of the separation layer is in the range of 0.05 μm or more and 50 μm or less, the desired alteration of the separation layer can be induced by short-term light irradiation and low-energy light irradiation. Furthermore, from the viewpoint of productivity, the thickness of the separation layer is particularly preferably in the range of 1 μm or less.

[0155] Preferably, the separation layer has a flat surface (no irregularities) on the side that contacts the adhesive layer. This facilitates the formation of the adhesive layer and makes it easy to uniformly bond the semiconductor substrate or electronic device to the support base.

[0156] ·Composition for forming separation layer Examples of materials for forming a separation layer include compositions containing fluorocarbons, polymers having repeating units with a light-absorbing structure, inorganic substances, compounds having an infrared-absorbing structure, infrared-absorbing materials, reactive polysilsesquioxanes, or resin components having a phenol skeleton. Furthermore, the separation layer formation composition may contain, as an optional component, a filler, a plasticizer, a thermoacid generator component, a photoacid generator component, an organic solvent component, a surfactant, a sensitizer, or a component that can improve the separation properties of the supporting substrate.

[0157] Fluorocarbon The separation layer may contain fluorocarbons. A separation layer composed of fluorocarbons is designed to change upon absorbing light, resulting in a loss of strength or adhesion compared to its pre-light-irradiated state. Therefore, by applying a slight external force (e.g., lifting the support), the separation layer can be broken, making it easier to separate the support from the semiconductor substrate or electronic device. The fluorocarbons constituting the separation layer can be suitably deposited by plasma CVD. Fluorocarbons absorb light with wavelengths specific to their type. By irradiating the separation layer with light of a wavelength within the range absorbed by the fluorocarbon used in the separation layer, the fluorocarbon can be suitably altered. The light absorption rate in the separation layer is preferably 80% or higher.

[0158] The light irradiated onto the separation layer can be any laser light or non-laser light appropriate to the wavelength absorbed by the fluorocarbon, such as solid-state lasers like YAG lasers, ruby ​​lasers, glass lasers, YVO4 lasers, LD lasers, and fiber lasers; liquid lasers like dye lasers; gas lasers like CO2 lasers, excimer lasers, Ar lasers, and He-Ne lasers; semiconductor lasers; free electron lasers; or other non-laser light. Wavelengths that can alter the fluorocarbon can be, for example, those in the range of 600 nm or less.

[0159] • Polymers having repeating units that include a light-absorbing structure The separation layer may contain a polymer having repeating units that include a light-absorbing structure. The polymer is altered upon irradiation with light. Examples of structures that exhibit light absorption include atomic groups containing a conjugated π-electron system consisting of substituted or unsubstituted benzene rings, fused rings, or heterocycles. More specifically, examples of structures that exhibit light absorption include cardi structures, or benzophenone structures, diphenyl sulfoxide structures, diphenyl sulfone structures (bisphenyl sulfone structures), diphenyl structures, or diphenylamine structures present in the side chains of the polymer. The above-described light-absorbing structure can absorb light having a desired range of wavelengths, depending on its type. For example, the wavelength of light that the above-described light-absorbing structure can absorb is preferably in the range of 100 to 2000 nm, and more preferably in the range of 100 to 500 nm.

[0160] Light that can be absorbed by the above-mentioned light-absorbing structure is, for example, light emitted from high-pressure mercury lamps (wavelength 254 nm or higher, 436 nm or lower), KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), F2 excimer lasers (wavelength 157 nm), XeCl lasers (wavelength 308 nm), XeF lasers (wavelength 351 nm), or solid-state UV lasers (wavelength 355 nm), or g-line (wavelength 436 nm), h-line (wavelength 405 nm), or i-line (wavelength 365 nm), etc.

[0161] ··Inorganic matter The separation layer may be made of inorganic material. This inorganic material only needs to be altered by absorbing light, and preferably one or more selected from the group consisting of metals, metal compounds, and carbon. Metal compounds are compounds containing metal atoms, and examples include metal oxides and metal nitrides. Examples of such inorganic materials include one or more selected from the group consisting of gold, silver, copper, iron, nickel, aluminum, titanium, chromium, SiO2, SiN, Si3N4, TiN, and carbon. Furthermore, the term "carbon" is a concept that can include allotropes of carbon, encompassing, for example, diamond, fullerene, diamond-like carbon, and carbon nanotubes. The inorganic substances mentioned above absorb light with wavelengths specific to their type.

[0162] The light irradiated onto the separation layer made of inorganic material can be any laser light or non-laser light appropriate to the wavelength that the inorganic material can absorb, such as solid-state lasers like YAG lasers, ruby ​​lasers, glass lasers, YVO4 lasers, LD lasers, and fiber lasers; liquid lasers like dye lasers; gaseous lasers like CO2 lasers, excimer lasers, Ar lasers, and He-Ne lasers; semiconductor lasers; free electron lasers; or other laser light. A separation layer made of inorganic material can be formed on a support substrate by known techniques such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, and spin coating.

[0163] Compounds having an infrared-absorbing structure The separation layer may contain a compound having an infrared-absorbing structure. This infrared-absorbing compound undergoes a transformation by absorbing infrared radiation. Structures that absorb infrared radiation, or compounds having such structures, include, for example, alkanes, alkenes (vinyl, trans, cis, vinylidene, trisubstituted, tetrasubstituted, conjugated, cumulene, cyclic), alkynes (monosubstituted, disubstituted), monocyclic aromatics (benzene, monosubstituted, disubstituted, trisubstituted), alcohols or phenols (free OH, intramolecular hydrogen bonding, intermolecular hydrogen bonding, saturated secondary, saturated tertiary, unsaturated secondary, unsaturated tertiary), acetals, ketals, aliphatic ethers, aromatic ethers, vinyl ethers, oxirane ring ethers, peroxide ethers, ketones, dialkylcarbonyls, aromatic carbonyls, 1,3-diketone enols, o-hydroxyaryl ketones, dialkylaldehydes, aromatic aldehydes, carboxylic acids (dimers, carboxylic acid anions), formic acid esters, acetate esters, conjugated esters, unconjugated esters, aromatic esters, lactones (β-, γ-, δ-), aliphatic acid chlorides, aromatic acid salts Compounds, acid anhydrides (conjugated, unconjugated, cyclic, acyclic), primary amides, secondary amides, lactams, primary amines (aliphatic, aromatic), secondary amines (aliphatic, aromatic), tertiary amines (aliphatic, aromatic), primary amine salts, secondary amine salts, tertiary amine salts, ammonium ions, aliphatic nitriles, aromatic nitriles, carbodiimides, aliphatic isonitriles, aromatic isonitriles, isocyanate esters, thiocyanate esters, aliphatic isothiocyanate esters, aromatic isothiocyanate esters, aliphatic nitro compounds, aromatic nitro compounds, nitroamines, nitrosamines, nitrate esters, nitrite esters, nitroso bonds (aliphatic, aromatic, monomers, dimers), sulfur compounds such as mercaptans, thiophenols, or thiolic acids, thiocarbonyl groups, sulfoxides, sulfones, sulfonyl chlorides, primary sulfonamides, secondary sulfonamides, sulfuric acid esters, carbon-halogen bonds, Si-A 1 Join(A 1 (H, C, O or halogen), PA 2 Join(A 2 Examples include H, C, or O, or Ti-O bonds.

[0164] Examples of structures containing the carbon-halogen bond mentioned above include -CH2Cl, -CH2Br, -CH2I, -CF2-, -CF3, -CH=CF2, -CF=CF2, aryl fluoride, or aryl chloride.

[0165] The above Si-A 1 Examples of structures containing bonds include SiH, SiH2, SiH3, Si-CH3, Si-CH2-, Si-C6H5, SiO-aliphatic, Si-OCH3, Si-OCH2CH3, Si-OC6H5, Si-O-Si, Si-OH, SiF, SiF2, or SiF3. 1 The structure containing the bond is preferably one that forms a siloxane skeleton or a silsesquioxane skeleton.

[0166] The above PA 2 Examples of structures containing bonds include PH, PH2, P-CH3, P-CH2-, P-C6H5, and A 3 3-PO(A 3 (A is an aliphatic group or an aromatic group), (A 4 O)3-PO(A 4 Examples include alkyl groups, P-OCH3, P-OCH2CH3, P-OC6H5, POP, P-OH, or O=P-OH.

[0167] Examples of compounds containing the above Ti-O bond include (i) alkoxy titanium such as tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis(2-ethylhexyloxy)titanium, or titanium-i-propoxyoctylene glycolate; (ii) chelated titanium such as di-i-propoxybis(acetylacetonate)titanium or propanedioxytitanium bis(ethylacetoacetate); and (iii) i-C3H7O-[-Ti(Oi-C3H7)2-O-] n -i-C3H7 or n-C4H9O-[-Ti(On-C4H9)2-O-] nExamples include titanium polymers such as n-C4H9; (iv) titanium acylates such as tri-n-butoxytitanium monostearate, titanium stearate, di-i-propoxytitanium diisostearate, or (2-n-butoxycarbonylbenzoyloxy)tributoxytitanium; and (v) water-soluble titanium compounds such as di-n-butoxybis(triethanolamineto)titanium. Among these, di-n-butoxybis(triethanolamine)titanium (Ti(OC4H9)2[OC2H4N(C2H4OH)2]2) is preferred as a compound containing a Ti-O bond.

[0168] The infrared-absorbing structure described above can absorb infrared radiation within a desired wavelength range, depending on the type selected. Specifically, the infrared-absorbing structure can absorb infrared radiation within a range of, for example, 1 to 20 μm, and more preferably within the range of 2 to 15 μm. Furthermore, if the above structure is a Si-O bond, Si-C bond, or Ti-O bond, a range of 9 to 11 μm is preferred.

[0169] Furthermore, the wavelengths of infrared radiation that each of the above structures can absorb can be easily understood by those skilled in the art. For example, for the absorption bands in each structure, refer to the descriptions on pages 146 to 151 of the non-patent document: "Spectral Identification Methods for Organic Compounds (5th Edition) - Combination of MS, IR, NMR, and UV" by Silverstein, Bassler, and Morrill (published in 1992).

[0170] The infrared-absorbing compound used to form the separation layer is not particularly limited, as long as it has the structure described above, can be dissolved in a solvent for coating, and can solidify to form a solid layer. However, in order to effectively alter the compound in the separation layer and facilitate the separation of the support substrate and the substrate, it is preferable that the infrared absorption in the separation layer is large, that is, that the infrared transmittance when infrared light is irradiated onto the separation layer is low. Specifically, it is preferable that the infrared transmittance in the separation layer is less than 90%, and more preferably less than 80%.

[0171] Infrared absorbing material The separation layer may contain an infrared absorbing material. This infrared absorbing material can be any material that changes upon absorbing light; for example, carbon black, iron particles, or aluminum particles can be suitably used. Infrared absorbing materials absorb light with wavelengths specific to their type. By irradiating the separation layer with light of wavelengths within the range absorbed by the infrared absorbing material used in the separation layer, the infrared absorbing material can be suitably altered.

[0172] Reactive polysilsesquioxane The separation layer can be formed by polymerizing reactive polysilsesquioxane. The resulting separation layer possesses high chemical resistance and high heat resistance.

[0173] "Reactive polysilsesquioxane" refers to polysilsesquioxane having a silanol group at the end of its polysilsesquioxane skeleton, or a functional group capable of forming a silanol group by hydrolysis. These silanol groups, or functional groups capable of forming silanol groups, can be polymerized with each other by condensation. Furthermore, reactive polysilsesquioxane can be any polysilsesquioxane skeleton having a random structure, cage structure, ladder structure, etc., as long as it has a silanol group, or a functional group capable of forming a silanol group.

[0174] The siloxane content of the reactive polysilsesquioxane is preferably 70 to 99 mol%, and more preferably 80 to 99 mol%. If the siloxane content of the reactive polysilsesquioxane is within the preferred range described above, a separation layer can be formed that can be suitably altered by irradiation with infrared light (preferably far-infrared light, more preferably light with a wavelength of 9 to 11 μm).

[0175] The weight-average molecular weight (Mw) of the reactive polysilsesquioxane is preferably 500 to 50,000, and more preferably 1,000 to 10,000. If the weight-average molecular weight (Mw) of the reactive polysilsesquioxane is within the aforementioned preferred range, it can be suitably dissolved in a solvent and suitably coated onto a support plate.

[0176] Examples of commercially available products that can be used as reactive polysilsesquioxanes include SR-13, SR-21, SR-23, or SR-33 (trade names) manufactured by Konishi Chemical Industry Co., Ltd.

[0177] • Resin components having a phenolic skeleton The separation layer may contain a resin component having a phenol skeleton. Having a phenol skeleton allows it to easily undergo alteration (oxidation, etc.) upon heating, thereby increasing its photoreactivity. As used herein, "having a phenol skeleton" means containing a hydroxybenzene structure. The resin component having a phenol skeleton has film-forming ability and preferably has a molecular weight of 1000 or more. When the molecular weight of the resin component is 1000 or more, the film-forming ability is improved. The molecular weight of the resin component is more preferably 1000 to 30000, even more preferably 1500 to 20000, and particularly preferably 2000 to 15000. When the molecular weight of the resin component is below the upper limit value of the above preferred range, the solubility of the composition for forming the separation layer in the solvent is increased. Note that, as the molecular weight of the resin component, the weight average molecular weight (Mw) in terms of polystyrene by GPC (gel permeation chromatography) shall be used.

[0178] Examples of the resin component having a phenol skeleton include novolak type phenol resin, resol type phenol resin, hydroxystyrene resin, hydroxyphenylsilsesquioxane resin, hydroxybenzylsilsesquioxane resin, phenol skeleton-containing acrylic resin, etc. Among these, novolak type phenol resin and resol type phenol resin are more preferred.

[0179] <Adhesive layer> The adhesive layer is provided to temporarily adhere a semiconductor substrate or an electronic device to a support. The adhesive layer is a cured product of the adhesive composition according to the first embodiment. More specifically, the adhesive layer is formed by the (P1) component and the (M1) component in the adhesive composition according to the first embodiment polymerizing and crosslinking through polymerizable carbon-carbon double bonds. The polymerization reaction of the (P1) component and the (M1) component can be carried out by heating the adhesive composition. The thickness of the adhesive layer is preferably within a range of, for example, 1 μm or more and 200 μm or less, and more preferably within a range of 5 μm or more and 150 μm or less.

[0180] As described above, the adhesive layer is a cured product of the adhesive composition, and it is preferable that the material (cured product) constituting this adhesive layer satisfies the following characteristics. In other words, when the complex modulus of the hardened material was measured under the following conditions, the complex modulus of the material at 200°C was 1.0 × 10⁻⁶. 6 It is preferable that it be Pa or higher, 5.0 × 10 6 It is more preferable that it be Pa or higher, 1.0 × 10 7 It is even more preferable that it be Pa or higher. An upper limit for the complex modulus at 200°C is, for example, 1.0 × 10⁻⁶. 10 It is below Pa. Furthermore, when the complex modulus of the hardened material was measured under the following conditions, the complex modulus of the material at 250°C was found to be 5.0 × 10⁻⁶. 6 Preferably Pa or higher, 1.0 × 10 7 It is more preferable that it be Pa or higher. An upper limit for the complex modulus at 250°C is, for example, 1.0 × 10⁻⁶. 10 It is below Pa.

[0181] The complex modulus of elasticity of the cured material can be measured using the Rheogel-E4000 dynamic viscoelasticity measuring device (manufactured by UBM Co., Ltd.). Specifically, the adhesive composition is applied to a PET film with a release agent, heated in an oven under a nitrogen atmosphere at 180°C for 1 hour to form a 50 μm thick test specimen, and then the test specimen (size 5 mm × 40 mm, thickness 50 μm) peeled off the PET film can be measured using the aforementioned measuring device. The measurement conditions should be tensile conditions at a frequency of 1 Hz, with the temperature raised from 50°C to 300°C at a heating rate of 5°C / min.

[0182] <Semiconductor substrates or electronic devices> The semiconductor substrate or electronic device is temporarily bonded to the support via an adhesive layer.

[0183] ≪Semiconductor Substrates≫ There are no particular restrictions on the semiconductor substrate, and examples similar to those exemplified in "(adhesive composition)" above are provided. The semiconductor substrate may be a semiconductor element or other element, and may have a single-layer or multi-layer structure.

[0184] Electronic Devices There are no particular limitations on the electronic device, and examples similar to those exemplified in "(adhesive composition)" above are provided. The electronic device is preferably a composite of a member made of metal or semiconductor and a resin that seals or insulates the member. Specifically, the electronic device includes at least one of a sealing material layer and a wiring layer, and may further include a semiconductor substrate. In the laminate 200 shown in Figure 2, the electronic device 456 is composed of a semiconductor substrate 4, a sealing layer 5, and a wiring layer 6. In the laminate 300 shown in Figure 3, the electronic device 6 is composed of a wiring layer 6. In the laminate 400 shown in Figure 4, the electronic device 645 is composed of a wiring layer 6, a semiconductor substrate 4, and a sealing layer 5.

[0185] [Encapsulant layer] The encapsulating layer is provided to encapsulate the semiconductor substrate and is formed using an encapsulating material. The encapsulating material used is a material that can insulate or encapsulate components made of metal or semiconductor. As the encapsulant, for example, a resin composition can be used. Preferably, the encapsulant layer 5 is not provided for each individual semiconductor substrate 4, but rather is provided to cover the entire semiconductor substrate 4 on the adhesive layer 3. The resin used as the encapsulant is not particularly limited as long as it is capable of encapsulating and / or insulating metals or semiconductors, but examples include epoxy resins and silicone resins. The sealing material may contain other components besides resin, such as fillers. Examples of fillers include spherical silica particles.

[0186] ≪Wiring layer≫ The wiring layer, also known as the RDL (Redistribution Layer), is a thin-film wiring structure that constitutes the wiring connected to the substrate, and can have a single-layer or multi-layer structure. The wiring layer is made of dielectric material (silicon oxide (SiO2)). xWiring may be formed between a photosensitive resin such as photosensitive epoxy, etc., using a conductor (for example, metals such as aluminum, copper, titanium, nickel, gold, and silver, and alloys such as silver-tin alloys).

[0187] In the laminates shown in Figures 1 to 4, the support substrate 1 and the separation layer 2 are adjacent, but the design is not limited to this, and other layers may be formed between the support substrate 1 and the separation layer 2. In this case, the other layers only need to be made of a light-transmitting material. This allows for the addition of layers that impart desirable properties to the laminates 100 to 400 without hindering the incidence of light into the separation layer 2. The wavelengths of light that can be used differ depending on the type of material constituting the separation layer 2. Therefore, the materials constituting the other layers do not need to transmit all wavelengths of light, and can be appropriately selected from materials that transmit wavelengths of light that can alter the material constituting the separation layer 2.

[0188] (Method for manufacturing a laminate (1)) A method for manufacturing a laminate according to a third aspect of the present invention is a method for manufacturing a laminate in which a support, an adhesive layer, and a semiconductor substrate are laminated in this order, and is characterized by comprising: a step of applying an adhesive composition according to the first aspect to the support or the semiconductor substrate to form an adhesive composition layer (hereinafter also referred to as the "adhesive composition layer formation step"); a step of placing the semiconductor substrate on the support via the adhesive composition layer (hereinafter also referred to as the "semiconductor substrate placement step"); and a step of curing the adhesive composition layer by a polymerization reaction of the urethane resin to form the adhesive layer (hereinafter also referred to as the "adhesive layer formation step").

[0189] Figures 5 and 6 are schematic process diagrams illustrating one embodiment of the manufacturing method for the laminate according to this embodiment. Figures 5(a) to 5(c) illustrate the manufacturing process of a laminate 100' in which a support 12, an adhesive composition layer 3', and a semiconductor substrate 4 are stacked in that order. Figure 5(a) shows the support 12. The support 12 is composed of a support base 1 and a separation layer 2. Figure 5(b) illustrates the adhesive composition layer formation process. Figure 5(c) illustrates the semiconductor substrate mounting process. Figure 6 illustrates the adhesive layer formation process. The adhesive composition layer 3' in the laminate 100' is heat-cured to form the adhesive layer 3, thereby obtaining the laminate 100.

[0190] [Adhesive composition layer formation process] The manufacturing method of the laminate according to this embodiment includes an adhesive composition layer formation step. The adhesive composition layer formation step is a step of applying an adhesive composition to a support or semiconductor substrate to form an adhesive composition layer. If the support has a separation layer, the adhesive composition layer is formed on the side of the support that has the separation layer. In Figure 5(b), an adhesive composition layer 3' is formed on the separation layer 2 side of the support 12 using the adhesive composition.

[0191] The method for forming the adhesive composition layer 3' on the support 12 is not particularly limited, but examples include spin coating, dipping, rollerblade coating, spray coating, and slit coating. The adhesive composition layer may be formed on the semiconductor substrate 4 in a similar manner.

[0192] After the adhesive composition layer is formed, a baking treatment may be performed. The baking temperature should be lower than the heating temperature in the adhesive layer formation process described later. The baking conditions may vary depending on the type of (P1) component contained in the adhesive composition, but examples include a temperature of 70 to 100°C for 1 to 10 minutes.

[0193] [Semiconductor substrate mounting process] The method for manufacturing a laminate according to this embodiment includes a semiconductor substrate placement step. The semiconductor substrate placement step is a step of placing a semiconductor substrate on a support via an adhesive composition layer. Thereby, the laminate 100' can be obtained. In FIG. 5(c), the semiconductor substrate 4 is placed on the support 12 via the adhesive composition layer 3' formed on the support 12.

[0194] The method of placing the semiconductor substrate 4 on the support 12 via the adhesive composition layer 3' is not particularly limited, and a method generally used as a method of placing the semiconductor substrate at a predetermined position can be adopted.

[0195] [Adhesive layer formation step] The method for manufacturing a laminate according to this embodiment includes an adhesive layer formation step. The adhesive layer formation step is a step of curing the adhesive composition layer to form an adhesive layer. Thereby, the laminate 100 can be obtained. In FIG. 6, the adhesive layer 3 is formed by curing the adhesive composition layer 3'.

[0196] The curing reaction of the adhesive composition layer can be advanced by selecting an appropriate method according to the type of polymerizable carbon-carbon double bond contained in the (P1) component. For example, when the (P1) component contains a methacryloyl group or an acryloyl group, the polymerization reaction of the (P1) component and the (M1) component can be advanced by heating.

[0197] Examples of the heating temperature include 80 to 350°C, 100 to 300°C, 130 to 300°C, or 150 to 300°C. The heating time is not particularly limited as long as it is sufficient for the (P1) component and the (M1) component to polymerize and cure. As the heating time, for example, 30 to 180 minutes is preferable, 45 to 120 minutes is more preferable, or 60 to 120 minutes is even more preferable. The curing reaction can be carried out, for example, in a nitrogen atmosphere.

[0198] In this process, components (P1) and (M1) in the adhesive composition layer 3' crosslink and harden, forming an adhesive layer 3, which is the hardened adhesive composition layer 3'. This temporarily bonds the support 12 and the semiconductor substrate 4. As a result, a laminate 100 can be obtained.

[0199] [Optional process] The method for manufacturing a laminate according to this embodiment may include other steps in addition to the steps described above. Examples of other steps include a separation layer formation step and various mechanical or chemical treatments (such as thin-film treatments like gliding or chemical mechanical polishing (CMP), high-temperature and vacuum treatments like chemical vapor deposition (CVD) or physical vapor deposition (PVD), treatments using chemicals such as organic solvents, acidic treatment solutions or basic treatment solutions, plating, irradiation with active light, heating and cooling treatments, etc.).

[0200] ·Separation layer formation process If the support includes a separation layer, the method for manufacturing the laminate according to this embodiment may include a separation layer formation step. The separation layer formation step is a step of forming a separation layer on one of the support substrates using a separation layer formation composition. In Figure 5(a), a separation layer 2 is formed on the support substrate 1 by using a separation layer-forming composition (containing fluorocarbons) (i.e., a support substrate with a separation layer is fabricated).

[0201] The method for forming the separation layer 2 on the support substrate 1 is not particularly limited, but examples include spin coating, dipping, rollerblade coating, spray coating, slit coating, and chemical vapor deposition (CVD). For example, in the separation layer formation process, the support 12 can be obtained by removing solvent components from the coating layer of the separation layer formation composition applied to the support substrate 1 under a heated or reduced pressure environment, or by forming a film on the support substrate 1 by vapor deposition.

[0202] (Method for manufacturing a laminate (2)) A method for manufacturing a laminate according to a fourth aspect of the present invention is characterized by further comprising an electronic device forming step, after obtaining a laminate by the method for manufacturing a laminate according to the third aspect, forming an electronic device which is a composite of a member made of a metal or semiconductor and a resin that seals or insulates the member.

[0203] The laminate obtained by the manufacturing method of the laminate according to this embodiment is a laminate in which a support, an adhesive layer, and an electronic device are laminated in that order. This laminate can be obtained by performing an electronic device formation step on the laminate obtained by the manufacturing method of the laminate according to the third embodiment.

[0204] [Electronic device formation process] The method for manufacturing a laminate according to this embodiment includes an electronic device formation step. The electronic device formation step is a step of forming an electronic device which is a composite of a member made of metal or semiconductor and a resin that seals or insulates the member. The electronic device formation process may include any of the following: a sealing process, a grinding process, or a wiring layer formation process. In one embodiment, the electronic device formation process includes a substrate fixing process and a sealing process. In this case, the electronic device formation process may further include a grinding process and a wiring layer formation process.

[0205] • Regarding the sealing process The sealing process is the process of sealing a substrate fixed on a support using a sealing material. In Figure 7(a), a laminate 110 is obtained in which the entire semiconductor substrate 4, which has been temporarily bonded to the support 12 via the adhesive layer 3, is sealed by the sealing material layer 5.

[0206] In the sealing process, for example, a sealing material heated to 130-170°C is supplied onto the adhesive layer 3 so as to cover the semiconductor substrate 4 while maintaining a high viscosity state, and is then compressed and molded to produce a laminate 110 in which a sealing material layer 5 is provided on the adhesive layer 3. In that case, the temperature conditions are, for example, 130-170°C. The pressure applied to the semiconductor substrate 4 is, for example, 50-500 N / cm². 2 That is the case.

[0207] Preferably, the sealing layer 5 is not provided for each individual semiconductor substrate 4, but rather is provided so as to cover the entire semiconductor substrate 4 on the adhesive layer 3.

[0208] ·Regarding the grinding process The grinding process is a process performed after the sealing process in which the sealing material portion (sealing material layer 5) of the sealing body is ground down so that a part of the semiconductor substrate is exposed. The sealing material portion is ground down by removing the sealing material layer 5 until it is approximately the same thickness as the semiconductor substrate 4, as shown in Figure 7(b).

[0209] • Regarding the wiring layer formation process The wiring layer formation process is a process of forming a wiring layer on the exposed semiconductor substrate after the grinding process. In Figure 7(c), a wiring layer 6 is formed on the semiconductor substrate 4 and the encapsulating layer 5. This allows for the creation of a laminate 120. In the laminate 120, the semiconductor substrate 4, the encapsulating layer 5, and the wiring layer 6 constitute an electronic device 456.

[0210] Examples of methods for forming the wiring layer 6 include the following: First, silicon oxide (SiO₂) is placed on the sealing material layer 5. x A dielectric layer, such as a photosensitive resin, is formed. The dielectric layer made of silicon oxide can be formed by, for example, sputtering or vacuum deposition. The dielectric layer made of a photosensitive resin can be formed by, for example, applying the photosensitive resin to the sealing material layer 5 by methods such as spin coating, dipping, rollerblade coating, spray coating, or slit coating.

[0211] Next, wiring is formed on the dielectric layer using a conductor such as a metal. Methods for forming the wiring include, for example, known semiconductor process techniques such as lithography (photolithography) and etching. Examples of such lithography processes include lithography using positive-type resist materials and lithography using negative-type resist materials.

[0212] In the manufacturing method of the laminate according to this embodiment, bumps can be formed on the wiring layer 6, or elements can be mounted. The elements can be mounted on the wiring layer 6, for example, using a chip mounter or the like.

[0213] (Method for manufacturing a laminate (3)) A method for manufacturing a laminate according to a fifth aspect of the present invention is a method for manufacturing a laminate in which a support, an adhesive layer, and an electronic device are laminated in this order, and is characterized by comprising: a step of applying the adhesive composition according to the first aspect onto the support to form a layer of the adhesive composition (adhesive composition layer formation step); an electronic device formation step of forming an electronic device, which is a composite of a member made of metal or semiconductor and a resin that seals or insulates the member, on the adhesive composition layer (electronic device formation step); and a step of curing the adhesive composition layer by a polymerization reaction of the urethane resin to form an adhesive layer (adhesive layer formation step).

[0214] The laminate obtained by the manufacturing method of this embodiment is a laminate in which a support, an adhesive layer, and an electronic device are laminated in that order, similar to the manufacturing method according to the fourth embodiment.

[0215] In the manufacturing method of this embodiment, the adhesive composition layer formation step can be carried out in the same manner as in the manufacturing method of the laminate according to the third embodiment.

[0216] In the manufacturing method of this embodiment, an electronic device formation step is performed after the adhesive composition layer formation step. This electronic device formation step may include a wiring layer formation step. The electronic device formation step may further include a semiconductor substrate mounting step, a sealing step, and a grinding step. Alternatively, the electronic device formation step may be a step in which a semiconductor substrate is placed on a support via an adhesive composition layer, forming a sealed body sealed with a sealing material.

[0217] The adhesive layer formation step can be carried out in the same manner as in the method for manufacturing a laminate according to the third embodiment.

[0218] After the adhesive layer formation step, an electronic device formation step may be performed as needed. Such an electronic device formation step may include, for example, a semiconductor substrate mounting step, a sealing step, and a grinding step.

[0219] According to the manufacturing method of the laminate according to the third to fifth aspects described above, the support and the semiconductor substrate or electronic device are temporarily bonded via a highly heat-resistant adhesive layer, so that a laminate in which the support, adhesive layer, and semiconductor substrate or electronic device are laminated in this order can be stably manufactured. Such a laminate is manufactured in a process based on fan-out technology in which terminals provided on the semiconductor substrate are mounted on a wiring layer that extends outside the chip area.

[0220] (Method of manufacturing electronic components) A method for manufacturing an electronic component according to the sixth aspect of the present invention is characterized by having a step (hereinafter also referred to as the "adhesive layer removal step") in which, after obtaining a laminate by the method for manufacturing a laminate according to any of the third to fifth aspects, the adhesive layer is removed by decomposing the urethane bonds of the urethane resin with an acid or alkali. If the support is composed of a support substrate and a separation layer, the method according to this embodiment may further include a separation step, prior to the adhesive layer removal step, in which the separation layer is irradiated with light through the support substrate to alter the separation layer, thereby separating the electronic device from the support substrate.

[0221] Figure 8 is a schematic process diagram illustrating one embodiment of a method for manufacturing a semiconductor package (electronic component). Figure 8(a) shows the laminate 120, Figure 8(b) illustrates the separation process, and Figure 8(c) illustrates the adhesive layer removal process.

[0222] [Separation process] If the support has a separation layer, the method for manufacturing an electronic component according to this embodiment may include a separation step. In this embodiment, the separation step is a step of separating the support substrate 1 from the electronic device 456 by irradiating the separation layer 2 with light (arrow) through the support substrate 1 to alter the separation layer 2. As shown in Figure 8(a), in the separation process, the separation layer 2 is altered by irradiating it with light (arrow) through the support substrate 1.

[0223] Wavelengths that can alter the separation layer 2 include, for example, those in the range of 600 nm or less. The type and wavelength of the irradiated light can be appropriately selected according to the transparency of the support substrate 1 and the material of the separation layer 2. For example, solid-state lasers such as YAG lasers, ruby ​​lasers, glass lasers, YVO4 lasers, LD lasers, and fiber lasers; liquid lasers such as dye lasers; gas lasers such as CO2 lasers, excimer lasers, Ar lasers, and He-Ne lasers; laser light such as semiconductor lasers and free electron lasers; and non-laser light can be used. This alters the separation layer 2, making it possible to easily separate the support substrate 1 and the electronic device 456.

[0224] When irradiating with laser light, the following conditions can be given as an example of laser light irradiation conditions. The average output power of the laser beam is preferably 1.0W or more and 5.0W or less, and more preferably 3.0W or more and 4.0W or less. The repetition frequency of the laser beam is preferably 20kHz or more and 60kHz or less, and more preferably 30kHz or more and 50kHz or less. The scanning speed of the laser beam is preferably 100mm / s or more and 10000mm / s or less.

[0225] After irradiating the separation layer 2 with light (arrow) to alter its properties, the support substrate 1 is separated from the electronic device 456 as shown in Figure 8(b). For example, the support base 1 and the electronic device 456 can be separated by applying a force that moves them apart. Specifically, the support base 1 and the electronic device 456 can be separated by fixing one side of the support base 1 or the electronic device 456 (wiring layer 6) to a stage, and then lifting the other side while holding it with a separation plate equipped with an adhesive pad such as a bellows pad. The force applied to the laminate 200 can be adjusted appropriately depending on the size of the laminate 200 and is not limited to any specific force. For example, if the laminate has a diameter of about 300 mm, applying a force of about 0.1 to 5 kgf (0.98 to 49 N) can effectively separate the support base 1 and the electronic device 456.

[0226] If the support does not have a separation layer, the separation of the support from the semiconductor substrate or electronic device can be performed by the adhesive layer removal process described later.

[0227] [Adhesive layer removal process] The method for manufacturing electronic components according to this embodiment includes an adhesive layer removal step. The adhesive layer removal step is a step of decomposing the crosslinked structure in the adhesive layer with an acid or alkali and removing the adhesive layer. In Figure 8(b), the adhesive layer 3 and separation layer 2 are attached to the electronic device 456 after the separation process. In this process, the adhesive layer 3 and separation layer 2 are removed by decomposing the adhesive layer 3 using an acid or alkali, thereby obtaining the electronic component 50.

[0228] In this process, the urethane bonds of component (P1) in the adhesive layer 3 are decomposed with an acid or alkali. The acid or alkali used to decompose the urethane bonds is not particularly limited as long as it is capable of decomposing the urethane bonds. Examples of acids capable of decomposing urethane bonds include, but are not limited to, hydrochloric acid, sulfuric acid, and nitric acid. Examples of alkalis capable of decomposing urethane bonds include, but are not limited to, inorganic bases such as potassium hydroxide and sodium hydroxide, and organic amines such as tetramethylammonium hydroxide and monoethanolamine.

[0229] The aforementioned acid or alkali can be dissolved in a solvent and used as a treatment solution for removing the adhesive layer. The solvent is preferably a polar solvent, such as dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), diethylene glycol monobutyl ether, diethylene glycol, ethylene glycol, or propylene glycol. The adhesive removal treatment solution may contain, in addition to the above components, known additives such as surfactants. The acid or alkali content in the treatment solution is not particularly limited, but for example, it may be 1 to 50% by mass. The polar solvent content in the treatment solution may be 50 to 99% by mass. For removing the adhesive layer, commercially available alkaline or acidic treatment solutions may be used. Examples of commercially available treatment solutions include ST-120 and ST-121 (both manufactured by Tokyo Ohka Kogyo Co., Ltd.). By bringing the aforementioned treatment solution containing an acid or alkali into contact with the adhesive layer 3, the urethane bonds of component (P1) in the adhesive layer 3 are decomposed, and the adhesive layer 3 can be removed.

[0230] According to the method for manufacturing electronic components of this embodiment, a urethane resin (P1) containing polymerizable carbon-carbon double bonds and caprolactone-modified urethane are used. (meta)An adhesive composition containing acrylate (M1) is used to temporarily bond a semiconductor substrate or electronic device to a support. The adhesive layer formed by the curing of the adhesive composition is formed by a polymerization reaction between component (P1) and component (M1). Caprolactone-modified urethane (meta) By using an adhesive composition containing acrylate (M1), it is possible to form an adhesive layer with high heat resistance and adhesion that can withstand high-temperature processing in electronic device formation processes, etc. Furthermore, since the urethane resin in the adhesive layer is decomposed by acid or alkali, the adhesive layer can be easily cleaned and removed after the completion of the electronic device formation process, etc. Cleanability is also improved by the inclusion of component (M1) in the adhesive composition.

[0231] In the manufacturing method of the electronic component of this embodiment, after the adhesive layer removal step described above, further processing such as solder ball formation, dicing, or oxide film formation may be performed on the electronic component 50. [Examples]

[0232] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0233] <Examples of urethane resin synthesis> (Synthesis Example 1: Urethane Resin (P1)-1) In a flask equipped with a stirrer, dropping funnel, condenser, and thermometer, 53 parts of propylene glycol monomethyl ether acetate (PGMEA), polycarbonate diol (Mw1000), 18 parts of pentaerythritol diacrylate (PEDA), 1 part of neopentyl glycol, and 2.5 parts of hydroxyethyl acrylate (HEA) were added and homogeneously mixed under a nitrogen stream. Next, 7 parts of diphenylmethane diisocyanate (MDI) and 21 parts of hydrogenated xylylene diisocyanate (H6XDI) were placed in the dropping funnel and added dropwise at a constant rate over 30 minutes. After the addition was complete, aging was performed for 30 minutes. Then, bismuth catalyst was added, the temperature was raised to 65°C, and aging was performed for 4-5 hours. Next, methanol was added, and aging was performed for 1 hour, terminating the reaction when the isocyanate group (NCO) disappeared. The molecular weight (Mw) of the obtained urethane resin (P1)-1 was 30,000.

[0234] The polycarbonate diol used was one represented by the following formula (PC-1-1) (R=-(CH2)6-,-(CH2)5-).

[0235] [ka]

[0236] <Preparation of adhesive composition> (Examples 1-2, Comparative Examples 1-5) The adhesive compositions for each example were prepared by mixing the components shown in Table 1.

[0237] [Table 1]

[0238] In Table 1, each abbreviation has the following meaning. The numbers in brackets [ ] represent the amount (parts by mass) of the ingredients. (P1)-1: Urethane resin (P1)-1 synthesized in the above synthesis example 1. (M1)-1: A mixture of the caprolactone-modified biuret-type urethane acrylate (M1-1) and the biuret-type urethane acrylate (M2-1) described below. It was synthesized by reacting the biuret form of hexamethylene diisocyanate with caprolactone-modified hydroxyethyl acrylate and hydroxyethyl acrylate (caprolactone-modified hydroxyethyl acrylate:hydroxyethyl acrylate = 80:20 (molar ratio)). (M1)-2: A mixture of the caprolactone-modified isocyanurate-type urethane acrylate (M1-2) and the isocyanurate-type urethane acrylate (M2-2) described below. It was synthesized by reacting the isocyanurate of hexamethylene diisocyanate with caprolactone-modified hydroxyethyl acrylate and hydroxyethyl acrylate (caprolactone-modified hydroxyethyl acrylate:hydroxyethyl acrylate = 80:20 (molar ratio)).

[0239] [ka]

[0240] [ka]

[0241] (M2)-1: The aforementioned biuret-type urethane acrylate (M2-1). (M2)-2: The isocyanurate-type urethane acrylate (M2-2) described above. (M2)-3: The following urethane acrylate (M2-3). (M2)-4: Caprolactone-modified acrylate (M2-4) as described below (Arronix M327 (trade name), Toagosei Co., Ltd.).

[0242] [ka]

[0243] (A)-1: The following peroxide-based thermal polymerization initiator (A-1) (Perkmyl® D (trade name), Nippon Oil & Fats Co., Ltd.). (Ad)-1: The following silane coupling agent (Ad-1) (OFS-6040Silane (product name), Dow-Toray Corporation). (Ad)-2: Polyester-modified polydimethylsiloxane (BYK-310 (trade name), Bic Chemie).

[0244] [ka]

[0245] Table 2 summarizes the (M) component used in Examples 1 and 2, and Comparative Examples 1 to 4.

[0246] [Table 2]

[0247] <Rating> ≪Measurement of Elastic Modulus≫ Each adhesive composition was applied to a silicon substrate using a spin coater and cured by heating in an oven under a nitrogen atmosphere at 180°C for 60 minutes (film thickness 50 μm). Test specimens of the cured adhesive film (film thickness 50 μm, width 5 mm, length 40 mm) were cut out, and the tensile modulus was measured using a Rheogel-E4000 (manufactured by UBM) at a frequency of 1 Hz in the range of 50 to 300°C.

[0248] Heat Resistance Test Each adhesive composition was applied to a silicon substrate by spin coating to form an adhesive composition layer (film thickness 50 μm). Next, a glass support substrate (diameter 20 cm, thickness 700 μm) was laminated on the adhesive composition layer. This laminate was heated in an oven under a nitrogen atmosphere at 180°C for 1 hour to cure the adhesive composition layer and form an adhesive layer. The laminate consisting of the glass support substrate, adhesive layer, and silicon substrate was heated in an oven under a nitrogen atmosphere at 230°C for 1 hour, and the time until delamination occurred was measured. The results are shown in Table 3 as "Delamination Suppression Time".

[0249] <<Cleaning properties>> Each adhesive composition was applied to a silicon substrate using a spin coater, and the substrate was heated in an oven under a nitrogen atmosphere at 180°C for 1 hour to form an adhesive layer. The silicon substrate with the adhesive layer formed was then immersed in an alkali-containing cleaning solution (ST-120 (product name), manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 35°C or 50°C for 15 minutes, and the dissolution rate (nm / s) of the adhesive layer was measured. The results are shown in Table 3 as "cleanability".

[0250] <<Adhesion>> Each adhesive composition was applied to a silicon substrate using a spin coater to form an adhesive composition layer (film thickness 50 μm). Next, a glass chip (5 mm x 5 mm, thickness 700 μm) containing a separation layer was laminated onto the adhesive composition layer. This laminate was heated in an oven under a nitrogen atmosphere at 180°C for 1 hour to cure the adhesive composition layer and form an adhesive layer. A shear strength test was performed on the laminate consisting of the glass chip, adhesive layer, and silicon substrate to measure the shear strength of the glass chip to the silicon substrate. The results are shown in Table 3 as "Adhesion".

[0251] [Table 3]

[0252] As shown in Table 3, the adhesive layers formed using the adhesive compositions of Examples 1 and 2 were confirmed to have good heat resistance (delamination suppression time), cleanability, and adhesion. On the other hand, Comparative Example 1 had excellent heat resistance, but its cleanability was extremely poor. Comparative Example 2 had good heat resistance and adhesion, but its cleanability was poor. Comparative Examples 3 and 4 were poor in heat resistance, cleanability, and adhesion, and their cleanability at low temperatures (35°C) was particularly poor. Comparative Example 5 was poor in heat resistance, cleanability, and adhesion. [Explanation of symbols]

[0253] 1 Supporting base 2 separation layer 3 Adhesive layer 3' Adhesive composition layer 4. Semiconductor substrates 5 Encapsulant layer 6 wiring layer 12 Support 20 Laminate 50 Electronic Components 100-layer structure 100' laminate 110 Laminate 120-layer structure 200-layer structure 300-layer structure 400-layer structure 456 Electronic Devices 645 Electronic Devices

Claims

1. An adhesive composition used to form an adhesive layer for temporarily bonding a semiconductor substrate or electronic device to a light-transmitting support, A urethane resin (P1) containing polymerizable carbon-carbon unsaturated bonds, A crosslinking agent component (M) containing caprolactone-modified urethane (meth)acrylate (M1) (excluding the urethane resin (P1)), Polymerization initiator (A), It contains, The content of the urethane resin (P1) is 40 to 80% by mass relative to the total mass of the adhesive composition. The content of the crosslinking agent component (M) is 10 to 40% by mass relative to the total mass of the adhesive composition. The proportion of the caprolactone-modified urethane (meth)acrylate (M1) in the crosslinking agent component (M) is 40 to 100% by mass relative to the total mass of the crosslinking agent component. The content of the polymerization initiator (A) is 0.1 to 10 parts by mass per 100 parts by mass of the urethane resin (P1). Adhesive composition.

2. The adhesive composition according to claim 1, wherein the caprolactone-modified urethane (meth)acrylate (M1) is of the biuret type or isocyanurate type.

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

4. A laminate comprising a light-transmitting support, an adhesive layer, and a semiconductor substrate or electronic device, stacked in this order, The adhesive layer is a cured body of the adhesive composition described in claim 1. Laminated structure.

5. The support is composed of a light-transmitting support substrate and a separation layer that is altered by light irradiation, and the adhesive layer is adjacent to the separation layer. The laminate according to claim 4.

6. A method for manufacturing a laminate in which a support, an adhesive layer, and a semiconductor substrate are stacked in this order, The steps include applying the adhesive composition described in claim 1 to the support or semiconductor substrate to form an adhesive composition layer, The steps include: placing the semiconductor substrate on the support via the adhesive composition layer; A step of curing the adhesive composition layer to form the adhesive layer, A method for manufacturing a laminate having the following characteristics.

7. The method for manufacturing a laminate according to claim 6 further comprises the step of forming an electronic device which is a composite of a member made of metal or semiconductor and a resin that seals or insulates the member. A method for manufacturing a laminate in which a support, an adhesive layer, and an electronic device are stacked in that order.

8. The support is composed of a light-transmitting support substrate and a separation layer that is altered by light irradiation, and in the laminate, the adhesive layer is adjacent to the separation layer. A method for manufacturing a laminate according to claim 7.

9. After obtaining a laminate by the method for manufacturing a laminate described in claim 7, The process includes a step of removing the adhesive layer by decomposing the urethane bonds of the urethane resin with an acid or alkali. Manufacturing methods for electronic components.

10. After obtaining a laminate by the method for manufacturing a laminate according to claim 8, A step of separating the electronic device from the support substrate by irradiating the separation layer with light through the support substrate to alter the separation layer, A step of removing the adhesive layer adhering to the electronic device by decomposing the urethane bonds of the urethane resin with an acid or alkali, A method for manufacturing electronic components, comprising:

Images